Chapter 9

A M O R P H O U S CARBON THIN FILMS

S. R. E Silva, J. D. Carey, R. U. A. Khan, E. G. Gerstner, J. V. Anguita

Large Area Electronics Group, School of Electronics, Computing and Mathematics,
University of Surrey, Guildford, United Kingdom

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . ............................ 404

1.1. Carbon and Its Allotropes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
1.2. Historical Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
1.3. Future Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
2. Deposition and Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
2.1. Deposition Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
2.2. Growth Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
3. Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
3.1. Experimental Determination of Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . 420
3.2. Computer Modelling of Growth and Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4. Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
4.2. Infrared Absorption Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
4.3. Photoluminescence Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
4.4. Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
4.5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
5. Defect Studies of Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
5.2. Lineshape Analysis and Relaxation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
5.3. g Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
5.4. Spin Densities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
5.5. Linewidths, Lineshapes, and Relaxation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . 460
5.6. Effects of Nitrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
5.7. Effects of Annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
5.8. Correlation Energies and Photoyield Measurements . . . . . . . . . . . . . . . . . . . . . . . . 465
5.9. Defects and Nonradiative Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
5.10. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
6. Electrical Properties of Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
6.1. Conduction and Amorphous Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
6.2. Electronic Band Structure of Amorphous Materials . . . . . . . . . . . . . . . . . . . . . . . . 468
6.3. Comparison with Amorphous Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
6.4. Generalized Conduction in Amorphous Materials: Low Field Conduction . . . . . . . . . . . . 469
6.5. High Field Conduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
6.6. Electronic Structure and Properties of Amorphous Carbon . . . . . . . . . . . . . . . . . . . . 471
6.7. Electronic Properties: GAC Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
6.8. Electronic Properties: DAC Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
6.9. Electronic Properties: TAC Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
6.10. Electronic Modification of Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . 478
6.11. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
7. Concepts of Localization and Delocalization in a-C . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482

Handbook of Thin Film Materials, edited by H.S. Nalwa

Volume 4: Semiconductor and Superconductor Thin Films
Copyright 9 2002 by Academic Press
ISBN 0-12-512912-2/$35.00 All rights of reproduction in any form reserved.

403
404 SILVA ET AL.

7.1. Ion I m p l a n t a t i o n o f a - C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483

8. Electron Field E m i s s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
8.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
8.2. T h e o r y o f Field E m i s s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
8.3. Planar E m i t t e r Structures Based on C a r b o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
8.4. M o d e l l i n g o f the Electron E m i s s i o n Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 492
8.5. Field E m i s s i o n as a Function o f Surface Modifications . . . . . . . . . . . . . . . . . . . . . . 496
9. A m o r p h o u s C a r b o n - B a s e d Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
9.1. Electronic Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
9.2. Novel Devices: Nonvolatile M e m o r i e s , Antifuses, and M I M s . . . . . . . . . . . . . . . . . . . 499
9.3. Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
9.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
10. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501

1. I N T R O D U C T I O N comparable with a tetrahedral structure [ 1]. It is believed that

"Carbon is the King of mediocrity. Standing as it does in the
midpoint of the periodic table, seeking neither other atom's
electrons nor willing particularly to surrender its own, it is con-
tent to bond to itself and to form chains and rings of intricate
form and of seemingly infinite variety." (P. W. Atkins, The Times
Higher Education Supplement, February 1995)
Carbon is unique in its structure by being able to form one
of the strongest materials known to man, diamond, or one that
is soft, graphite, by virtue of the way in which each atom bonds
to another. The material could have an bandgap as great as
5.5 eV or one that is negative. All of these variations have been
made possible by the three different bond hybridizations that
are available to carbon. These are tetrahedral diamondlike s p 3
bonds, trigonal graphitelike s p 2 bonds, and linear acetylenelike
s p I bonds. See Figure 1. As in the crystalline case, each of these
bond variations is available to its amorphous counterparts, and
this enables the unique and large variation in the physical and
material properties to be extended to amorphous carbon (a-C)
thin films.
Due to the very many combinations of bond hybridizations
available to amorphous carbon films, there is also a significant
amount of confusion as to the terminology used to refer to a
particular type of a-C thin film. It should be noted that the term
diamondlike carbon (DLC) should generally be reserved for
polycrystalline or nanocrystalline carbon films, whereas amor-
phous carbon films should generally fall into the categories of
(a) polymerlike amorphous carbon (PAC),
(b) graphitelike amorphous carbon (GAC),
(c) diamondlike amorphous carbon (DAC),
(d) tetrahedral amorphous carbon (TAC), and
(e) nanocomposite amorphous carbon (NAC).
We shall use the terms a-C and a-C:H as generic terms for
amorphous carbon and its hydrogenated counterparts. The nota-
tion introduced above will be based more on the microstructure
of the films as opposed to its properties which become more and
more difficult to associate simply with a given structure due to
the major advances being made in deposition techniques. As
an example, we have seen the birth of a three-dimensional (3D)
graphite structure based on a nanocomposite amorphous carbon
whose nanoparticles are planar but still give a hardness that is
the strength of this 3D planar structure arises from the closer
in-plane bond lengths of the s p 2 rings. Two examples of NAC
films are shown in Figure 2, where there is a mixed amorphous-
nanocrystalline phase present, with the nanocrystals usually
embedded in the amorphous carbon matrix giving it its unique
properties. Due to the small dimensions of the nanocrystallites,
the a-C films maintain their smooth mirrorlike surface finish
with root-mean-square (RMS) values that are of the order of a
fraction of a nanometer. It should be noted that in general TAC
films are nonhydrogenated and are considered to have a higher
s p 3 fraction and hardness when compared to DAC films. This is
primarily due to the fact that DAC films have hydrogen in their
structure, and the C - H bonds in s p 3 hybridizations contribute
to the higher s p 3 ratio.
In this review chapter we will attempt to cover the evolu-
tion of a-C thin films and map out the significant contributions
to the field by numerous research laboratories. We will exam-
ine the deposition and growth aspects as well as the growth
models, which will bring us to the microstructure of these
films. Then the impact of the microstructure and growth on the
optical and electrical properties will be examined. The effect
that defects play in the optoelectronic properties will then be
mapped. We will then cover the electronic density of states of
the material and evaluate the impact of defects on the measured
electrical and optical properties. Subsequently, we will intro-
duce some new results that show how ion implantation may
allow a methodology to delocalize gap states within these films.
It is indeed quite significant that it appears that this addition of
disorder into the amorphous material helps to allow for better
control of the conduction properties.
Finally, we will look toward the future uses of this material
in the form of applications. The area which has generated the
most amount of interest in the recent past has been electron field
emission. We firmly believe that this interest will continue and
develop and so we devote a full section to this subject. Other
applications which include both passive and active thin a-C
films will be covered separately. It should be noted that a-C has
been used as a hard disc wear resistant coating commercially
for many years and at present it is thought that all major hard
disc drive manufacturers use an a-C protective film. All the in-
formation used in the applications section is from information
 A M O R P H O U S C A R B O N THIN FILMS 405

Fig. 1. A schematic representation of s p I , s p 2, and s p 3 hybridized bonds and the resultant crystalline and model amorphous structures. The structures
shown for s p 1 hybridized carbon are hypothetical structures showing the formation of triple bonded carbon from a graphite plane [36], and the packing of
the carbon chain around Na atoms [37]. The model amorphous structure for s p 3 bonded carbon illustrates a TAC film that is hydrogenated (light circles)
and has a density of 3.0 g cm-3 [38]. The model amorphous s p 2 structure is from [39] which is a-C that has 86% s p 2 bonding and has a density close to
2.0 g cm-3.

available in the public domain. The authors do realize that a
significant quantity of research is being conducted in compa-
nies on a number of commercially sensitive areas at present.
1.1. Carbon and Its Allotropes
Until the mid 1980s there were two main allotropic forms of
carbon that could be readily identified and available, namely,
diamond and graphite. Russian scientists in the mid 1970s at-
tempted to introduce a third allotropic form of carbon called
carbynes [2, 3] which was not accepted by the larger scien-
tific community as a whole [4, 5]. In the mid 1980s C60 or
buckminster-fullerene [6, 7] was added to the list of allotropic
forms of carbon. The reason that each of these allotropic forms
is of interest to us is their bond hybridization. Also each of these
crystalline forms has a unique structure that can give rise to
properties that are mimicked in its amorphous counterparts.
1.1.1. Diamond
Diamond is the hardest substance known. In its crystalline form
a completely tetrahedral structure gives it an optical bandgap
of 5.5 eV due to the covalently bonded s p 3 C - C structure with
only cr bond hybridizations. Diamond also has the distinction of
having the largest known thermal conductivity due to the high
speed of its acoustic phonon coupling. The first reported syn-
thesis of diamond was in 1911 by von Bolton [8] using low
temperature (100~ and low pressure decomposition of acety-
lene. Systematic synthesis of diamond was then undertaken by
Bundy [9] and Eversol [10] in the 1950s and 1960s. The main
406
Fig. 2. Examplesof NAC films that show (a) dendritic growth of crystallites
as discussed in [5] and (b) graphite nanoparticles in a TAC matrix (see [1]).
problem faced by the diamond community in using this material
to its full capacity as an active device has been the suitability to
confidently electrically dope the material n-type. Although N
atoms which are found naturally in type lib diamond can be in-
troduced and sit substitutionally, they create a very deep donor
state 1.7 eV below the conduction band edge. At present there is
much excitement in the possible use of phosphorous as a shal-
low n-type donor in diamond. On the other hand, B can be used
to dope this material p-type (0.37 eV above the valence band).
Recently, a number of useful electronic devices have been fab-
ricated using a surface conducting layer of hydrogen terminated
diamond [ 11, 12].
1.1.2. Graphite
Graphite is a fully trigonal network of bonds that forms planar
six-member aromatic rings of single and double bonded carbon.
The sheets of planar s p 2 hybridized carbon are connected to
planar bonds on either side by weak zr bonds. The C-C distance
of the planar double bonds is 1.42 A in length when compared
to the single bond length of 1.54 A for s p 3 bonded carbon. The
graphite sheets are 3.54 A apart and due to the weak van der
Vaals zr bonds the sheets can slide relative to each other and this
gives rise to good lubrication properties. In terms of bandgap,
due to the highly delocalized yr bonds between the s p 2 bonded
graphite sheets there is an overlapping of the 7r-yr* density of
states (DOS) which makes the material behave as a metallic
conductor.
SILVA ET AL.
1.1.3. Carbynes
Carbynes have a fully crystalline s p 1 bonded chainlike structure
giving rise to a material whose bandgap and structure resemble
that of an acetylenelike chain molecule with a mixture of sin-
gle and triple bonded carbon forming a solid crystalline with a
face-centered-cubic (fcc) structure [3]. As stated in the Intro-
duction there is much debate as to the validity of these results
[4]. To date, at least six forms of crosslinked linear carbon poly-
types have been reported [ 13]. There are a number of reports
that show carbon crystalline structures that do not conform to
any of the above structures [5].
1.1.4. Cn0 ( B u c k m i n s t e r - F u l l e r e n e s )
This can be classified as an allotropic form by virtue of its struc-
ture being unique in that it consists of 60 carbon atoms formed
into a large molecule which has a shape similar to that of a
football. This form of carbon was initially observed in inter-
stellar space [6] and now is being commercialized for various
potential applications [ 14]. The 60 carbon atoms form into 20
hexagons and 12 pentagons. The pentagons give rise to the cur-
vature in the otherwise fully sp 2 bonded network and thereby
close the molecular cagelike structure. Although each carbon
atom in C60 is threefold coordinated, due to the curvature in-
volved in its bonding the films have a hybridization that can be
regarded as an s p 25 hybridization [ 15]. Despite this fact, it can
be used as a standard for a fully 100% Jr bonded network in
electron energy loss analysis due to the intensities of the 7r to cr
bond being compared against an unknown sample [16].
1.1.5. Amorphous Carbon (a-C)
Amorphous carbon is the generic term used to describe most
disordered carbon films. Although there is no long range or-
der present, both short and medium range order is preserved
which gives rise to physical properties that can mimic those
found in the crystalline material. In these materials by examin-
ing the nearest neighbor distance and the next nearest neighbor
distance it is clear that the short/medium range order is very
close to its crystalline counterpart. It is generally the bond an-
gle that is different from that of the crystalline case which gives
a-C no long range order. This angular or bond angle variation
can also give rise to the narrowing of the bandgap by virtue of it
creating highly localized states within the bandgap. Amorphous
carbon films in general are broken down once more into two
distinct categories; hydrogenated and nonhydrogenated films.
(See Table I.)
Whenever a hydrocarbon source gas or plasma system is
used to deposit the films some quantity of hydrogen gets incor-
porated within its microstructure. Since the hydrogen prefers
to bond in an s p 3 hybridized manner, by terminating single
bonds they tend to enhance the s p 3 or tetrahedral nature within
the films. Using techniques such as the plasma beam source it
has been reported that an s p 3 content as high as 80% has been
recorded in the presence of 30% hydrogen within these highly
 AMORPHOUS CARBON THIN FILMS
Table I. Typical Physical Properties for the Different Forms of Amorphous Carbon Thin Films
Category Hardness (GPa) sp 3 (%)
PAC soft 60-80
GAC soft 0-30
DAC 20-40 40-60
TAC 40-65 65-90
NAC 20-40 30-80
tetrahedral hydrogenated a-C films [ 17]. This is in contrast to
the more usual 40-60% s p 3 bonding found in the DAC films de-
posited using radiofrequency plasma enhanced chemical vapor
deposition (RF PECVD), with ion bombardment (and H --~ 30-
40 at.%). When no ion bombardment is used, as in the case of
earthed electrode RF PECVD systems, highly polymeric a-C:H
(PAC:H) films are deposited. These films have an s p 3 content
between 60 and 80% (but mostly C - H bonds with little s p 3
C-C bonds) and high hydrogen contents (H 40-65 at.%). At
the high end of the hydrogen contents, thin films deposited are
more similar to hydrocarbon polymers such as polythene which
possesses 66 at.% of H.
1.1.6. Nonhydrogenated a-C Films
Sputtering (with or without the use of a magnetron), evapora-
tion, filtered cathodic vacuum arc (FCVA), mass selected ion
beams (MSIB), and laser arcs are some of the more popular
systems used for the deposition of nonhydrogenated or hydro-
genated films with the deliberate addition of controlled amounts
of hydrogen. In the case of hydrogenated carbon films, as the
C-H bond energy (4.3 eV) is significantly higher than that of
the Si-H bond (3.3 eV) it allows both the hydrogenated and
nonhydrogenated films to be used in relatively high temper-
ature environments. In fact these a-C(:H) films are extremely
robust and are seldom attacked by concentrated acids or alka-
lis. Oxygen plasmas are one method in which the films can be
etched, when required. In the case of sputtering it was thought
that only highly s p 2 hybridized films could be obtained using
this technique. Schwan et al. [18] clearly demonstrated that
using a magnetron source which included an intense Ar ion
plating environment, highly s p 3 bonded films could be created
under the correct conditions. FCVA is a well known technique
that has been used to deposit a-C films with high s p 3 contents
that have ranged from 20 and 87%. Recently, Xu et al. [19]
has shown that such a system can be produced commercially
using an off axis energy filter to remove macroparticles gener-
ally transported as part of the plasma stream due to electrostatic
considerations. Scheibe et al. [20] also have demonstrated the
ability to deposit highly TAC films using a laser initiated
plasma. Lifshitz et al. [21] have been using ion implantation
to deposit a-C films using a model system, MSIB. They too get
highly s p 3 films utilizing the ion bombardment effect which
creates a metastable structure within the films that promotes s p 3
bond formation.
407
Optical bandgap (eV) Density (g cm-3) H (at.%)
2.0-5.0 0.6-1.2 40-65
0.0-0.6 1.2-2.0 0-40
0.8-4.0 1.5-3.0 20-40
1.6-2.6 2.5-3.5 0-30
0.8-2.6 2.0-3.2 0-30
Laser initiated carbon arcs also have been reported to pro-
duce a-C films with high s p 3 contents. In a comparison of the
two types of TAC films produced by laser vacuum arc and
FCVA it was found that the physical properties of the films
greatly differ despite the fact that both types of films have high
s p 3 contents [22]. Therefore, the distribution of s p 2 sites as
well as their atomic percentage must govern the material prop-
erties. Also, it has often been reported that the DC self-bias or
the incident ion energy controls the s p 3 content. Xu et al. have
produced TAC films under no bias, which are highly s p 3 hy-
bridized, which suggests that the density of the plasma plays
a key role in the deposition process. Early work by Davan-
loo et al. [23] on laser ablated a-C films reported high s p 3
films which have now been reclassified as moderately high s p 3
(closer to 60%). Preliminary results within our laboratory us-
ing plasma immersion ion implantation (PI 3) indicates that it
is possible to grow high s p 3 films using the system in a CH4
plasma under DC bias.
A recent addition to the nonhydrogenated family of samples
has been the graphite nanoparticle containing TAC films [ 1]. In
this case, the films are grown using a cathodic arc in a high He
plasma regime that condenses some of the C ions into graphite
nanoparticles before they impinge on the target (NAC).
Other nonhydrogenated films such as evaporated or sput-
tered carbon fall into the category of high s p 2 films as these
a-C films are deposited at close to room (or low) temperature
and there is no surface energy available for the bonds to rear-
range themselves other than in their lowest energy configuration
which is s p 2 or graphitelike (GAC).
1.1.7. H y d r o g e n a t e d a - C F i l m s
In the case of the hydrogenated films, hydrogen can be deliber-
ately leaked into the deposition chamber in controlled quantities
to change the properties of a-C films. More usually a hydro-
carbon plasma is used during the deposition which means that
H contents may vary between 20 and 60% depending on the
type of growth system used. There are a number of different
and varied configurations used and we will concentrate on the
more popular systems covered in the literature. RF PECVD has
been used to produce (good quality) films with varied proper-
ties and H contents between 20 and 60% with a bandgap Eg
that ranges from 1 to 4 eV [24, 25]. Films can be deposited on
the RF driven electrode to give a metastable structure that con-
tains higher s p 3 diamondlike C-C contents. If films are to be
408 SILVA ET AL.
grown on the earthed electrode, similar to the a-Si:H, the films
generally contain a smaller number of defects as measured by
electron paramagnetic resonance (EPR), higher hydrogen con-
tent, and higher bandgap [26]. Hydrocarbons containing gases
such as CH4, C6H6 and C2H2 are commonly used. Amorphous
carbon films have also been grown using microwave plasmas as
well as hybrid RF-microwave plasma systems.
The plasma beam source [ 17] provides a method of increas-
ing the s p 3 content while decreasing the H content of DAC
films by confining the plasma into a highly ionized dense beam.
More recently, electron cyclotron wave resonance systems have
achieved similar results [27]. This can be compared to the
use of magnetically confined RF PECVD [28] which results
in a significant variation in the film properties. The enhanced
dissociation within the plasma helps electronically dope the de-
posited films [29]. Other methods to grow a-C:H films include
the use of natural sources such as Camphor (C10H160) [30] and
C8C1403 [31 ]. Another interesting technique has been the heli-
con plasma system. In this case an antenna is used to excite the
plasma at a resonance that gives rise to high dissociation. In-
ductively coupled plasmas too have been used to deposit films
that are soft and have a high s p 2 content.
1.2. Historical Perspective
Since Aisenberg [32] in 1971 coined the term DLC (which
more correctly should have been called DAC) for ion beam
deposited carbon films that had some physical properties that
could be associated with diamond, there has been much interest
in the deposition, characterization, and utilization of a-C films.
The field opened up in 1976 when Holland and Ojha used a
RF PECVD system to produce hydrogen containing a-C thin
films. Aksenov [33] then used a cathodic arc to produce TAC
films. This allowed for the growth of a-C films that contained
s p 3 contents that ranged from 20 to 80%, while the material
still remains amorphous. Evaporation and the sputtering of car-
bon from solid sources has been performed for many years with
little or no commercial applications as yet.
The drive in the area of thin film carbon deposition in the
early days was based on the growth of polycrystalline diamond
films [34]. But with time and a better appreciation of the prop-
erties of amorphous carbon films this area of material science
has grown steadily with as many researchers or more work-
ing on this topic when compared to diamond films. The main
difference associated with the two types of films was that in or-
der to grow polycrystalline diamond films metastably, a highly
ionized plasma such as a microwave dissociated plasma was
required. In addition to the hydrocarbon source gas CH4, a
high percentage of H2 dilution was required before the plasma
impinged on a hot substrate of 800-1100~ The high tempera-
ture made sure that there was enough surface energy associated
with the process for the atomic H in the hydrocarbon to be
dissociated. The hydrogen dilution gas also etched away the
nondiamond component at this temperature to allow for the
growth of diamond films. Other techniques used included hot
filament CVD and oxyacetylene torch methods.
When initially proposed for industrial applications, a-C
films were considered for hard transparent coatings that were
infrared (IR) transparent. Since then with the knowledge gained
in the study of these materials, the number of potential applica-
tions and uses has increased significantly.
1.3. Future Applications
At present, hard a-C coatings are used in hard disc drives to
provide a wear resistant coating for the read/write media. It is
also used to coat the read heads in CD and video head appli-
cations. The advantages of a-C coatings for these applications
lie in the fact that by mixing s p 2 bonds with s p 3 bonds it is
possible to add some lubricious qualities to the coating due to
the stratified nature of the planar s p 2 bonds. The mixing of s p 2
with s p 3 also prevents the coating from becoming too brittle
and prevents cracks propagating on impact. Similar wear resis-
tant properties are used in a plethora of applications such as
shaving blades, cutting edges, nails, pistons in car engines, dec-
orative coatings such as jewelery and watches, etc. Other areas
that utilize these wear resistant coating properties have been in
the biomedical and optical lens areas. The properties of hard
wear resistant DAC were predicted and demonstrated back in
the early 1970s and since then they have been used as a pro-
prietary technology by manufacturers. Another interesting and
hitherto unutilized area has been in low fouling applications in
heat exchangers. Hard a-C coatings have proved to be one of
the best barrier layers that prevent the buildup of calcium based
coatings that lower the efficiency of heat exchangers which is
a multimillion dollar industry. These applications give a flavor
as to the use of a-C as a mechanical coating. As the applica-
tions above have used a-C as a passive layer, its value-added
component has not been as significant.
It is predicted that the impact a-C films will have in the
future as an active layer material will be much more signifi-
cant. Already prototype displays that utilize a-C cathodes have
been demonstrated that utilize the property of low electric field
threshold for electron emission. This property that was initially
associated with negative electron affinity is now attributed to
the electronic structure of the material and will be discussed
more fully in a later chapter. As the cathodes used based on
a-C are "nominally" flat, they will have a large number of ad-
vantageous properties for large area displays when compared to
the use of conventional "Spindt" tips in field emission displays.
This market is a multibillion dollar activity and has the poten-
tial of moving a-C to the status of one of the most value-added
products available in advanced materials.
Other active applications in which the tuneable qualities of
the bandgap are expected to portray a-C as a unique material
are in electronic applications. Starting with the most basic com-
ponent a blocking diode, the gap states in a-C have thus far
prevented the fabrication of such a device. This is because any
metal placed against a-C would allow carriers to leak into gap
states and thus prevent the observation of a Schottky barrier.
This has now been overcome by improvements to the material
 AMORPHOUS CARBON THIN FILMS 409

properties (see Section 6) as well as by the growth of super-

lattice structures [35]. What this allows is the possibility of a
plethora of electronic devices starting with the Schottky barrier
and then moving to three-terminal MESFET and TFT appli-
cations. With this comes the possibility of providing tuneable
electronic barriers. With the possibility of delocalized conduc-
tion proposed in Section 6 by the addition of disorder by ion
implantation, the use of electronic components to exploit in-
jection devices for electroluminescence applications becomes a
distinct possibility. The use of a-C as a pseudo direct gap mate-
rial for light emission also then becomes possible together with
applications in sensors and photovoltaics. Some recent work
also suggests the advantages of using a-C in electrochemical Fig. 3. Schematicdiagram for a RF PECVD system.
cells.

2. DEPOSITION AND GROWTH

Amorphous carbon films can be deposited in a large number of

ways. For example if only a s p 2 bonded material is required any
simple evaporation technique will be capable of producing such
a film. On the other hand, a-C films have been prepared using
ion implanters where growth has been virtually layer-by-layer.
Due to the vast variety of deposition equipment available this
has meant that these films need to be characterized and care-
fully categorized according to the various classes of materials
so that they can be compared with each other meaningfully. It
Fig. 4. Variationof (a) the average voltage distribution in a RF PECVD sys-
will be seen that the growth process of the films will be inti- tem at the driven and earthed electrodes, and (b) the RF modulation potential
mately controlled by the deposition process and in particular by with time together with the averaged bias potential experienced at the two elec-
the plasma conditions that prevail during the growth. trodes.

2.1. Deposition Techniques

Due to the wide variety of deposition systems available for
the growth of a-C films we will concentrate only on the more
popular techniques that cover the full range of the material
properties obtained in these films. A number of hybrid depo-
sition techniques also exist and generally have a niche category
of materials with specialist applications in mind. In general all
techniques rely on positive C ions that are transported to the
substrate from the source via a plasma, arc, ion beam, or evap-
oration.
2.1.1. Chemical Vapor Deposition
The research by Holland and Ojha [40] in 1976 can be cited
as one of the most influential works that popularized a-C film
deposition when they showed these films can be grown using
a CVD process. They [40] replaced the Sill4 used for a-Si:H
deposition with CH4 and obtained properties that were similar
to those of Aisenberg [32]. PECVD is the most popular method
and uses 13.56 MHz RF excitation of a hydrocarbon gas at a
low pressure (< 1 Torr). The growth temperature can be varied
between 30 and 350~ but in a large number of cases the de-
position is performed at room temperature. In RF PECVD the
gases are ionized between the two electrodes, one driven and
the other which is maintained at ground potential. See Figures 3
and 4.
The plasma developed between the plates depends critically
on the chamber configuration but this would be fixed for each
deposition system. The greater the asymmetry between the
driven and the earthed plate (i.e., the driven electrode being
smaller) the higher the self-bias that is developed. In general,
due to the higher mobility of the electrons with respect to the
ions a relatively large negative self-bias is observed across the
plasma and the driven electrode. On the other hand some de-
position systems are configured to have the driven electrode on
top with the samples being placed on the bottom earthed elec-
trode. In this case, although the DC self-bias developed across
the sheath is negative, the value is very small and is comparable
to the plasma potential, which can be monitored using a Lang-
muir probe. The substrate on either external electrode (driven or
earthed) is bombarded by ions that acquire the plasma potential,
which is critical in dictating the quality of the films. When films
are grown on the earthed electrode they acquire a PAC structure
that has a low defect density, wide bandgap, and high hydro-
gen content. Films grown on the driven electrode are generally
DAC films with high defect densities, low bandgaps, and high
hardness. It can be shown using the Child-Langmuir equation
and the presence of a space charge limited current that the max-
410 SILVA ET AL.
imum energy of an ion striking a substrate placed on a driven
electrode is
Vp =
[AT]4
~pp = [Ratio] 4 (2.1)
where VT, Vp, Ap, and AT are the DC self-bias plus plasma
potential (VT = VDC + Vp), plasma potential, earthed elec-
trode area, and the driven electrode area. Ions within the plasma
sheath will not acquire a total energy equal to e VT as there are
likely to be many inelastic collisions within the mean free path
of the ion. Assuming that the plasma chamber configuration
were to be kept constant, Bubenzer et al. [41 ] developed an em-
pirical relationship between the total energy ET acquired by the
ion before impacting on the substrate surface, VT, and the pres-
sure within the chamber. This was given as
Vx
E ~ p0.5 (2.2)
where P is the pressure. In most RF PECVD reactors the RF
power can be equated to (VT)2, which then gives rise to the
equation
E~[ P~ ]~
(2.3)
Pressure
RF plasmas have an average electron energy of 2-3 eV with
a low ionization efficiency of 10-4-10 -6. Depending on the
hydrocarbon gas used, the mixing gases (dilutant gases), pres-
sure, and flow rate, the energy distribution of the ions that take
part in the growth process can be very varied. Catherine [42]
showed that by using a low frequency (25-125 kHz) discharge
in place of the standard 13.56 MHz power supply, hard transpar-
ent crosslinked films too could be deposited. But no significant
advantages were observed by using the lower frequency.
Koidl et al. [24] conducted a thorough study of the varia-
tions in the material properties as a function of negative DC
self-bias (power) and showed that as the negative self-bias was
increased from close to 0 to 1000 V, there was a steady de-
crease in the optical bandgap from 2.0 to 1.0 eV and hydrogen
content from 40 to 25 at.%. Concomitant increases in the film
density, refractive index, and microhardness were measured.
These films were deposited at room temperature using only a
hydrocarbon gas, C6H6, with the variation shown in Figure 5a.
They further showed that if the process gas were to be changed
from benzene (C6H6) to cyclo-hexane or n-hexane or methane
(CH4) this would have little effect on the refractive index, opti-
cal bandgap, hydrogen content, and s p 3 to s p 2 ratio at a DC bias
of - 4 0 0 V. They attributed this surprising fact to the efficient
fragmentation of the energetic hydrocarbon on the growth sur-
face. It was shown that for films that were deposited at low bias
voltages and were polymerlike in nature, such a process gas in-
dependent phase was not observed, and that larger process gas
molecules were incorporated in the growing films.
Catherine's [42] work showed the variation of the PECVD
deposited a-C:H films when one diluted the hydrocarbon gas
(CH4) in a noble gas (Ar). As the ionization energies of noble
gases such as Ar and He are significantly higher than the vari-
ous radicals of the CH4 molecule it is expected that the whole
energy distribution of the RF discharge is shifted to higher en-
ergies. This also results in a higher dissociation rate as well as
higher electron temperatures within the plasma. In the experi-
ments of Catherine it was shown that the emission intensities of
CH, H, and H2 species all increased linearly with increasing Ar
concentration within the plasma. More interestingly, when an
80% He dilution was used with CH4 in their films, they clearly
showed an energy window in the bias voltage at which films
with an optimum density would be deposited. These data are
shown in Figure 5b. Some additional points have been added
from data calculated using Rotherford backscattering and elas-
tic recoil detection analysis from the authors' group, which
confirm the reproducibility of these experiments. The varia-
tion of a number of physical properties of hydrogenated a-C
(a-C:H) when deposited using a hydrocarbon:noble gas mix-
ture is shown in the Figure 5b. Amaratunga et al. [43] discussed
the variation of the properties of hard DAC films giving rise to
a deposition-etch process when a CH4 gas is mixed with Ar
during deposition of a-C films. In their data they showed that
as the DC bias increased the growth rate decreased, with a con-
comitant increase in the refractive index. They showed that the
refractive index is inversely related to the compressive stress,
and that the compressive stress goes through a peak close to a
negative self bias of 375 V during deposition (see Fig. 5b).
Silva et al. [25] followed this work by showing that a large
controllable variation in the material properties can be obtained
by using Ar dilution in PECVD plasmas, where once more the
data pointed toward an optimum energy window at which a
turning point to the material properties is observed. They indi-
cated that as the DC self-bias is gradually increased the a-C:H
films deposited go through a polymerlike (PAC) to diamondlike
(DAC) transition which at very high bias energies converts back
to a high s p 2 film due to extensive bombardment of the grow-
ing surface. They showed that a very small quantity, if any, of
Ar is retained in the thin film with the large Ar atoms helping
to compact the films during growth. The variation of the mate-
rial properties as a function of DC self-bias for films deposited
with a noble gas dilution is shown in Figure 5b. Two sets of
EPR results are shownm(i) when Ar dilution is used and (ii)
when He dilution is used. Clearly, all the properties shown do
not peak at a particular energy but show that the behavior of the
deposited film when diluted with a noble gas is different than
when using only a hydrocarbon source gas. The low loss plas-
mon peak energy shown in the figure would give a measure of
the valence electron density, which in theory should follow the
density variation as shown in Catherine's work.
Typically, driven electrode deposited hard DAC films us-
ing this technique could have hydrogen contents of 20-40
at.%, while the soft PAC films deposited on the earthed elec-
trode would generally have 40-60% of hydrogen. As hydrogen
prefers to bond in a s p 3 hybridization, the PAC films could have
an s p 3 content comparable to the DAC films. But most of these
s p 3 bonds are in CH3 and CHa configurations as observed by
Fourier transform infrared, in comparison to the C-C s p 3 bond-
 AMORPHOUS CARBON THIN FILMS 411

(a) 45

40

35
(b)
v
o

"-~ 30
I
~8~ ".o"o....
,.,. 2.0,a), '. e* '" 'o
.~. ~'" 1.8
25 "~ E 9
o 1.6 n
> I O~
o
2.0
1.8
1.4 t, ,-ff I ~
< @
(.9 1.6 10201_(b/o 9 9
J< 1.4 N ~ 1019/-
o
1.2 ='8...
(3_ .C
Cm v 16 ) [] D
O 1.0 r 1017
9 9 . . . . , , . . . . . . . . .

CO
I I
I , , I
X
W
o
2.2

2.1
=>~ 10~~ c)
z ~, a. oe
2.0 ~ v
d
u.
W
nr

"~
1.9

1.8

2.0
f B. ~ 109

46)
I 9 ,
' -'
9

, ,
,
E
o 1.9
- 9
~.8
>" 1.7
U~z 1.6
w 1.51
/ o

~"
2

25'
@
~
9149
i ol
o ~ 9 e~ ~
n
O 10 ! 0 t,-

o
W
z
n
I , I
<
T
/ 21 0 200 400
O _ l ~. . . . . . . . . . . . . . .
o 0 200 400 600 800 1000
B=AS-VOLTACE (V) Negative self bias (V)
Fig. 5. Variationof the material properties as a function of negative self-bias voltage for (a) a pure
methane plasma from Koidl et al. [24] and (b) for a methane/noble gas (He or Ar) mixture.

ing present in the DAC films. It is worth noting at this early 2.1.2. Sputtering
stage that FTIR should never be used to estimate the hydrogen
content in a-C:H films as up to 50% of the hydrogen has been In CVD or sputtering the growth occurs atom-by-atom or
shown by Grill and Patel [44] to be unbonded. molecule-by-molecule at temperatures much below the melt-
An interesting and potentially very useful variant to PECVD ing point of the material. The atom (or molecule) that arrives at
deposition was introduced by Silva et al. in 1994 [28]. They the surface will tend to bind itself to the surface at a local mini-
showed that by introducing magnetic confinement to the RF mum energy configuration by moving in a short range. As most
PECVD plasma they could get enhanced thin film properties growth is either at room temperature or close to that, there is lit-
due to the very high dissociation rates and higher electron tem- tle surface kinetic energy for the arriving atom (or molecule) to
peratures within the plasma. For the first time they were able to be able to find a global minimum either by atomic rearrange-
move the Fermi level within the a-C:H films by up to 1 eV, ments or diffusion. This ensures that the deposited material
which allowed them to demonstrate some evidence of elec- possesses short range order but in an amorphous/disordered
tronic doping [29]. They were able to introduce up to 15 at.% state. The above discussion applies to CVD or sputter pro-
of nitrogen to their films without distorting the optical bandgap cesses where no DC bias has been applied. When either a
significantly and study the variation in the material properties. self-bias or other energy source supplies the arriving species
Also, it was shown for the first time that changes in the joint with superthermal energy, this would mean that the adatom
density of states were occurring as a result of the nitrogen in- could displace bulk or surface atoms and have enough energy to
corporation using electron energy loss spectroscopy (EELS) as activate chemical reactions. This allows much more versatility
shown in Figure 6 [29], and that these films allowed for the first to the growth techniques and therefore is widely utilized. Two
demonstration of electron field emission at low threshold fields main techniques are used for the growth of a-C by sputtering:
[45]. RF bias sputtering and magnetron sputtering.
412 SILVA ET AL.

4000
' I ' ' I ' ' I , , I (ai
0
14at. % N

3000
/I:*
v

r
2000
I1)
t"
K edge~~_.~~
1000

N K?dge
o I i i i I i i i i i I
270 300 330 360 390 420

Energy loss (eV)

(b)
L ' -'1 i ' ! i ~
c N= 0at.%

i 200 . . . . ,
i

,
I
-
" ~
o
~. 150

J , [a]
100 / , , I ,./.~p~
~5 / : N - 7at.%
N Oat % L
"~ 50 =

L~ 0 5 10 15 20 25
Energy loss (eV)

I_ , ~ J , , [b].
0.0 1.0 2.0 3.0 4.0 5.0
Energy loss (eV)

Fig. 6. (a) Typical EELS spectrum for a DAC:N film with assignment of the prominent bands and (b)
the joint density of states as determined by EELS, from Silva et al. [29].

In the case of RF sputtering, an Ar plasma is struck below
a graphite cathode which is connected to the driven electrode
with respect to the system earth. The substrates are generally
placed on the lower water cooled electrode which is negatively
biased with respect to the system (and plasma). Typically the
plasma potential is positive and varies between 10 and 20 V.
Unhydrogenated films then can be deposited on the biased sub-
strate as a function of negative bias, which varies the kinetic
energy of the film forming species once it crosses the sheath
space. In general, this technique is more used for metalliza-
tion by the microelectronic industry, and in the case of a-C film
deposition the magnetron sputtering technique is more widely
used.
The main difference between the two sputter processes is
that, in the case of magnetron sputtering, a transverse magnetic
field with respect to the graphite cathode is applied such that
the E x B field confines the drift of the electrons to the target
surface. This means that a more intense plasma with a higher
ionization efficiency is produced which allows for a higher de-
position rate of the thin films. The higher carrier density within
the plasma also allows for it to be operated at a lower pressure.
Most often in the case of a-C films the unbalanced magnetron
configuration is preferred over the balanced setup such that the
plasma extends over both the target and the substrate. In this
case, if Ar is used as the sputter gas it provides both the sputter-
ing flux as well as the ion plating flux over the growing film.
The unbalanced magnetron was developed by Savvides [46]
and a schematic of the deposition system is shown in Figure 7.
Using this technique Schwan et al. [18] have shown that it is
possible to create a similar type of film developed by mass se-
 AMORPHOUS CARBON THIN FILMS
Fig. 7. Schematicof the unbalanced magnetron sputtering system from Sav-
vides [48].
lected ion beams or filtered cathodic vacuum arc which have
a high s p 3 content (87% by EELS). The density of these non-
hydrogenated films was close to 3.1 g cm -3. Interestingly, in
these films the optical bandgap is close to zero which seems
to indicate that all the s p 2 bonds must be clustered and perco-
lating through the structure due to its high conductivity. In this
case the high s p 3 content is attributed to a stress induced trans-
formation from s p 2 to s p 3 states at compressive stresses above
14 GPa. The deposited films have quite unique properties when
compared to other deposition processes for a-C thin films with
evidence for highly ordered s p 2 graphitic planes oriented in the
[002] direction with respect to the silicon (100) substrate [47].
Since the demonstration of the unbalanced magnetron to
produce a-C films by Savvides [48] many other systems based
on similar themes have been pursued by others. Cuomo et al.
[49] produced highly TAC films using a dual ion beam sputter-
ing process on cooled substrates. Andre et al. [50] produced a-C
films with high densities with a different variant based on dual
ion beam sputtering and ion assisted DC magnetron sputtering.
Kleber et al. [51 ] produced a-C films in the balanced magnetron
configuration with a film density of 2.0 g cm -3. This is typical
of sputtered films and a high s p 3 content is not expected.
413
2.1.3. Ion Beam Techniques
One of the major advantages of this type of system is that the
process to produce the ion beam and the deposition process are
independent of each other. This means that it is easier to opti-
mize the various individual parameters or study a model system
more easily using ion beam techniques. Any system whose pro-
cess is based on ion beams would need to have the following
components: an independent means of controlling the ion en-
ergy and flux, isolation of the ion generation from the thin film
growth process, a narrow energy spread for the ion beam, and
low pressure growth with control of the angle of incidence of
the bombarding ions. Some of the more popular sources are
broad beam Kaufman ion sources, ion beam accelerators, and
ionized cluster beam sources. More recently some growth us-
ing plasma immersion ion implantation (PI 3) has also been
reported.
Broad beam Kaufman ion sources were first developed in the
1960s for space propulsion applications as ion thrusters. Since
then it has been used more so for thin film deposition with en-
ergy ranges typically 100-1000 eV. Deposition is carried out at
very low pressures downstream of the source, with the process
working best at high energies, resulting in high current densities
such that potentially useful growth rates are achieved. The ion
flux, ion energy, and direction of the flux can be fully character-
ized and can be independent of the deposition flux. Aisenberg
and Chabot [32] produced the first a-C films using a C + ion
source which was followed by Spencer et al. [52]. Weissmantel
et al. [53] used a dual ion beam deposition system to produce
similar DAC films where one beam provided the C + ions and
the second beam provided Ar +. A second ion beam may be an
ideal way to get ionized nitrogen into the films and therefore
could be examined either as a doping source or to produce high
nitrogen containing carbon nitride films. Xu et al. [54] used a
nitrogen ion source coupled with their cathodic arc system to
introduce nitrogen very efficiently into the TAC films.
The use of ion beam accelerators to obtain MSIBs for bet-
ter control and fundamental studies of the growth of high s p 3
TAC films was first proposed by Lifshitz et al. [55]. Subse-
quently, a number of research groups including Miyazawa [56],
Hofsass [57], and Hirvonen [58] have examined films grown
with MSIB. The deposition is carried out atom by atom using
modified ion beam accelerators which offer isotropically pure
C beams at very low pressures with excellent control over the
flux and ion energy. Magnetic filtering is used to separate ion to
mass ratios which are required for well collimated beams that
are raster scanned over the sample area. The main limitations
stem from the fact that ion beam self-sputtering and ion beam
damage are present in the growth process and at low energies
the growth rate is quite slow. Due to the excellent control of-
fered by the process, beams of C +, C - , and C 2- have been
used to deposit DAC thin films.
Cluster beams to deposit carbon films, especially for nan-
ocluster deposition, have been pioneered by Milani et al. [59].
Cluster beam growth by macroaggregates having 500-2000
atoms loosely bound together are formed by an adiabatic expan-
sion of evaporated material through a nozzle into a high vacuum
414 SILVA ET AL.

chamber. The technique was developed by Takagi et al. [60] and

is now widely used for intermetallic compounds and nanostruc-
tured materials. The advantages associated with the technique
are due to the fact that any charge placed upon the cluster is
equally distributed across each of the constituent atoms and
thereby its use for ultrashallow implants cannot be overempha-
sized. Each of the atoms therefore imparts precisely the total
ion energy given to the cluster divided by the size of the cluster
upon impact with a surface. So the growth process possesses
very low charge to mass ratios for the ionized cluster which
prevents the buildup of surface space charge. The films grown
using this technique have shown unique properties that avail
themselves to electron field emission [61 ] and supercapacitors
[62].
Plasma immersion ion processing (or deposition) has also
been used to deposit DAC films. The work of Nastasi and
co-workers [63, 64] shows that using a C2H2-Ar plasma im-
mersion ion implantation process it is possible to produce films
with varying sp2/sp 3 ratios. In their work they clearly show a
critical dependence of the microstructure of the film to negative
pulse bias and the pulse bias duty factor. In our laboratory we
Fig. 8. Schematicof the filtered cathodic vacuum arc system.
have used a pure CH4 plasma in DC pulse bias mode to produce
DAC films with sp 3 contents as high as 80%. The advantage of
using the PI 3 system is that it allows for high density plasmas
to be used to produce non-line-of-sight coatings on nonplanar
substrates with independent control of the ion energy. raster scanning the plasma beam over the substrate area. A neg-
ative bias is further applied to the substrate with respect to the
2.1.4. Filtered Cathodic Vacuum Arc anode (and system earth) which controls the growth proper-
ties. Films deposited using this technique are nanometer smooth
The FCVA technique has become synonymous with the de-
(RMS roughness of less than an angstrom), with hardnesses ap-
position of TAC films the world over. Since the first films
proaching 60% of that of diamond, a friction coefficient below
were grown by Aksenov et al. [33] and then the technique
was adopted by McKenzie et al. [65] a large number of groups 0.10, and a Young's modulus close to 500 GPa. The ion energy
have begun working with this system [66-70] and made many distribution obtained shows the energy of this highly ionized
improvements to the growth process and fundamental under- beam without any applied bias to be close to 30 eV, with a full
standing of the material properties. It is now considered to width at half maximum of 18 eV.
be a commercially viable system that is capable of producing The versatility of the cathodic arc system in producing a
macroparticle-free films to industry at close to room tempera- range of materials with different properties has been well il-
ture [ 19]. The films produced are highly tetrahedral in nature lustrated in the work of Amaratunga [1] and Coil [70]. It is
(>80% sp 3) and extremely hard. The properties of the de- shown that by having a high density gaseous environment or
posited films are crucially dependent on the ion energy of the a gas jet next to the arc it is possible to rapidly condense the
carbon arc used for deposition. A schematic of the system typ- carbon ions in such a manner as to be able to produce nanopar-
ically used is shown in Figure 8. Xu et al. [19] have recently ticle containing thin films. These nanoparticles in most cases
introduced an off plane double bend that further reduces the have a structure close to those of fullerenes and nanotubes em-
macroparticles in the thin films.
bedded in the a-C thin films. Despite the high sp 3 content of the
A carbon arc is struck between the cathode and a graphite
TAC films, with or without nanoparticles, close to 10% of sp 2
striker (earthed anode), which is retracted once the arc has
bonding within the films controls the optical bandgap and elec-
been struck. This produces a highly ionized beam of C + ions
tronic conduction properties. The bandgap is generally below
and neutrals which are further collimated by the use of an ax-
ial magnetic field. This curvilinear magnetic field is then used 2.5 eV, and the electronic properties are critically dependent on
to steer the ionized C particles through a curved toroidal duct the impurities admitted into the system either in a gaseous form
which makes use of the cross product of the electric and mag- or by solid state incorporation in the graphite cathode. Fallon
netic fields to filter out the neutrals. Therefore, the arc that is et al. [68] have conducted a detailed study of the microstructure
self-sustaining for a few minutes arrives at the off-line-of-sight of these films as a function of ion energy, with Chhowalla et al.
target as a close to 100% ionized plasma, minus the neutrals and [69] conducting a study on the behavior of the growth proper-
the macroparticles. The area of deposition may be increased by ties as a function of substrate temperature.
 AMORPHOUS CARBON THIN FILMS
Fig. 9. Schematicof the laser arc system used by Scheibe et al. [96].
2.1.5. L a s e r Techniques
In the mid 1980s it was shown that using laser ablation of
graphite targets, or pulsed laser deposition (PLD) as it is bet-
ter known, a-C films with properties varying from graphitelike
(GAC) to diamondlike (DAC) can be deposited [71]. Recent
work has taken this technique to the forefront of modern thin
film growth by producing films with some of the highest sp 3
contents as well as hardness (60-80 GPa). The technique is
popular due to its versatility in being able to deposit metal, ce-
ramic, and polymer films with a high degree of control of its
growth kinetics and, due to the rapid progress being made in
the excimer laser field by providing high power pulsed lasers,
increased growth rates. A very good review of the subject can
be found in the paper by Voevodin and Zabinski [72].
An excimer laser focused through a transparent window im-
pinges on a graphite target held in vacuum. This creates a high
pressure carbon plasma that expands hypersonically in vacuum
forming a high energy plume. The carbon ions thus created will
415
form a-C films with varying properties when they condense on
the substrate depending on the laser, vacuum environment, and
substrate condition. The laser fluence and surrounding environ-
ment need to be optimized in order to produce DAC thin films.
Investigations of the plume dynamics have shown the leading
edge (40 ns after laser initiation) of the plasma to have car-
bon atoms of energy close to 1500 eV, with a secondary peak
(100 ns after initiation) at around 100-400 eV. The energy tail
is shown to be composed of clusters of atoms. The leading edge
has fast single atoms and ions with the subsequent peak being
made up of slower ions, neutrals, and molecules. The mechani-
cal properties of the films produced by PLD are second to none,
but it is difficult to filter out macroparticles with this setup.
Much work has also been conducted in producing nanocompos-
ite coatings using this technique. By either having a composite
sputtering target or a secondary sputter target for the mixing
material, superhard amorphous composites can be produced.
Most often due to the high kinetic energy associated with the
plume the incorporated composite crystallizes in nanocrystals
416 SILVA ET AL.

whose motions of dislocation are suppressed in favor of defor-

mations at the grain boundaries which improve the toughness
of the material [73].
A variant of PLD, namely laser controlled pulsed vac-
uum arc deposition or laser arc deposition, was introduced by
Scheibe et al. [20]; see Figure 9. In this case a Q-switched Nd-
YAG laser is used to ablate a graphite target which generates
the plume of carbon ions. The laser in this case is only used
to initiate a plasma that is sustained for a period of 100 ms
with currents as high as 1000 A by a pulsed current source. The
100 ns laser pulse which is repeated at 1 kHz helps achieve a
10 mm/hour growth rate, with systematic erosion of the circular
graphite drum. Variations of the film properties as a function of
substrate temperature have been published by Silva et al. [22].
S p 3 contents in excess of 80% with high (> 700 GPa) Young's
modulus have been demonstrated. The variations of the proper-
ties of the laser arc film with FCVA films have been compared
as a function of growth temperature [22].

2.1.6. Other Techniques

There are a number of techniques being used today which are
a hybrid of one or two of the above deposition systems. One of
the more popular techniques is the dual electron cyclotron reso-
nance (ECR)/RF plasma source where the surface wave couples
microwaves at 2.45 GHz which are used to excite and dissociate
the gas. A capacitively coupled RF supply is then used to trans-
port ions to a downstream substrate holder at which the films
are grown. The system was initially discussed by Martinu et al.
[74] to grow DAC films. Subsequently, Turban et al. [75] and
Godet et al. [76] have performed studies that have illuminated
the physics of the plasma and growth process, including the ma-
terial properties. Once more the films are generally kept at room
temperature on a cooled electrode and the material properties
vary critically as a function of the generated RF self-bias volt-
age. The uniqueness of the system lies in the fact that the plasma
is ionized very efficiently by the ECR source, and by having
a dual source involved the film growth is decoupled from the
plasma generation stage. Therefore, much better control of the
plasma can be afforded, together with the advantageous proper-
ties of RF thin film deposition.
One other technique that has produced some very interesting
properties in the recent past has been the plasma beam source.
A review of the technique can be found in the work of Weiler
et al. [ 17]. As shown in Figure 10, RF power is applied via a
capacitor and matching network to a moveable powered elec-
trode. The magnets around the earthed and powered electrode
help dissociate the plasma more efficiently as well as confine
the plasma into a stream/beam. This beam is then directed to-
ward the substrate on which the film growth takes place. Gases
introduced into the plasma source ionize efficiently to produce
a very well mixed plasma beam. Evidence for electronic doping
of these a-C films has been published with the incorporation of
nitrogen to the C2Hz/Ar mixture which acts as a shallow dopant
for the Jr* states within the gap. Mobility values comparable to
a-Si:H films have been obtained from Hall measurements [77].
Fig. 10. Schematicof a plasma beam source from Weiler et al. [97].
2.2. Growth Models
2.2.1. G r o w t h
Amorphous carbon films, especially the DAC and TAC films,
are metastable in nature. Graphitelike s p 2 bonding is the ener-
getically favorable hybridization in comparison to diamondlike
s p a bonds. Metastable films are formed by raising the energy
of the starting material either by thermal or chemical activation
and then allowing the films to lose energy in a rapid manner
(or quench). This de-energizing process is usually in the form
of quenching and the films could move through a number of
unstable and metastable phases before stabilizing to the final
frozen-in configuration. Metastability could be compositional,
structural, or morphological, where the free energy is lower
than that which is required for atomic relaxation or rearrange-
ment.
There have been many models put forward for the growth
of a-C films. Of these, some of the more significant models are
discussed below. It should be noted that in terms of the struc-
ture of a-C films there is still an ongoing debate as to the most
energetically favorable configuration. Early work by Robertson
[78] proposed a carbon structure that was composed mainly of
 AMORPHOUS CARBON THIN FILMS
2.0 I I I I I III I I I I I I III
1.5
>
L
(9 1.0
r -1
LU
0.5 m
Graphite
Ii111 I I I IIIIJ I I I I IIII
1 Flat
10
Number of sites
Fig. 11. Estimationof the total energy versus cluster size by Robertson [79].
benzene like sixfold aromatic rings that fused together to form
graphitic clusters. In the early models large s p 2 clusters were
separated/segregated by the surrounding s p 3 matrix which con-
trolled the material's mechanical properties. The reasons for the
forming of the clusters were based on an energy gain argument
where adjacent zr bonds would pair up to form s p 2 sites and sta-
bilize each other by forming parallel oriented pairs. These states
would gain further energy if they were to form planar sixfold
rings, which transformed themselves into a yet more favorable
energy minima by clustering. See Figure 11 (from [79]) which
shows the energy gain that can incurred by Jr states pairing up
or clustering. As shown the isolated zr state is quite unstable,
with a energy gain of nearly 1.5 eV per site purely by pairing up
with another zr state. On the other hand, the energy gain beyond
a six-member ring is minimal compared to the predicted disor-
der potential which is greater than 0.2 eV [80], and closer to
0.5 eV [38]. Therefore, with the current calculations, the driv-
ing force for clustering is not observed. In the original model
[78] a relationship between the cluster size and the bandgap of
Eg -- 6 / M ~
where M is the number of rings in the cluster, was derived. Yet,
experimental values of DAC films prevented this model from
being universally accepted due to the fact that a typical bandgap
of 1.2 eV would have meant a 25-ring cluster with dimensions
of the order of 1.2 nm. Neither high resolution transmission
electron microscope [81] nor neutron diffraction studies [82,
83] support this view, although it is difficult to disprove such a
model based on a handful of experimental results. Therefore, it
was noticed that for the cluster model to be reconciled with the
optical bandgap values there needs to be some modification to
the theory.
Since then a number of simulation models have shown that
the bonding within a-C is less structured, with a much higher
probability of olefinic chainlike structures. Frauenheim et al.
[84] computed the structure of a large number of a-C film den-
417
6-fold rings 5+7-fold dngs
9 R7 +
v 0
9 I Gap
OR G
9 o [] o
-2
o .b_ +
E1 E2 E2 B Flat Chair
100
Boat Chair
13= 1.6 eV [] - Distortion only
9 - Distortion + rotation
Fig. 12. Band edge calculations using a Huckel approximation based cluster
model by Robertson for 6-fold and 5-7-fold ring configurations from Robertson
[79].
sities using local orbital simulations and found that in their
work it was more likely for the s p 2 sites to be arranged in
chains rather than rings. The bandgap values obtained by them
matched those measured experimentally. In the case of TAC
once more Drabold et al. [85] also found s p 2 sites to favor
pairing up, which was expected due to the much smaller per-
centage of Jr bonds in their films. Recent experimental results
by Anguita et al. [86] and Godet [76] in the PAC films clearly
point toward a more olefinic chainlike structure with significant
branching as opposed to clustering, but it should be noted that
in the simulations by Galli et al. [80] and Wang et al. [87] there
is evidence for clustering of s p 2 sites.
Robertson [79] has taken these contradictory findings and
modified his original Huckel approximation based cluster
model such that he incorporates the distortion of the sixfold (to-
(2.4) gether with five- and seven-member rings) tings and shows that
this would cause the mixing of tr and Jr states such that it tends
to close the bandgap of a-C films. By this he reconciles the un-
usually large bandgap predicted in the previous work and also
gives reasons as to why large areas of ordered regions cannot be
observed in the microstructure of these films. In this later model
the a-C films are proposed to be composed of roughly equal
numbers of chains and ring structures. But, in order to account
for the room temperature luminescence [88] and polarization
memory effects observed in these films, the addition of nega-
tively charged fivefold rings and positively charged sevenfold
rings is included. These structures will give rise to germinate
pair excitation of carriers but are distorted such that they pull
down the bandgap of the material (see Fig. 12). Although Ra-
man analysis in general supported the need for clusters in a-C
films, results by Schwan et al. [ 18, 77] showed that there is still
418
Fig. 13. Ternary phase diagram for hydrocarbon (a) initially proposed by
Reinke et al. [89] and (b) the compositional space occupied by TAC, DAC,
PAC, and GAC thin films.
room for improvement of this model to universally cover all
types of a-C films.
A ternary phase diagram for hydrocarbon films was intro-
duced by Reinke et al. [89] for the analysis of a-C films in 1993.
It has now been modified extensively and is used to categorize
a-C films [90]. See Figure 13a and b. The diagram represents
the allowed configurations for a-C films that have varying sp 2,
sp 3, and hydrogen contents. Figure 13a shows the original di-
agram used by Reinke, whereas Figure 13b has been adapted
to show the compositional space for the films defined in this
review as TAC, DAC, PAC, and GAC. NAC cannot be repre-
sented on the diagram as it is generally restricted to TAC and
DLC films that have diamond nanocrystallites or TAC and GAC
films that have graphite nanocrystallites embedded in the ma-
trix.
SILVA ET AL.
Fig. 14. Schematicof the surface atoms caused by ions impinging on a surface
in (a) single thermal spike and (b) displacement spike, from Weissmantel et al.
[53].
Fig. 15. The pressure-temperature phase diagram showing the Berman-
Simon curve for carbon.
2.2.2. Thermal Spike
The proposal of a thermal spike for the formation of metastable
phases of a-C was proposed by Weissmantel et al. [53] using the
concepts introduced by Seitz and Koehler [91 ]. It was proposed
that the temperature variation T at a distance r at a time t could
be given by
E ( CpF2) (2.5)
T = 8[zrKt]3/2[C1~ exp 4Kt
where E is the energy provided by the impinging particle, K
is the thermal conductivity of the film, C is the heat capacity,
and p is the density. It was calculated that for an ion energy
E of 100 eV, a region of radius 0.75 nm would be heated at
least to the melting point, 3823 K, of diamond, with the ther-
mal spike persisting over a time period of 7 • 10 -11 s. This
is long compared to the Debye temperature based vibrational

I Ion source
/ I
T 9 ~ (L), ~ (H) En (L) < T < En (H)
Surface Surface
j-,,,
&-- High Low High Low
Ea Ea E~
i while dissipating an average energy of below 1 meV per target
i
|
| atom. The final stage would be a long relaxation step that could
T > Ea(L) i
P qi
L---
o
Radiation damage Preferential displacement+
na ~ 0.8T 12En Mold effect +
Thermal spike
Fig. 16. A schematic illustration of the subplantation process where T is the
energy transferred in a primary ion collision and Ed is the high and low dis-
placement energies, from Lifshitz et al. [98].
period of 10 -14 s. A schematic of the predicted variation of
the surface of the thin film is shown in Figure 14, which has a
predicted shock front giving rise to a pressure of 13 GPa. This
pressure is well beyond the transformation stress of a s p 2 bond
to a sp 3 according to the Bermon-Simon curve for carbon, Fig-
ure 15. Therefore, the thermal spike model of Weissmantel was
one of the first to consolidate the concept of high quench rates
(10-14 K/s) freezing in metastable phases of atomic arrange-
ments in a-C films. The propagation of thermal spikes affecting
a volume of the material and the vacancies and displacements
left in the wake of a high energy collision are illustrated in Fig-
ure 14. One of the problems associated with this model was the
concept of how effective a low mass ion such as carbon would
be in creating energy cascades via thermal spikes at low ion
energies within a material.
2.2.3. S u b p l a n t a t i o n
Subplantation as a concept was first proposed by Lifshitz et al.
[55] for the growth of diamond from C + ions. In this model
it was proposed that hyperthermal species with energies be-
tween 1 and 1000 eV could impinge on a substrate with enough
energy to subimplant into the thin film and help form a con-
tinuous layer of thin film by subsurface growth. Although the
initial model used incorrect displacement energies to show that
one phase of carbon formed preferentially over another, the ba-
sic concept of subplantation has been universally accepted as a
plausible route to the formation of highly metastable films such
as a-C. In general the C + will lose energy by atomic displace-
ments, phonon excitation, or electron excitation. If the energy
of the carbon ion is greater than 25-30 eV, which is the dis-
placement energy for graphite, there is a good chance that the
displaced atom will be trapped interstitially or at a vacancy.
AMORPHOUS CARBON THIN FILMS 419
This would then constitute the first steps of a subsurface growth
process. Ion penetrations of 0.3 to 30 nm have been calculated
as the range with TRIM for C + energies of 10-10,000 eV. In
T < En(L)
this model it is proposed that three different time scales are
present. At the outset a collisional stage gives rise to a ther-
surface
,/-,,,, mal spike at a time step of 10 -14 s to a small volume close to
High Low 1 nm. Energies per target atom could exceed 1 eV. These highly
Ed Ed agitated atoms would then thermalize in a time step of 10 -12 s
last as long as 10-10 s, where chemical interaction, phase trans-
formations, and diffusion could take place. Many experiments
have been performed in developing this model and relating the
growth process to material properties. Some of the variations
with ion energy are shown in Figure 16, where three clear re-
Moldeffect + gions can be identified. First, at very low energies there is not
Thermal spike enough energy for ions to penetrate the surface of the growing
film and therefore there is surface growth. In this case most of
the film is sp 2 bonded with low density and low bandgap. As the
film growth only occurs via surface mobility there is much sur-
face roughness associated with this phase. In the second stage
the C + penetrates the subsurface and starts to densify this layer.
An optimum high sp 3 content can be obtained during this pe-
riod, with very smooth layers of film due to the smoothing out
of any surface undulations by the energetic carbon deposition.
The third stage of the energy regime is when enough energy
is imparted into the film such that the carbon ions have in-
creased mobility such that it suppresses the growth of the sp 3
rich metastable phase. C ions will tend to agglomerate into an
energetically favorable sp 2 phase that will tend to increase the
roughness of the film surface.
Variations of the material properties for MSIB [21], TAC
[66, 92], and DAC [43] can be found in the literature. In the case
of DAC films clear energy windows for optimum bandgap have
been experimentally verified [25]. Robertson [90] and Davis
[93] have independently analyzed the growth process that oc-
curs during subplantation and introduced analytical expressions
that describe the densificaton process as a function of energy.
This can then be related to the sp 3 content, as there is a lin-
ear relationship between density and sp 3 content as shown in
Figure 17 for magnetron sputtered films. A similar relationship
can be found for most types of a-C films. The variation of the
change in density arrived at by both Robertson and Davis is
given by
Af f
(2.6)
f0 ( 1 / q ~ ) - f + O.O16p(Ei/Eo)5/3
where A f is the densification of the film at ion energy Ei, ~b
is the fraction of fast ions, f is the fraction of atoms that pen-
etrate the surface, p is a constant close to unity, and E0 is the
excitation energy to escape from a trapped state to the surface.
The O.O16p(Ei/Eo) 5/3 is taken from the thermal spike model
of Seitz and Koehler [91 ], and therefore this equation could be
seen as a hybrid model. Using suitable fitting parameters the
equation has been used to fit data from a number of groups.
420 SILVA ET AL.

Ion Energy / eV
! ! 1 1 ! !

28 48 68 88 108 128 148 zero loss

3.20
=
3.15 E
U
3.10

90 3.05 .~m>"
(/3
E
3.00 a
8s
~ plasmon
2.95
E
80

75 __L_
t L _ I I I I.
[a]
I
-

-lo o
L
I ~
__

lo
i

20
I

30
I

40
I

so
I

60 70
0 20 40 60 80 100 120 Energy loss (eV)
Negative dc bias / V Fig. 18. Low-loss EELS spectrum for TAC.

100
0 Present work J /,/,
80 -
0 Fallon d~bd:D.~/To their material with the s p 3 bonds being compressive and s p 2
McKenzie o*~ I ~ ' ~ D i a m o n d bonds being tensile. This implies that if the balance of bond-
0 Lifshitz * .9 ~ 1
60 -
Weiler o o* ,.,-/ _~ ing and the distribution of the s p 2 bonding is correct, there is a
possibility of having stress stabilized s p 3 bonding with close to
Q.
r
40 - ."Y 1 zero macroscopic stress.

20 - 0 * A ;,'ej~ rk, -~
3. M I C R O S T R U C T U R E

1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.1. Experimental Determination of Microstructure
Density / gcma 3.1.1. Electron Energy Loss Spectroscopy
Fig. 17. (a) The variation of carbon s p 3 bonding and density in TAC films
as a fraction of ion energy and negative DC bias voltage. (b) Comparison of In a transmission electron microscope, "fast" electrons can
the s p 3 bonding in TAC films as a function of film density [17, 68, 99, 100]. be used to form magnified images of the microstructure of a
The variation predicted [101] using a "rule of mixtures" is also shown (dashed specimen. In addition, because of the many different interac-
lines). tions that high energy electrons undergo as they travel through
matter, electron microscopy allows a host of microanalytical
techniques (such as cathodoluminescence, Auger electron spec-
2.2.4. Stress Induced Phase Transition troscopy, and energy dispersive X-ray spectroscopy). Among
these perhaps the most valuable in ascertaining the structure
The importance of stress to the formation of s p 3 bonds was
and composition of amorphous carbon films is EELS.
proposed and discussed by McKenzie et al. [94]. They were
Electron energy loss spectra are obtained by passing the
the first group to show evidence for the diamondlike bonding
electron beam transmitted through a sample through an en-
structure of TAC films, and they attributed the high s p 3 con-
ergy dispersive magnetic prism onto a parallel electron detector
tent to the compressive stress present in their films. When the
array. By measuring the energy lost by electrons transmitted
compressive stress, as measured using a curvature method, is
through the sample, information about thickness, electronic en-
converted to the effective hydrostatic pressure within the film
ergy band structure, atomic density, chemical composition, and
it was shown that the points lay above the Berman-Simon
chemical b~nding can be obtained.
curve, which demarcates the graphite/diamond boundary on a
temperature-pressure phase diagram, Figure 15. This allows for
the nominally energetically less stable s p 3 bonds to form un- 3.1.1.1. L o w - L o s s R e g i o n
der stable phase conditions of high stress. The model proposes
Figure 18 shows the low energy loss region of an EELS spec-
that it would be equally applicable to other material systems
trum for TAC. The zero-loss peak corresponds to electrons that
where more than one phase can be present by changing the pres-
have undergone either "elastic" scattering in the forward di-
sure range via compressive stress. Recent results by the Sandia
rection or have passed through the specimen unscattered. The
group have shown that stress-free, freestanding, highly tetrahe-
width of this peak reflects the energy resolution of the system.
dral films can be produced by annealing out any compressive
The integrated intensity of the zero-loss peak, I0, is related to
stress. This appears to be feasible according to the models of
the integrated intensity over the entire spectrum,/total, by
Kelires [95] who using Monte Carlo simulations predicts highly
inhomogeneous microscopic stresses of the order of GPa within I0 - - /total exp(-t/X) (3.1)
 AMORPHOUS CARBON THIN FILMS
(/)
E
3 E
1s-~*
e'-
I I
270 280 290 300 31 o 320 330
Energy loss (eV)
Fig. 19. EELS spectrum of a typical K-edge for highly graphitic carbon.
where t is the thickness of the specimen and X is the mean free
path for all inelastic processes in the material. Equation (3.1)
allows comparison of the thickness of samples of the same ma-
terial, or if X is measured from a sample of known thickness
(or calculated from theoretical cross-sections) it can be used to
calculate the absolute thickness for a sample. Additionally, the
ratio t/X can be used as a measure of the importance of multi-
ple inelastic scattering and its effect on the extended EELS fine
structure.
The broad peak in the low-loss region corresponds to energy
loss to modes of collective excitation of valence electrons in
the material known as plasmons (analogous to phonons in the
vibrational modes of an atomic lattice). The plasmon energy Ep
is given by
Ep = ~ p (3.2)
where COp is the plasmon frequency. Using a "quasi-free" elec-
tron model [ 102], COp is related to the valence electron density
Nv by
o92 -- Nvq2 (3.3)
60m
where qe is the charge of an electron, G0 is the permittivity of
free space, and m is the effective mass of an electron (in this
case approximately equal to the rest mass of a free electron).
For many materials, including insulators, Eq. (3.3) can be used
to estimate the atomic density (and hence physical density) of a
sample, if the involvement of all electrons in the outer valence
shells (four electrons per atom in the case of carbon) is as-
sumed. Thus, given the marked difference between the density
of graphitic carbon and diamond (1.3-1.55 g cm -3 for glassy
carbon and 3.515 g cm -3 for diamond [102]), measurement
of the plasmon energy loss gives an approximate gauge of the
tetrahedral (or otherwise graphitic) nature of a given amorphous
carbon film. Plasmon energies of around 31 eV are typical of
highly tetrahedral, predominantly sp 3 bonded carbon films (cf.
33 eV for diamond [ 104] and <24 eV for graphitic amorphous
carbon films) [ 105].
421
/ .l~ ~ ,-~ --~, " %
,'~ /
glassy e
,- carbon J /" "~'~- ,~.~
r a-C:H
r
TAC
1 I , , 1
270 280 290 300 310
Energy loss (eV)
Fig. 20. CarbonK-edge EELS spectra for TAC deposited by filtered cathodic
vacuum arc and a-C:H deposited by glow discharge from methane from Martin
et al. [65], compared with that of glassy carbon.
3.1.1.2. Inner-Shell Excitations
At higher energies in the EELS spectrum, features arising from
the excitation of core electrons are observed. Such excitations
generally involve the transition of inner-shell electrons to states
in unoccupied levels above the Fermi energy of the solid. In
materials with an electronic bandgap, the shape and structure
of resulting EELS "edges" provide valuable information about
the density of unoccupied states near the edge of the conduction
band as well as the chemical makeup and bonding in a sample.
Figure 19 shows the EELS K-edge (corresponding to transitions
from K-shell states) for carbon with a high graphitic bonding
component. The feature marked " l s - Jr*" is characteristic of
states arising from sp 2 bonding and can be used to quantify
the fraction of sp 2 bonded carbon atoms. This is done by com-
paring the integrated intensity of this feature as a fraction of
the total main core-loss edge, to that measured from a standard
of known sp 2 fractionmideally glassy carbon with 100% sp 2
bonding but with no crystal structuremby the equation
Isamplezr* Istandard(AE) exp(tsample/~.)
fsample -- Istandardrr* Isample(AE) exp(tstandarO/,k) fstandard
(3.4)
where IsampleJr* and Istandardrr* are the integrated intensities
under the Jr* peak for the sample and standard, respectively,
Isample(AE) and Istandard(AE) are the integrated intensities
over an energy window of width A E , and exp(tsample/X) and
exp(tstandard/X) are thickness and material dependent factors
which introduce a minor correction to account for the weak-
ening of the Jr* feature with multiple scattering (and can be
determined using Eq. (3.1)).
3.1.1.3. EELS from Amorphous Carbon
Along with neutron diffraction (see Section 3.1.2) EELS pro-
vided some of the first evidence of the high atomic density and
tetrahedral nature of TAC thin films deposited by filtered ca-
thodic vacuum arc. Figure 20 shows the carbon K-edge from
Martin et al. [65] showing the absence of the ls - zr* feature in
422 SILVA ET AL.
, , , i . . . . i . . . . i . . . . i . . . . i . . . . i . . . . ~ . . . . I . . . . 32 i i i

f
M c K e n z i e et al
I s-x 31 A., ^/',= - 0 - - Fallon et al
",,. ~ ~ " = / " ' " Gerstner et al
30

L glassy I / \ t ~ 29 -
c
~O
e- 28

E 27
u3
r
~. 26

25

v 24
.__>, 10 ~ 101 102 103 104
u)
e- 69% sp 3 Ion e n e r g y (eV)
.....

2 x I 0 la
Fallon et al
73% sp 3 ,3- - - - ~ -~-- Grossman et al -
80 z~. . . . ~ ' r 1 7 6 -.'%~', - - ~ - - Gerstner et al

lx1013
._e-o_ 60 ~
.X. -

undamaged
t._ |
ta-C
U'J 40 I: ~ -

270.0 ~ 0 . 0 290.0 300.0 310.0 320.0 330.0 ~0.0 350.0 "

i
\
Energy loss (eV) ~o- / i -

Fig. 21. Evolution of the carbon K-edge in ion damaged TAC as a function
of 200 keV Xe + ion fluence, and a glassy carbon sample for comparison, from 0 i i I i ......
McCulloch et al. [107]. 101 102 103 104

Ion e n e r g y (eV)

Fig. 22. Plasmon energy as a function of incident carbon ion energy from
tetrahedral amorphous carbon deposited by FCVA indicating a McKenzie et al. [94], Fallon et al. [68], and Gerstner et al. [ 110], and s p 3 frac-
tion as incident carbon ion energy from Fallon et al. [68], Grossman et al. [ 108],
low concentration of s p 2 bonding compared to a-C:H deposited
and Gerstner et al. [ 110].
by a methane glow discharge. Subsequent investigations calcu-
lated the total fraction of s p 3 bonded carbon atoms in these
films from the K-edge EELS spectra to be in excess of 80% nitrogen was introduced in order to dope it. The incorporation
[106]. Figure 21 shows the evolution of the ls - 7r* feature as of hydrogen had little effect on both the s p 3 fraction, and only
a result of 200 keV Xe + ion damage induced graphitization of a small decrease in the density as inferred from the plasmon
TAC as a function of ion fluence (and the resultant s p 3 fraction energy as higher flow rates, and was found to decrease the de-
calculated from the spectra) from McCulloch et al. [107]. fect density by around an order of magnitude at flow rates up
EELS also provides an invaluable tool for determining the to 0.05 sccm (as inferred from space charge limited electrical
effect of different growth conditions on the bonding and den- characteristics; see Section 6) then to increase again at flows
sity in carbon films. Of particular importance in the growth of in excess of 0.1 sccm. In contrast and perhaps not surprisingly,
tetrahedral carbon films is the role of the substrate bias and ion the incorporation of nitrogen has a much greater influence on
energy. Many groups have found maxima in both plasmon en- both the bonding and density, with s p 3 fraction and plasmon en-
ergy and s p 3 fraction as a function of incident ion energy [68, ergy decreasing gradually with nitrogen flow rates up to around
94, 108, 109]. However, where this maximum occurs appears 4 sccm and decreasing rapidly above this. The effect of electron
to vary from group to group (see Fig. 22), probably as a result beam radiation damage while in the electron microscope was
of other factors such as ion fluence and substrate temperature. also found to be significantly greater for films containing as lit-
Indeed Gerstner et al. [ 110] found no maximum in s p 3 fraction tle as 1 at.% nitrogen, indicating a reduction in the structural
above the ion energy of films deposited without applied sub- stability of the carbon network with nitrogen incorporation.
strate bias.
Another important factor is the effect on the density and
3.1.2. Electron and Neutron Diffraction
bonding in films with the incorporation of impurities introduced
to alter their electrical properties. Figure 23 shows the plasmon While information about the chemical bonding in a film can
energy and s p 3 fraction as a function of hydrogen and nitrogen be obtained from energy loss spectra, detailed structural infor-
flow rate from Davis et al. [111, 112]. Hydrogen was intro- mation and the coordination and separation of atoms from one
duced in an attempt to reduce the defect density in TAC and another in a sample can only be obtained by diffraction mea-
 AMORPHOUS CARBON THIN FILMS 423
_ !

TAC:H
30
1001}
VI-----, - - ' - - ~ ,. _
29
(/1
28
/ _ t-,
-I
t,- TAC:N \
t-
O
27 \ t,_
[]
E
r/)
t~
_ t,_
28 !110}
Q. v
A
25 ov

24
b _
(/1
-1350 V, 48~ sp 3

I 1 I i r
0.01 0.1 1 10 10
t,-
H 2 and N 2 gas flow rate (sccm) C3) -1000 V, 6 4 % sp 3
t--
100 ! i i t,,.
1==
TAC:H r

80
-600 V, 72~ ,%o3

v
t- 60
0V, 80%sp 3
O
\
TAC:N ~ 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
40
%.
1/1 Scattering vector Q (nm -z)
Fig. 24. Energy filtered electron diffraction intensities for TAC films de-
,D posited at various substrates biases from Gerstneret al. [ 110].

0 I I i

0.01 0.1 1 10 10

H 2 and N 2 gas flow rate (sccm)
Fig. 23. Plasmon energy and s p 3 fraction as a function of hydrogen gas flow
and nitrogen gas flow from Davis et al. [ 111, 112].
surement techniques. In the case of amorphous carbon films,
electron diffraction and neutron diffraction have been particu-
larly useful.
The principle advantage of electron diffraction over X-ray
and neutron diffraction is that information can be obtained
from extremely small regions of a specimen and significantly
less material (particularly important in the case of thin films)
is required. However, due to the difficulty in obtaining good
qualitative reflection intensity data and the removal of the con-
tribution of inelastically scattered electrons from the signal, it
is only through the advent of computer interfaced electron en-
ergy loss spectrometers that both of these problems have been
overcome and allowed electron diffraction to become a useful
tool in the analysis of amorphous and polycrystalline materials.
By stepwise scanning the selected area electron diffraction
pattern from a specimen across the entrance aperture to an
electron energy loss spectrometer, a zero energy loss (elastic)
diffraction intensity as a function of scattering angle can be ob-
tained. The first practical use of this technique for the analysis
of amorphous and polycrystalline films was demonstrated by
Cockayne and McKenzie [ 113, 114].
Figure 24 shows the energy filtered diffraction pattern as
a function of scattering vector Q, for TAC films deposited in
the filtered cathodic vacuum arc at various substrate biases by
Gerstner et al. [ 110]. The appearance and evolution of a peak
corresponding to the {002} reflection in graphite (correspond-
ing to a lattice spacing of 0.335 nm) with increasing substrate
bias indicate the emergence and clustering of sp 2 bonded atoms
within the sp 3 network in the form of sheets, which are to some
extent parallel and correlated in position.
In order to obtain more detailed quantitative information
about structural parameters such as average bond length, bond
angle, and coordination number in an amorphous material, both
electron and neutron scattering intensity data can be use to ob-
tain the reduced radial density function G(r). The G(r) is a
measure of the spherical average of the deviation of the radial
atomic density p(r) from the average atomic density P0 for the
sample at a distance r from a typical or average atom center and
is most commonly defined by the expression
G(r) -- 4zrr[p(r) - Po] (3.5)
which can be calculated from a Fourier-sine transformation of
the diffraction data given by
a(r) --
~2__ f0 arnax
. Q[S(Q) - 1]D(Q) s i n ( Q r ) d Q (3.6)
where Q is the scattering vector (given by 4n" sin(0)/1, where
0 is the scattering angle and ~. is the wavelength of the inci-
dent radiation), D(Q) is a damping factor (commonly a sinc
function in the case of electron diffraction [115]), and S(Q)
is the structure factor calculated from the scattering intensity
I (Q) which in the case of neutron diffraction takes into account
attenuation, background, and container, multiple, and inelastic
424 SILVA ET AL.
' ' 1 . . . . ! . . . . r . . . . i . . . .

neighbor coordination number of 0.153 nm, 110 ~ and 4.0 re-

.S't

,a ~ Waltem et al. - a-C:H (propane) spectively from electron diffraction [94, 115] and 0.152 nm,
I #'l .I I. 0''. (neutron)
110 ~ and 3.8 respectively from neutron diffraction [ 116, 117].
I '; / ^~. ; ", ,,. .... , . . . . . . . . . . .
~I . : ,.; ;/i,...,.,.,.,. . . . . _ These values are consistent with a predominantly tetrahedrally
~1
1 1"!'~ " ; : W a l t e m otal. - a-C:l-I (acetylene) bonded carbon network, compared to 0.154 nm, 109.47 ~ and
/ : TI '0 / t- ."~ (neutron)
/ ; 9 I / ~ ..... ._. 4.0 respectively for diamond and 0.142 nm, 120 ~ and 3.0 for
graphite.
_
However, less straightforward is the comparison of the sec-
t,.-
ond nearest neighbor coordination number calculated from the
E',
GI
t._ .% second peak in the G(r). It is evident both in the study by
r
I,..
I ./'.~ " - x J i ~.. a,~,,t,,i.- rAc Gaskell et al. [116] and in a subsequent higher resolution neu-
t,tl [ i ! ! \ (neutron)
v
I ! i i ", .,"- .-,, .......
. . .- tron diffraction study by Gilkes et al. [ 119] that this second peak
/,,t.. ~ ,,. ,.- _
v

L9 9.... . "~' i "" ....

I ....... : i ';
I----, //\\
0.1 0.2
Fig. 25. Radialdensity functions for TAC from electron diffraction [94] and
neutron diffraction [ 116, 119]for sputtered a-C from neutron diffraction (Li and
Lannin [118] taken from Frauenheim et al. [84]), and for a-C:H from acetylene
and propane precursors from neutron diffraction [83].
scattering (see Waiters et al. [83] and Gaskell et al. [116]). In
the case of inelastic electron scattering it is calculated by
S(Q) - I(Q)/Nf
where N is number of atoms in the sample (obtained by a least
squares fitting (3.7) to I ( Q ) at large scattering angles) and
f ( Q ) is the atomic scattering factor for electrons (see Cock-
ayne and McKenzie [113, 114] and McKenzie et al. [94, 115]).
By fitting appropriate peaks (Gaussians convolved by an ap-
propriate function to account for experimental parameters such
as maximum collection angle) to the resulting G(r) the average
bond length and nearest neighbor distances can be determined,
and the bond angle can be calculated by
0 -- 2sin-1 ( ~r~
r2 )
where rl and re are the first and second nearest neighbor dis-
tances, respectively. The average number of atoms bonded per
atom, or coordination number, is then given by
C(rl, r 2 ) - fr r2 r G ( r ) d r + --~-po[r32
47r -r31]
1
Figure 25 shows the reduced radial density functions for
TAC from electron diffraction [94] and neutron diffraction
[ 116, 117], sputtered a-C from neutron diffraction [ 118], and
a-C:H from neutron diffraction [83]. For TAC the G(r) gives
a first nearest neighbor distance, bond angle, and first nearest
is in fact made of two Gaussians at 0.248 and 0.275 nm. Gaskell
.." ,'\ et al. assume that both peaks are due to contributions by sec-
ond nearest neighbors and arrive at a second nearest neighbor
coordination number of 8.9. Gilkes et al., on the other hand,
i A / concede that the second peak at 0.275 nm may be made up of
both second and third nearest neighbors and calculate a sec-
ond nearest neighbor coordination of between 7.66 (in which
all contributions to the second peak are third nearest neighbors)
0.3 0.4 0.5
and 11.06 (in which the majority of contributions to the sec-
r(nm) ond peak are second nearest neighbors). It is important to note
that if some number of atoms at 0.275 nm are indeed second
nearest neighbors then the average bond angle will be some-
what higher than the tetrahedral angle 109.47 ~ This ambiguity
underlines the fact that the structural information contained in
G (r) is not unique to any single structure, with many structures
potentially resulting in the same G(r). To some extent, there-
fore, any accurate discrimination between these structures must
include reference to information obtained by other methods
such as infrared and Raman spectroscopy (see Section 4.4.1).
(Q) 2 (3.7) It is also helpful to compare these properties with those of com-
puter models to form a better picture of the probable structure
of these materials, and such models are reviewed in Section 3.2
with particular reference interpretation of the second coordina-
tion sphere in the G(r).
Interpretation of the G(r) for a-C:H with a high hydrogen
content and mixture of sp 1, sp 2, and sp 3 bonding is similarly
complex but perhaps less subtle than that of TAC. Peaks at near-
est neighbor distances corresponding to hydrogen-hydrogen,
carbon-hydrogen, and double and single carbon-carbon bonds
are all evident [83]. While a determination of the relative pro-
portion each of these bonding types is difficult, the accuracy in
(3.8) the determination of the peak positions does allow differentia-
tion, in the case of sp 2 bonds, between chainlike olefinic bond-
ing (with a first nearest neighbor distance of around 0.134 nm)
and ringlike aromatic bonding (with a first nearest neighbor dis-
tance of around 0.142 nm). In the case of both samples analyzed
by Walter et al. olefinic bonding was found to predominate,
(3.9) which is important with respect to the labels "polymeric" and
"graphitelike" in the case of sp 2 rich films.
3.2. Computer Modelling of Growth and Structure
Computer simulation and modelling of amorphous materials
range in sophistication from hand built structural models, to
 AMORPHOUS CARBON THIN FILMS
classical molecular dynamics using empirical interatomic po-
tentials, to full blown ab initio quantum mechanical molecular
dynamics. The advantage of less rigorous empirical approaches
is their ability to model large systems, surfaces, and equilibrium
processes, such as thermal annealing, without unreasonably
long computation times. The main disadvantage, however, is
their limited ability to model the complexity of large range of
potential bonding environments of carbon atoms including mix-
tures of hybrid bonding states (sp 1, sp 2, and sp 3 bonding), and
in particular zr bonding.
3.2.1. Empirical Models
Owing to the fact that graphite is the stable allotrope of car-
bon at standard temperature and pressure, and that in most
disordered forms of carbon sp 2 bonding is the favored phase,
an important question regarding TAC is that of its formation
mechanism (see Section 2). A key to this question may lie
in the fact that when films of a high sp 3 bonded content are
deposited, they always form with high compressive stresses,
typically in the order of 5-6 GPa [120]. McKenzie et al. [94,
99, 115, 121 ] proposed that it is the formation of compressive
stress due to the subplantation of carbon ions, either by direct
or knock-on implantation into the growth region below the sur-
face of the film, that creates an environment for the formation
of carbon in which sp 3 or diamondlike bonding is the preferred
phase--analogous to the way in which synthetic diamond is
made industrially. Robertson [122], however, has proposed a
different mechanism in which densification leads to preferen-
tial sp 3 bonding and compressive stress is simply a by-product
of such densification. At best, it is contentious as to whether
or not the formation of sp 3 carbon bonding is the result of
compressive stresses or vice versa, or whether they just ap-
pear simultaneously in a related though not necessarily causal
way. In simulations of two-dimensional systems analogous to
carbon, Marks showed the evolution of compressive stresses in-
duced during the growth of films with ions in a similar range to
those produced in the cathodic arc, without any subplantation
[123, 124]. Furthermore, a number of groups have shown that
some of the stress in TAC can be relieved without a significant
reduction in the sp 3 fraction [ 125, 126]. However, whether or
not its formation is contingent on the presence of compressive
stress during growth is as yet unresolved.
3.2.1.1. Hand Built Models
One of the first attempts to model the structure of amorphous
carbon was conducted by Beeman et al. [127]. Carried out be-
fore the tetrahedral nature of filtered cathodic arc deposited
amorphous carbon was confirmed, one of the aims of this study
was to investigate the feasibility of tetrahedral bonding in a-C
films proposed by Kakinoki et al. [128]. In this work hand built
atomic models of random carbon networks containing various
fractions of trigonal and tetrahedral bonding were constructed.
These models were then relaxed by allowing the atoms to move
in order to minimize their elastic strain energy as described by
425
a potential developed by Keating [ 129], and their radial density
functions, vibrational density of states, and Raman spectra were
calculated and compared to experiment. While it was found that
the fraction of tetrahedral bonding was likely to be negligible in
the majority of carbon films for which experimental data were
available at the time, comparison of the experimental results
from films analyzed by Kakinoki et al. was consistent with Bee-
man's model containing 9% fourfold coordinated carbon atoms.
3.2.1.2. Stillinger-Weber Potential
One of the first successful simulations of group IV semiconduc-
tors was applied to silicon in both solid and liquid phases by
Stillinger and Weber [130]. The generalized potential energy
function describing interactions between N identical particles
can be expressed as the sum of all individual n-body contribu-
tions Vn by
U-- Zvl(i) + Zv2(i' J) + Z v3 (i, j, k)
i i,j i,j,k
i<j i<j<k
+ " ' " - + - UN(1 . . . . . N) (3.10)
The Stillinger-Weber potential approximates this potential
function by considering only two- and three-body contribu-
tions. The two-body term v2 (i, j ) depends only on the distance
between atom pairs rij and is given by
V2 (rij) - - E A ra - 1 e x p rij < a
rij -- a (3.1 l)
= 0 otherwise
and the three-body term v3(i, j, k) depending on the atomic
separations rij and r j k and the triplet bonding angle 0 is given
by
v3(rij, rjk, 0 ) - - ~ i ~ . [ y t ~ ]
rij -- a rjk - a
• [cos(O) - cos(O0)] 2 , rij < a and rjk < a (3.12)
= 0 otherwise
where 00 is the ideal bond angle for a triplet, E is the bond
strength, X represents the resistance to change in bond angle,
a is the maximum bond length, and A, B, and y are "fitting"
constants. The advantage of the Stillinger-Weber potential over
those typified by the Keating potential used by Beeman et al.
[ 127] is that it more accurately describes large atomic displace-
ments from the ideal tetrahedral geometry of crystalline silicon
thereby allowing both its liquid and amorphous phases to be
modelled.
While originally intended for application to exclusively sp 3
bonded systems such as silicon and germanium, Bensan [ 131 ]
and Mahon et al. [132] showed that the ~r bond contribution
of sp 2 and sp 3 carbon bonds had the same functional forms
(when considered in reduced units) and could therefore both
be implemented with the same potential. Using Hartree-Fock
self-consistent field calculations of the energy of small car-
bon clusters, the Stillinger-Weber Eqs. (3.11) and (3.12) were
426 SILVA ET AL.
thereby reparameterized to model trigonally [131] and tetra-
hedrally [132] bonded carbon atoms. Gerstner and Pailthorpe
[133] then integrated both these modified potentials into one
molecular dynamics simulation to investigate the effects of
many successive carbon ion impacts, simulating film growth
with energies in the range of those used in the growth of TAC,
into the surface of a 320-atom diamond lattice. The bonding
hybridization of each individual atom in the lattice was dynam-
ically determined using an algorithm developed by Marks [ 134]
based on bond energy minimization, and modelling of the po-
tential between s p 2 and s p 3 hybridized atoms was implemented
using average values for E and cr between those for diamond and
graphite. Periodic boundary conditions were applied in the x-
and y-directions to minimize the computation time required for
the system to reach equilibrium. Thermal energy was extracted
through the bottom-most layer using a random thermostating
procedure [135]. The molecular dynamics of the system was
carried out by solving Newton's equations of motion discretely
using the Verlet algorithm [ 136, 137].
While the systems studied were too shallow to simulate the
tetrahedral growth beyond the top graphitic layer observed ex-
perimentally on the surface of all TAC films, they did indicate,
not surprisingly, that the rate of graphitization of the dia-
mond surface increased with both incident energy and substrate
temperature. The main deficiencies of the Stillinger-Weber po-
tential with respect to carbon are its inability to effectively
model Jr orbital interactions and the absence of a four-body
term resulting in potentially unphysical dihedral angles. How-
ever, this is generally true of all empirical potentials for carbon.
3.2.1.3. Tersoff Potential
The Tersoff potential, also constructed to model silicon atomic
networks which depart significantly from ideal tetrahedral ge-
ometries, attempts to solve the problem of simulating such
systems with a more general approach than that adopted by
Stillinger and Weber. Instead of considering interactions be-
tween atoms in the system in terms of one- to n-body interac-
tions, Tersoff [ 138, 139] began from the observation that, from
simple quantum mechanical arguments, the most important in-
fluence on the strength of bonding between pairs of atoms is the
coordination number--the number of neighboring atoms which
are close enough to form bonds--of both atoms. In general,
the fewer atoms any given atom is bonded to, the stronger the
bonds between those atoms--for example, the strength of in-
dividual bonds between trigonally bonded carbon atoms within
a graphite plane is in fact greater than that between tetrahe-
drally bonded carbon atoms in diamond (the difference in bulk
hardness being explained by the very weak zr-bonding between
planes). In the Tersoff potential then, the concept of b o n d or-
der is introduced, and total potential energy of the system U is
expressed only as the sum of pairwise potentials of each atom
with every other atom in the system by
1 induced by thermal energy spikes caused by ion impacts, an-
U =~ y ~ Vij (3.13)
i, j:~i
Vij -- fcutoff(rij)[aij frepulsive(rij)+ bij fattractive(rij)] (3.14)
where fcutoff(rij) is a smooth cutoff function to limit the range
of the potential for computational convenience, frepulsive(rij)
represents the simple repulsive term between two atoms which
includes the orthogonalization energy when atomic wavefunc-
tions overlap (chosen to be a simple exponential of the form
f r e p u l s i v e ( r ) - - A exp(-Xlr)), and fattractive(rij) is the attrac-
tive term that represents bonding (also chosen to be a simple
exponential of the form f a t t r a c t i v e ( r ) = - B exp(-~2r)), the co-
e f f i c i e n t aij is approximated in most cases to unity, and bij is an
implicit measure of the b o n d order, which is dependent on the
local environment and is a monotonically decreasing function
of the coordination of atoms i and j, the strength of competing
bonds, and the cosines of the angles with competing bonds. Fur-
ther details of the form and nature of this potential with respect
to amorphous silicon can be found in [ 138, 139].
The original intent in implementing the Tersoff potential was
to attempt to make fewer assumptions about the specific nature
of local bonding geometries and thereby be potentially more
flexible in its ability to model undercoordinated forms of cova-
lently bonded solids such as amorphous silicon and amorphous
carbon. Specifically, it was felt that previous approaches artifi-
cially imposed a higher degree of coordination and arbitrarily
excluded lower coordinated structures from the resulting mod-
els. The first attempts to use it to model amorphous carbon
networks were made by Tersoff [ 140, 141] which yielded rea-
sonable agreement with respect to experimentally determined
elastic constants. However, they resulted in structures of sig-
nificantly higher density for their s p 2 bonding content than
experiment. In the latter paper [141]nin which the role of
hydrogen in relieving strain in hydrogenated amorphous car-
bon was investigatedmsp 3 bonding in pure carbon networks
appears to be so unfavored by the Tersoff potential as to be
unphysical, which suggests that in trying to allow for underco-
ordinated structures, in amorphous materials it has gone too far
in the other direction. As in the case of the Stillinger-Weber po-
tential, it seems that a neglect of zr bonding and an inadequate
account of modelling the dihedral angle in carbon are the main
sources of difficulty. The principal effect of this, as pointed out
by Stephan and Haase [142], is that in the absence of a signifi-
cant repulsive term for rr bonded atoms, an artificial excess of
s p 2 bonding is allowed at high densities.
With this in mind, useful insights have been gained from
simulations of amorphous carbon using the Tersoff potential.
Ion beam growth of thin amorphous carbon films onto a crys-
talline diamond substrate at differing incident energies was
simulated by Kaukonen and Nieminen [ 143]. While the density
of their simulated films was higher and the s p 3 fraction lower
than experimental results, they did reproduce the finding that
maximums in density and s p 3 fraction occur with respect to ion
energy at around 40-70 eV. They found that the formation of
tetrahedral bonding results from competing effects of defects
nealing of these defects at higher energies, and the high thermal
 AMORPHOUS CARBON THIN FILMS
conductivity of the diamond substrate preventing such anneal-
ing.
The largest body of work on the modelling of amorphous
carbon using the Tersoff potential has been conducted by Ke-
lires [144-146] and is reviewed in [95]. Amorphous carbon
networks of various densities were generated by starting with
between 216 and 550 atoms in a well equilibrated liquid state
at approximately 9000 K which were then rapidly quenched
to room temperature. While it is accepted that such a process
does not directly mimic the thin film deposition process, it does
produce stable structures which are believed to bear some re-
semblance to those in amorphous carbon films and so for its
computational convenience is widely used (and used exclu-
sively in tight-binding and ab initio approaches) throughout the
literature. In investigating the structural stability of TAC, Ke-
lires found his simulated networks were thermally stable up to
a temperature of around 1200 K at which point they underwent
a transition to a dense sp2-rich phase, consistent with annealing
experiments. Decomposition of the local bond stress found an
inhomogeneous stress distribution between sp 2 and sp 3 bonded
atoms, with sp 2 sites found mainly in tension and sp 3 sites
found mainly in compression. This demonstrates the role that
sp 2 sites may play in relieving the internal strain in the network,
similar to the role of hydrogen found by Tersoff in a-C:H [ 141 ].
3.2.2. Tight-Binding Approaches
The next level of sophistication in modelling of amorphous ma-
terials employs an approach known as the tight-binding method
and attempts to reach a compromise between the rigor of a com-
putationally expensive ab initio quantum mechanical treatment
and the limitations of a completely empirical approach. The
term "tight-binding" covers a variety of approaches within fun-
damental electronic-structure theory which approximate a fully
ab initio treatment by constraining the expansion of electron
wavefunctions in the system to a basis set of atomiclike orbitals
of the valence electrons only.
Following the treatment given by Frauenheim et al. [84]
the initial step in the procedure is the quantum mechani-
cal self-consistent determination of the effective one-electron
potentials and corresponding wavefunctions using density-
functional (DF) theory [147] within the local density approx-
imation (LDA). These single-atom valence electron wavefunc-
tions r (r) are thereby used in the expansion of the electron
wavefunction for all atoms at positions Rt by
1/ri (r) = E cixq~ix
i (r- RI) (3.15)
Ix
i are evaluated by diagonalization of the sec-
The coefficients c Ix
ular matrix
i
E(hixv - ~iS~v) =0 (3.16)
Ix
where hixu is the tight-binding Hamiltonian which introduces
the contributions to the effective one-particle potential (which
427
includes the electron-electron (Hartree) term and exchange-
correlation term within the LDA), and Sixv is the overlap matrix
to correct for the nonorthogonality of the basis functions at dif-
ferent atom sites, to yield orbital energies Ei and corresponding
eigenfunctions. Then, in its simplest form, tight-binding ex-
presses the total energy in the form
Utotal = Ubinding({R/}) -+- Urepulsive({R/ - Rk})
: E i n i ~ i ( { R l } ) -~- E l , k>l Vrepulsive({Rl - Rk})
(3.17)
where ni is the occupation number of orbital energy ei. The
first term in (3.17) represents the binding or "band structure"
energy, which includes the self-consistent LDA calculation of
the single-atom valence electron orbitals. The second term in
(3.17) represents the shortrange repulsive energy, which is gen-
erally modelled by an empirical short-range two-body potential
Vrepulsive, because of the computational expense of inclusion
of the extended basis required to make an accurate quantum-
mechanical calculation of this term. In sophisticated treatments
Vrepulsive is chosen so that the potential energy curves of the
bonded atomic pairs within the system reproduce those evalu-
ated separately with a full LDA calculation.
Once an expression for the total energy of the system as
a function of all atomic coordinates is found, the interatomic
forces can be found from the gradients of this total energy at all
atom sites. Frauenheim [84] uses the expression
. 0 Utotal
. . E n i. E E i i l . O h i x v [- 6 i OSixvJ
FI ORl i Ix v cixcv ORI ORi
_ 0 Urepulsive (3.18)
ORI
for calculating the force on atom I and position RI.
In the most extensive body of work of carbon using tight-
binding Frauenheim et al. [38, 84, 148] have modelled a variety
of pure and hydrogenated carbon networks with densities of be-
tween 2.0 and 3.5 g cm -3 by the rapid quenching of carbon
atoms from a liquid state at approximately 8000 K. Systems
sizes of 64 carbon atoms [84] and 128 carbon atoms, in addition
to various numbers of hydrogen atoms, give structures of vary-
ing hydrogen content. As with many other simulation schemes,
when compared with experimental results, the resulting films
exhibited either lower sp 3 fractions at similar densities, or
higher densities at similar sp 3 fractions with a discrepancy of
around 1.2-1.5 times that of experimentally determined den-
sities. It is probably that at least some of this may be due to
an underestimation of the experimental density as a result of
either the inclusion of lower density macroparticles during de-
position, or other medium range density fluctuations larger than
the size of the simulated supercell. The trends, however, are
consistent with experiment demonstrating increasing sp 3 bond-
ing with increasing density for networks of constant hydrogen
content (including pure films) and increasing hydrogen content
for networks of fixed density (with the exception of the highest
density sample which showed a slight initial decrease hydrogen
incorporation). The reduced radial distribution functions (G(r))
428 SILVA ET AL.

. . . . ' . . . . ' . . . . ' . . . . ' . . . . ' . . . . . ' . . . . ' . . . . ' 1

Frauenheim et al. /~.

lit
~cm 3
TACC33~'r r, ~,~ /'
r.-

ri , .
A
r
..Q
t._ 0/cm3
r v
r

g/cm3

o
v
el)
r
v
C9 "o g/cm3
O

Frauenheim et al. /X =o
- -O-H /.;\ cm') -

uJ
g/cm 3
-

i~ "% - - . . = . . . . = . . " ' P " """.., g/cm 3

[ . . . . t .... t .... a-Ci:H ,(ace,tyl:ne?

0 0.1 0.2 0.3 0.4 -30 -25 -20 -15 -10 EF 0 5 10

r(nm) Ene rgy (eV)

Fig. 26. Reduced radial density functions from various simulated carbon net- Fig. 27. Electronic density of states for hydrogen-free amorphous carbon
works from Frauenheim et al. [84] compared with equivalent experimental structures at various macroscopic densities between 2.0 and 3.3 g cm - 3 from
results of Waiters et al. [83], Li and Lannin [118] (taken from Frauenheim et al. Frauenheim et al. [84].
[84]), and Gilkes et al. [119].

from 2.0 g cm -3, which then widened again up to the maximum

for various characteristic networks are shown in Figure 26 along
with equivalent experimentally obtained G(r)'s from elsewhere
in the literature for comparison.
In the highest density networks, most analogous to ion
beam deposited TAC, analysis of the three-dimensional bond-
ing topologies generally shows s p 2 bonded atoms in isolation or
in pairs within an s p 3 bonded matrix with no extended aromatic
ring structures present9 At higher hydrogen contents and lower
densities the structure increasingly becomes one of clusters
of s p 3 bonded regions interconnected by s p 2 onded chainlike
segments. In the lowest density networks containing interme-
diate concentrations of hydrogen (~20 at.%), most analogous
to plasma-enhanced CVD grown a-C:H, the network is dom-
inated by a Jr bonded network of principally s p 2 hybridized
atoms, with a small fraction of s p 1 and s p 3 bonding homoge-
neously distributed in chainlike segments. Consistent with the
experimental neutron diffraction results of Waiters et al. [83]
(see Section 3.1.2), s p 2 bonding in these films also exhibits very
little aromatic nature. Increasing the incorporation of hydrogen
in these films removes all s p ] bonding in favor of both s p 2 and
s p 3 bonding.
It is generally accepted that the electronic properties of
amorphous carbon films are dominated by contributions to the
electronic density of states (EDOS) by Jr bonding states asso-
ciated with s p 2 hybridized atoms within the material, which is
confirmed in an analysis of the EDOS of all networks simulated
by Frauenheim et al. [84]. An initial narrowing of the bandgap
of their pure carbon networks occurred with increasing density
simulated density of 3.3 g cm -3 (see Fig. 27). In a subsequent
work from the same group Stephan et al. [ 149] found that the
EDOS is sensitive to the size and topology of Jr bonded clusters,
with s p e atom pairs resulting in the widest bandgaps of around
3 eV. With the incorporation of hydrogen into these highest den-
sity networks an additional study found that reductions in the
strain on Jr bonding resulted in the opening of an even greater
bandgap of 3.3 eV [ 148].
A approach similar to that of Frauenheim et al. has been
carried out by Wang et al. following a tight-binding treatment
developed for carbon by Xu et al. [ 150]. Both unhydrogenated
low density (2.2 g cm -3) carbon networks analogous to sput-
tered a-C [39, 87] and high density (3.5 g cm -3) carbon
networks analogous to ion beam TAC [39, 151 ] were simulated.
The structure factor S(Q) of the low density model gives a
good fit to the experimental S ( Q ) obtained by Li and Lannin
[118] from sputtered a-C using neutron diffraction. The s p 1,
s p e, and s p 3 fractions in this model were 12%, 80.6%, and
7.4%, respectively, and its electronic properties were consis-
tent with experimental observation of a small mobility gap of
around 0.5 eV opening up between zr states in a-C.
With respect to their high density carbon network [39, 151 ],
as in the work by Frauenheim et al. [38, 84, 148], while a s p 3
fraction of around 80% is consistent with experiment, its den-
sity of 3.5 g cm -3 is again somewhat higher than expected.
Similarly the peak corresponding to the second coordination
sphere in the calculated reduced radial distribution function (see
Fig. 28) is markedly higher than that determined by experiment.
 AMORPHOUS CARBON THIN FILMS 429
. . . . i . . . . ! . . . . i . . . . i . . . . ! . . . . ! . . . .

mechanical molecular dynamics algorithm developed by Car

A.~......_ Wang et al. and Parrinello [153]. Car-Parrinello molecular dynamics
//~\ TAC (3.5 g/cms)
(CPMD) is based on the unification of classical molecular dy-
li"..Al~ o , k , , , , =. namics used to describe the motion of atoms under the influence
of a given potential, with the DF theory of Kohn and Sham
I: l ,.t,"''~ [147] which allows the accurate determination of electronic
properties of an atomic network, with no prior assumptions
about the interaction potentials and without constraining the
description of the electron wavefunctions to a reduced basis
_
set of atomlike orbitals (as in tight-binding approaches). As
a consequence of the generality of this approach it is ideally
i i , , i . . . . i . . . . i . . . . i . . . . i . . . . i . . . .

0.05 O.1 O.15 0.2 0.25 0.3 0.35 0.4 suited (given enough computational power) to dealing with in-
r (nrn) teractions between carbon atoms in different and intermediate
hybridization states (such as sp2-sp 2, sp3-sp 3, and sp2-sp 3
Fig. 28. Reduced radial density function of 3.5 g cm - 3 simulated carbon net-
work from Wang et al. [151] compared to that obtained for TAC by neutron bonded atom interactions) and therefore to amorphous carbon
diffraction from Gilkes et al. [ 119]. systems.
Applied to carbon the Car-Parrinello method treats the
A more sophisticated technique developed by Sankey and atoms as positively charged cores (described by an appropriate
Niklewski [152], which uses an extended atomic orbital basis pseudo-potential), each surrounded by four valence electrons.
set and avoids the need for an empirically fitted repulsive term The total electron density is expressed in terms of occupied or-
(Vrepulsive({R/ - R k } ) in (3.17)), has been applied in a study of thonormal Kohn-Sham (KS) orbitals by
the structural, electronic, and vibration properties of TAC by
Drabold et al. [85]. At a density of 3.0 g cm -3 (cf. 2.9 g cm -3 n(r) -- Z I~i(r)[2 (3.19)
obtained experimentally) the 64-atom network they simulated i
had an sp 3 fraction of 91%, which sets it apart from most other i
whose wavefunctions ~i(r) (= Y~kCkXk) are expressed in
models in that it is simultaneously the highest sp 3 fraction of
terms of an expansion in terms of a large basis of plane waves
any simulated amorphous carbon system and one of the lowest
X1 . . . . . Xm. For a given static atomic configuration the ground
simulated densities for a predominantly tetrahedrally bonded
electronic state is given by a point on the Born-Oppenheimer
network.
(BO) surface which is found by minimization of the energy
In this work they identify three types of defects of im-
portance to the electronic structure of TACm(i) Jr defects functional
consisting of predominantly paired sp 3 bonded atoms, (ii)
strain defects consisting of fourfold coordinated atom bond
E({~i}, {R,}, {c~v}) -- Z f. ~ * ( r ) l - [ h 2 / Z m ] V 2 l ~ / i ( r ) d r
l

angles well in excess (> 150 ~ of the ideal tetrahedral angle

+ U(n(r), {Rt}, {otv}) (3.20)
(> 109.47 ~ which in amorphous silicon are known to con-
tribute to localized electronic states within the mobility gap, where {Rt } is the set of atomic coordinates, {otv} is the set of all
and (iii) stretched bond defects consisting of fourfold coordi- possible external constraints such as volume f2, strain, etc., and
nated atoms with bond lengths in excess of 0.173 nm. The the potential U (n(r), {Rt }, {otv}) includes the Coulombic repul-
most important of these is the zr defect which is the principal sion between ion cores, the electron-ion interaction, the Hartree
structural difference between carbon and silicon bonding, and electron-electron interaction, and the exchange and correlation
whose propensity to form pairs, identified throughout the litera- interaction treated in the LDA.
ture, has significant implications with respect to the localization Conventionally, minimization of Eq. (3.20) subject to or-
of associated electronic states, electronic conduction, and its
thonormality of the orbitals ~r i leads to the self-consistent
contribution (or lack thereof) to the electron paramagnetic res-
Kohn-Sham equations
onance signal of TAC. However, in simulations of systems in
the order of 100 atoms it is perhaps not surprising that isolated
- h2 V 2 + Oi (r) - ei Oi (r) (3.21)
sp 2 bonded atoms are rarely seen, as the presence of just one 2m On(r)
such atom in 100 would suggest defect densities well in excess
of the ~ 10 20 spin cm -3 calculated from EPR measurements whose solution requires repeated matrix diagonalization until
[ 109, 110] (see Section 5). self-consistency is achieved, the computational effort of which
increases dramatically with system size and basis set. In prin-
ciple this calculation must be executed for each and every new
3.2.3. Ab Initio Molecular Dynamics atomic configuration, i.e., at every time step if the ion cores
At the top of the spectrum of computer modelling approaches are to be allowed to move toward a structural minimum, which
for both physical sophistication (in terms of interatomic po- makes any straightforward implementation of it into a conven-
tentials) and computational intensity is the ab initio quantum- tional molecular dynamics scheme computationally prohibitive
430 SILVA ET AL.
for any but the smallest systems. Furthermore, no such calcu-
lation can ever be completely self-consistent, which results in
errors that give rise uncontrollable energy losses or gains within
a system causing problems with stability [154]. However, the
Car-Parrinello technique overcomes both these difficulties by
approaching the specific problem of minimization of Eq. (3.20)
by applying a variation on the concept of simulated annealing
[155].
In conventional simulated annealing, a given functional,
such as that in Eq. (3.20), is minimized with respect to a set
of n free parameters which form an n-dimensional coordinate
hyperspace by searching through that hyperspace randomly via
a Monte Carlo algorithm, reducing the search radius as conver-
gence is approached, in a manner analogous to the way in which
the molecules of a liquid (their coordinates being analogous
to the free parameters of the coordinate hyperspace) find their
minimum (crystallize) as it is cooled. However, owing to the
orthonormality constraint on the KS orbitals l/ri, implementa-
tion of such minimization by random Monte Carlo means is not
straightforward. Instead, the Car-Parrinello technique imple-
ments dynamic simulated annealing of the coordinate system
by approaching it as a dynamic system and treating the varia-
tion of the free parameters of the system in the same way as
motion of atomic coordinates in classical molecular dynamics.
This is achieved by introducing the Lagrangian
t : E2" 1
i
fo [~ri d r + E 2 1MIll 2
l
1 cell at a constant density of 2.0 g cm -3 in a liquid state from a
-+- E 2/zv~2 -- E({Ipi}, {RI}, {O~v}) (3.22)
P
where ~i, R,l, and &v are the time derivatives of the KS orbital,
ionic position, and external constraint coordinates, respectively,
Ml are the ionic masses, and/z and #v are arbitrary "masslike"
parameters of appropriate units. From the dynamics of the
coordinate-space (i.e., the simulated annealing hyperspace), pa-
rameters {1/Zi }, {R/}, and {c~u} can then be described through the
equations of motion
/z~)/(r, t) - 0 E / 0 O * ( r , t) + E AikOk(r, t) (3.23)
k putational power which, it has been argued, in turn limits the
oo
MtRt -- --VRt E (3.24)
lzvrtv = -(O E/Oc~v) (3.25)
where Aik are Lagrange multipliers introduced to ensure or-
thonormality of the KS orbitals. The physical significance of
the ion dynamics described by Eq. (3.24) is real, relating the
positions and velocities of ion centers, whereas the dynam-
ics associated with Eqs. (3.23) and (3.25) are mathematical
constructs introduced to perform the dynamical simulated an-
nealing.
The important and innovative aspect of this approach is that
the solution of Eqs. (3.23)-(3.25) allows the calculation and re-
laxation of the evolving electronic structure (embodied in the
electron density distribution n(r)) and relaxation of the phys-
ical structure (through the molecular dynamics embodied in
the evolving positions of the ion centers {RI }) to be achieved
simultaneously. Not only does Car and Parl'inello's dynamic
simulated annealing provide an efficient means of determining
the electronic configuration of a system (i.e., its ground state on
the BO surface) which then generates the forces which cause
the ion cores to move, but it also tracks the electronic coeffi-
cients in such a way that it updates the total wavefunction to the
BO surface corresponding to the new ionic configuration with
each time step (provided that time step is sufficiently short).
Furthermore, oscillation of the electronic coordinates within
a narrow "envelope" in coordination-space (mediated by the
small "fictitious temperature" associated with dynamics of the
electronic orbitals embodied in Eq. (3.23)) close to the BO sur-
face surprisingly results in negligible net energy accumulation
or loss, to or from the system [ 154].
While CPMD implements the most accurate and general de-
scription of the molecular dynamics of small systems of around
100 atoms over real time periods of the order of picoseconds,
it has been argued that the computational difficulty of ensur-
ing the attainment of equilibrium by running for longer time
periods, of achieving better statistics by repeating simulations
more than a few times, limits the physical significance of any
conclusions drawn from its results. However, with this caveat
in mind, the generality of the method does allow for the poten-
tial of providing insights particularly into the applicability of
various assumptions made by other simulation techniques.
The first application of the CPMD method to amorphous car-
bon was conducted by Galli et al. [80] by quenching a 54-atom
temperature of 5000 K down to 300 K over a period of 0.5 ps,
which was then allowed to equilibrate for a further 0.3 ps.
Two simulations where undertaken with different size basis sets
for describing the KS orbitals with the greater using a set of
12,000 plane waves. A significant overestimation (~6%) of the
bond lengths was observed in the structure modelled using the
smaller basis, and a smaller though noticeable overestimation
(~3%) in the G(r) in comparison to both the experimental re-
suits of Li and Lannin and tight-binding results of Frauenheim
et al. [84] when using the greater basis set was observed. Use
of a larger basis is obviously limited by the available com-
applicability and potential generality of the Car-Parrinello ap-
proach to real systems. However, with the exponential increase
in available computational power over the last decade, and with
the obvious caveats in mind, this has become a less and less
applicable objection to the technique.
Using CPMD code developed and maintained by the Par-
rinello laboratory at the Max Planck Institut fur Festktirper-
forschung, Stuttgart, this technique was applied by Marks et al.
[ 156, 157], with 64 carbon atoms and a greater plane wave basis
set than that used by Galli to the simulation of TAC. Similarly
to Galli, the system was first heated to 5000 K, allowed to equi-
librate for 0.36 ps, cooled to 300 K over a period of 0.5 ps,
and allowed to equilibrate for a further 0.5 ps. The volume
of the system was constrained to give a density of 3 g cm -3.
In contrast to the formation mechanisms of low density amor-
 AMORPHOUS CARBON THIN H L M S 431
. . . . ! . . . . i . . . . i . . . . ! . . . .

phous carbon films, this simulated formation regime may not Marks et al.

be entirely removed from the physical mechanism by which _

TAC may be formed (apart from the important absence of the ." " < ~ T A C (2.9 g/cm s) _
simulation of actual atomic impacts into a surface). In a sep-
arate paper Marks presents an analytical model based on the
"thermal spike" theory of TAC formation (see Section 2.2.2) in
addition to evidence from empirical molecular dynamics and
'.,. "'-.,
CPMD simulations, along with the invariance of sp 3 fraction
with various long quench times in tight-binding simulations,
which suggest that subpicosecond cooling times from 5000 K
_

to room temperature are not necessarily unphysical. , , i , I i , i i I , , , , I , i , , 1 . . . . I . . . . I . . . .

The sp 3 fraction in the resulting network was found to be 0.05 O.1 O.15 0.2 0.25 0.3 0.35 0.4
65 %, lower than that found experimentally and similar to those r(nm)
found in other simulations carried out at the same density Fig. 29. Reduced radial density function of 3.0 g cm - 3 simulated carbon net-
(with the exception of Drabold et al. [85]). The most surpris- work from Marks et al. [ 156] compared to that obtained for TAC by neutron
ing result of this work was the appearance of both three- and diffraction from Gilkes et al. [119].
four-membered rings (three occurrences of each in the 64-atom
simulation), long thought to be energetically unfeasible in bulk
amorphous carbon films (it is an interesting historical point
0O
to note that TAC itself was also thought to be too energeti- 13 13"
cally unfeasible to exist [158]). It has been argued [38] that
the three- and four-membered rings present in these simulations O . - ~ _

~g
are simply minor statistical artifacts of the individual simulation f/)

Q
runs themselves, with little net contribution to the topology of
o'~
TAC as a whole. However, a detailed comparison of the results
ov
with the unresolved issue of the surprisingly low coordination
number calculated from neutron diffraction for a predominantly m

w
tetrahedrally bonded matrix suggests the occurrence and impact
of these structures are perhaps more significant. i i . . . . i . . . . i . . . . 1 . . . . i . . . . i . . . . 1 . . . .

As presented in Section 3.1.2, analysis of the experimentally -20 -15 -10 -5 0 5 10 5

obtained reduced radial distribution function from TAC sug-
gests a coordination number of around 8-9, significantly less
than the expected value of just less than 12 for a material with
up to 90% fourfold sp 3 bonding. In an attempt to resolve this
discrepancy Gilkes et al. [ 119] suggested an asymmetric second
neighbor distribution with the peak at 0.275 nm in the G(r) con-
sisting mainly of contributions by second neighbors. However,
in their simulations Marks et al. found that by decomposing
their results into pair distribution functions for first and sec-
ond neighbor bond lengths the second neighbor peak is in fact
symmetric, though broader than expected, and that therefore the
asymmetry in the G(r) is in fact entirely due to contributions
by third nearest neighbors. Furthermore, the very presence of
three- and four-membered rings in the network effectively re-
duces the total number of second nearest neighbors with respect
to first nearest neighbors as the low second neighbor coordina-
tion indicates. In a three-member ring the second neighbor in
one direction around the ring is in fact a first neighbor in the
other, and in a four-membered ring the second neighbor in both
directions contributes only one atom to the distribution instead
of two. As further evidence of the presence of four-membered
rings they point out that the peak at 0.215 nm identified in the
G(r) by Gilkes et al. can only conceivably be generated by
the diagonal distance across a quadrilateral. The unexpected
appearance of three- and four-membered rings underlines the
importance of the generality of the CPMD approach in its po-
Energy (eV)
Fig. 30. The electronic density of states of 3.0 g cm - 3 simulated carbon net-
work from Marks et al. [ 156].
tential to provide insights that are less constrained by prior
assumptions about the expected structure of a given atomic net-
work.
Comparison of the G(r) obtained in this work with that ob-
tained by Gilkes et al. is shown in Figure 29. Apart from the
agreement in both position and shape of the first two coordi-
nation peaks, the relative height of the two peaks is arguably
better reproduced than any other simulated G(r) in the litera-
ture at the time. Specifically, the tight-binding simulations of
both Wang and Ho [151] and Frauenheim et al. [84] resulted in
second neighbor peaks which were greater than the first neigh-
bor peaks in contrast to that found from the experimental G(r)
for TAC and that found by Marks.
With respect to the nature of sp 2 sites, this work confirms the
tendency for clustering found in other works including Frauen-
heim et al. [84, 148] and Drabold et al. [85], as well as their
olefinic or chainlike nature. It also confirms the absence of iso-
lated sp 2 sites, and their overwhelming tendency to form pairs.
As pointed out by Drabold this pairing is consistent with EPR
results which would make the occurrence of isolated sites un-
likely in such small systems.
432
. . . . i . . . . i . .
McCulloch et al.
= -. / / I 1
A Li and Lannin
McCulloch et al. tl ~
a-C (2 0 g/crn 3) i |
" I
0 0.1 0.2
r (nm)
Fig. 31. Reduced radial density functions from various simulated carbon net-
works from McCulloch et al. [159], compared with equivalent experimental
results of Li and Lannin [ 118] (taken from Frauenheim et al. [84]), and Gilkes
etal. [119].
The electronic density of states of the structure is shown in
Figure 30. It is difficult to infer too much from the electronic
results of such a small system, or to determine the resultant
mobility gap when the states at no point in an amorphous
semiconductor go exactly to zero. Therefore, in order to relate
the EDOS to a measurable quantity in TAC which reflects the
EDOS, the Tauc gap (see Section 4.1) was calculated from a
convolution of occupied and unoccupied states in this distri-
bution, and using the assumption that the matrix elements for
dipole transitions are independent of energy. This resulted in a
Tauc gap of 0.5 eV, significantly lower than the measured value
of around 2-2.5 eV in TAC, almost certainly due to the size
of the system, and possibly also due somewhat to the over-
representation of low-membered ring structures (as suggested
by Frauenheim et al.).
Work by McCulloch et al. [159] has extended the work of
Marks et al. with almost twice the number of atoms (125 carbon
atoms), an even greater plane wave basis set, and the simu-
lation of systems at a range of densities at 2.0, 2.6, 2.9, and
3.2 g cm -3. Figure 31 shows the resultant reduced radial den-
sity functions at each of these densities compared to equivalent
experimental results.
In the 2.0 g cm -3 network s p 2 bonding was found to pre-
dominate in layered regions bounded by s p 3 bonded atoms,
indicated by the presence of a graphitic (002) reflection in the
calculated reduced diffraction intensity. A significant amount of
s p 1 bonding (15%) was also found, similar to the tight-binding
results of Wang et al. [87] and Stephan et al. [149].
SILVA ET AL.
. . 1 . . . .
With respect to the high density networks, the best fit to the
G ( r ) data of Gilkes et al. is obtained from the 2.9 g cm -3 net-
i\ work with an s p 3 fraction of 57.6%, rather than the 3.2 g cm -3
!/'~', t
network with an s p 3 fraction of 79.2%, closer to that found
experimentally. This is attributed to the inclusion of signifi-
cant amounts of sp2-rich carbon in experimental samples (in
part due to the insufficient filtering of macroparticles during
deposition) during the collection of the large amount material
required to carry out both an accurate measurement of density
% and the collection of neutron diffraction data. This argument
could equally explain similar discrepancies found throughout
the literature on the modelling of TAC and suggests that diffrac-
tion data will be best reproduced by simulated films with a
density of up to 3.0 g cm -3, but that high s p 3 fractions will
be better reproduced at densities in excess of this.
In comparing the ring statistics of the 2.9 g cm -3 model
/ .
/ ~~ a-C (2.0 g/cm") to those of the TAC network simulated by Marks et al. the
_
number of three-membered rings remains constant (at a total
of three) even though the number of atoms in the system was
doubled, while the number of four-membered tings was more
0.3 0.4
consistent in that it exactly doubled (from three to six). This
perhaps justifies the caution about the statistical significance of
such structures raised by Frauenheim et al. [38] with respect
to three-membered rings, though probably less so with respect
to four-membered rings given the appearance (as mentioned
above) of a peak corresponding to the quadrilateral diagonal
distance at 0.215 nm in the neutron diffraction data.
4. O P T I C A L P R O P E R T I E S
4.1. Introduction
The optical properties of amorphous semiconductors are usu-
ally discussed in terms of a breakdown of the k conservation
number with a loss of distinction between direct and indirect
transitions. Band-to-band optical transitions are conventionally
discussed in terms of a transition between the valence and con-
duction band, the strength of which is determined by the matrix
elements. In this manner information with regard to the band
tails and optical constants can be obtained. The refractive in-
dex n and absorption coefficient a can be related to the real, el,
and imaginary, e2, parts of the dielectric constant. In the one-
electron approximation E2 takes the form [160]
- V-2[ 27t"
2 wem_1
] 3-'11 ...,,(flPli),eS[Ef - Ei- ~/Lo] (4.1)
i f
where V is the sample volume, P is the momentum opera-
tor, and the summations are over the initial states Ii) and final
states If). For transitions between extended states (i.e., those
that are delocalized), the matrix element evaluates to a3/192 v
with Pcv ~ h / a . Equation (4.1) then can be expressed as
-- a3p2 v gVB(--E)gcB(hW- E)dw
ogm .j
(4.2)
 AMORPHOUS CARBON THIN FILMS 433

I [ i
2.5 ruled by the sp 2 content and was first examined in the cluster
~7 a-C:H
V 9 TAC:H model.
V O TAG The optical gap can be varied by changing the deposition
conditions (e.g., self-bias in PECVD systems, C + ion energy in
2.0 -- 0 FCVA systems), by addition of N, or through annealing. Exam-
> 0 V 9
v
ples of the Tauc and E04 gaps as function of different deposition
C2.
m V V conditions will be presented later in this section and also in con-
O
V junction with the electrical properties of a-C films.
W 1.5 O V
V
V E
4.1.1. Optical Gap a n d Density o f States
O
V
1.0 -- V OE EV -- In 1997 Robertson and O'Reilly [78] proposed that the bandgap
I l I i I i I in amorphous carbon could be related to the size of the sp 2
0.2 0.4 0.6 0.8 clusters. They found that the most stable arrangement of sp 2
sites is in compact clusters of fused sixfold rings. For M six-
sp 2 content
fold rings the bandgap could be expressed as Eg -- 6 / M 1/2 eV.
Fig. 32. Variation of the E04 gap with sp 2 content for DAC, hydrogenated, However, a number of deficiencies with this model became ap-
and nonhydrogenated TAC films. Adapted from Robertson [242] and references parent. First, the size of the clusters required to explain the
therein.
observed bandgaps would have to be so large that they should
be readily observable by electron diffraction studies--which to
From Eq. (4.2) it is evident that E2 is a function of the joint date they have not been. For example, a bandgap of 1.2 eV in
density of states of the respective bands and will therefore de- DAC would require a 25-ring cluster of approximately 1.2 nm
pend on the shape of the bands. Furthermore, the absorption in diameter. Such a well organized structure is unlikely to
coefficient ct is related to E2 via occur, especially in highly disordered DAC. In addition five-
and seven-membered rings have been observed in the neutron
09E2 (0))
ct (co) = (4.3) diffraction of a-C [ 118]. In light of these experimental facts,
nc
Robertson revised his earlier model so that distorted clusters
where n is the refractive index of the material. Equations (4.2) now play a more dominant role [79]. Various possible distor-
and (4.3) indicate that the absorption coefficient will depend tions of a sixfold ring were considered (cf. Fig. 12). In the case
upon the convolution of the density of states of the conduction of the "chair" configuration a significant narrowing of the gap
and valence bands. To a first order the density of states can be occurred. Furthermore, the gap was no longer symmetric about
expressed as a power law taking the general form
the midpoint as it was for planar sixfold rings. A fully dis-
gVB (-- E) cx E p and gcB(E) cx ( E - ET) q (4.4) torted sixfold ring in the chair configuration gives a bandgap
of 1.16 eV. On this basis it was proposed that the bandgap of
where ET can be regarded as a measure of the separation be-
1.5 eV could be formed by the partial deformation of a pla-
tween the two bands. Inserting Eq. (4.4) into Eq. (4.2) results
nar sixfold ring. In the case of odd numbered rings, especially
in
five- and sevenfold, it was noted in [78] that these would give
O92~2(O9) (X ( ~ _ O - ET) p+q+l (4.5) rise to states near the Fermi level and would be singly occu-
pied. In this way they would be paramagnetic. By considering
For the case of parabolic bands p = q -- 1/2, and Eq. (4.5)
negatively charged fivefold rings and positively charged seven-
results in the well known Tauc energy gap relation
fold rings together Robertson proposed that such a combination
c~ho9 = B ( h o 9 - ET) 2 (4.6) would produce a bandgap of about 3 eV. However, if such a two-
A plot of ( ~ ) 1 / 2 against ho9 has an intercept which gives ring configuration could become distorted it would produce a
ET, the Tauc gap, and the parameter B, which has units of bandgap of 0.8 eV.
cm -1 eV -1. The Tauc gap ET is therefore an extrapolation of In the original model of the DOS from Dasgupta et al. [ 160]
the density of states (for parabolic bands). In addition to the the DOS consisted of a pair of symmetric bands, each with
Tauc gap, the energy at which the absorption reaches certain Gaussian shape and width. These distributions were symmetric
values, most commonly 103 and 104 cm -1 , is often quoted. The and were separated by about 4 eV, corresponding to the separa-
energy gaps are usually referred to as the E03 and E04 gaps, re- tion of sixfold rings put forward by the cluster model together
spectively. The variation of the E04 gap on sp 2 content for DAC with another pair of bands 0.3 eV above and below EF due to
and hydrogenated and nonhydrogenated TAC is shown in Fig- five- and sevenfold rings. Dasgupta et al. originally proposed
ure 32. The E04 gap clearly depends on the sp 2 content with that the former states were responsible for the optical absorp-
a clear trend of a decrease in the E04 gap as the sp 2 fraction tion, whereas the latter were responsible for the observation of
increases. This leads us to the conclusion that the optical gap is EPR signal.
434
I J I I I i I gies above 2 eV. By considering many body effects within the
2 ~
O4
1 D
ot
i I i I i I
1 2 3 4
Energy (eV)
Fig. 33. Fits to the imaginary part ~2 of the dielectric constant for sp 2 and
sp3-rich assuming a symmetric Gaussian model for the DOS as proposed in
[160] (dashed) and the asymmetricband model (solid) of[161].
This model in which the shape of the bands could be mod-
elled as a Gaussian with a particular energy position and width
led to a number of consequences"
(i) There is no difference in the origin of the states sitting
above or below the optical band edges.
(ii) There is no connection to the mobility gap and the
degree of localization is related to the number of states
at a particular energy.
(iii) Following from (ii), it is Still possible for both the 7r
and zr* states to be completely localized and still
obtain a Tauc energy gap. This point is important since
MD calculations reveal that even with s p 2 contents
above 92% the zr states are localized.
(iv) The value of the optical gap should be regarded purely
as a method of characterizing the film and values such
as E04, etc., do not necessarily have any significance.
(v) Since the optical gap is controlled by the size of the
sixfold rings then only an infinitely large sixfold
cluster would produce states at the Fermi energy. No
significant contribution from the tail states is expected
in the EPR signal.
While this model has been used to explain the general feature of
the DOS there have been problems applying it to the values of
~2 obtained from spectroscopic ellipsometry [ 161 ]. The concept
of asymmetric bands was employed by Fanchini et al. [ 161 ] in
their explanation of the energy dependence of the imaginary
part of the dielectric constant. Figure 33 shows the fits (dashed
lines) to the imaginary part ~52 for an s p 2- and for an sp3-rich
film assuming a symmetric Gaussian model for the DOS as pro-
posed in [ 160]. It is evident that for the high s p 3 containing film
that an adequate fit is obtained to the data only for E > 2.5 eV
but not at lower energies. By contrast, for the sp2-rich film a
good fit is obtained at lower energies but not at higher ener-
SILVA ET AL.
Huckel model in which overlap between nearest neighbor atoms
is non-negligible, Fanchini et al. obtained a much better fit to
data as shown (solid lines).
Arena et al. [ 162] studied the DOS in TAC using conductiv-
ity spectra obtained from scanning tunnelling microscopy and
observed EF to be below the midgap (indicating an intrinsi-
cally p-type material). They also found that the valence band
tail, associated with the yr states, is steeper than the conduction
band tail (Jr* states), opposite to the case of a-Si [ 163]. They at-
tributed the asymmetry to the effects of disorder. However, this
result also shows that the disorder present is not simply due to
the presence of different s p 2 configurations.
The optical properties (refractive index n and extinction co-
efficient k) as a function of wavelength of various a-C films
have also be modelled in the confines of the Forouhi-Bloomer
model (FB) [ 164] by Alterovitz et al. [ 165]. This early work
showed that fits to n and k for both wide (2.3 eV) and narrow
(1.2 eV) gap films were only possible over a limited energy
range. It was also found in the fitting that the long wavelength
refractive index decreased with increasing bandgap contrary to
what should be observed as the amount of absorption from cr
bonding becomes more dominant in the higher bandgap films.
McGahan et al. modified the FB model by regarding the density
of states to be of the form [ 166]
A1 ( E - Eg) 2 + A 2 ( E - Eg) 3/2 (4.7)
and obtained better fits to the data. They noted that assuming a
Gaussian conduction and valence band density of states did not
fit the measured values of n and k.
4.1.2. Urbach Tail E n e r g y
In the vicinity of the band edge the optical absorption has an
exponential energy dependence usually expressed in the form
c~(hw) = c~0 exp([E - hzo]/Eu) (4.8)
where Eu is the Urbach energy. In a crystalline material Eu
depends upon phonon induced structural disorder or the effects
of charged impurities. In the case of an amorphous material Eu
is governed by the static disorder (bond angle and bond length
variation). In this way the Urbach absorption edge is a measure
of the joint density of states and reflects the disorder broadening
of the respective bands. In the case of low defect density a-Si:H
the valence band tail has an exponential slope of about 45 meV
which is larger than the slope of the conduction band (25 meV).
In this way the Urbach energy of 55 meV for low defect den-
sity a-Si:H is mainly determined by the valence band. In the
case of a-C based materials values of Eu tend to be higher and
depend upon the optical gap. In PAC materials Eu tends to be
about 520 meV for an E04 gap of 3.5 eV [88]. This reduces to
about 250 meV for E04 -- 2.6 eV. Addition of N affects both
the optical gap and the Urbach energy. In the case of TAC films
the optical gap remains approximately constant at about 2 eV
for N concentrations of up to 0.2 at.% and then decreases to
0.75 eV (2 at.%) with subsequent increases in N closing the gap
 AMORPHOUS CARBON THIN FILMS 435

2.5
at about 10 at.% (see Fig. 34a). This is indicative of graphitiza- I I I (a) I
tion of the film and is mirrored by an increase in Etj from 250 2.0
to over 550 meV at the highest N content. The increase in Eu
ca. 1.5
is a reflection of the broadening of the Jr and Jr* bands which
ultimately leads to closure of the gap. "~ 1.0
A different behavior was reported by Silva et al. [29] in their
DAC:N films. The optical gap first increases from about 1.6 eV, O 0.5

reaching a maximum about 7 at.% N, and then decreases. The

~ I I
Urbach tail width decreases from about 260 meV to reach its 0.6- ! I I
minimum around 7 at.% (175 meV) and then rises slightly to >
(b)
v
remain at around 200 meV. The increase in the optical gap and >,, 0.5
the reduction in Eu could be explained in terms of an initial re- t-
duction in the disorder in the films--mopping away some of 0.4
c-
O
the band tail states. The subsequent reduction of the optical tll
0.3
gap is again due the inset of graphization. It is interesting to
note that the electron paramagnetic spin density also reduces 0.2 I I 1...
0.01 0.1 1 10
with the inclusion of N and then remains constant. Annealing
of TAC films also shows the effects of graphization on the band N content (at. %)
tails. Conway et al. [ 167] showed that E04 gap is approximately
constant to about 300~ and then begins to decrease. Over the Fig. 34. (a) Optical gap and (b) Urbach energy for 100 eV C+ FCVA de-
posited TAC as a function of N content. Adapted from [243].
same range of annealing Eu does not change significantly but
increases above 350~

symmetry breaking and the relaxation of the optical selection

4.2. Infrared A b s o r p t i o n Studies
4.2.1. Introduction
The useful electro-optical and mechanical properties of a-C thin
films and its alloys are attributed to their microstructure. There
are numerous reports in the literature that offer valuable insight
into the microstructure of these films using various characteri-
zation techniques.
The complications in determining the microstructure of the
films arise from a combination of factors. First, a-C(:H) films
can only be grown to a maximum thickness of a few hun-
dred nanometers on silicon substrates. This value is reduced to
a few hundred angstroms for the case of ultrahard DAC and
TAC(:H) films. Attempts to grow thicker films result in the
detrimental delamination of the films. Second, the metastable
nature of the film's microstructure makes them extremely deli-
cate to most characterization techniques. Even the small energy
doses supplied by most characterization techniques, in the form
of a particle beam or high energy electromagnetic radiation,
will change the film's microstructure during the experimental
measurement. This will lead to the determination of the mi-
crostructure of a different type of film than the one initially
prepared.
The low energies involved in optical spectroscopic tech-
niques make them particularly well suited for the investigation
of such delicate microstructures. Infrared optical spectroscopy
is an extremely powerful technique in characterizing the bond-
ing found within the films. The high matrix element of the
optically active stretching and bending modes of the C-H bonds
give rise to a strong signal-to-noise ratio in modern Fourier
transform spectrometers and yield strong absorption bands in
the spectra. Also, the amorphous nature of the films causes
rules, allowing for the stretching modes of homonuclear cova-
lent bonds to be observed. It is also a powerful and extremely
sensitive technique used to determine the existence of alloying
elements or impurities, covalently bonded to the structure of the
films.
It should be noted that Fourier transform IR (FTIR) com-
plements Raman scattering by providing detailed information
on the nonsymmetric bonds in a-C thin films. It was shown
by Kaufman et al. [168] that in the case of a-C films that
contained aromatic sixfold benzenelike carbon rings that were
IR-inactive, the addition of planar N bonds made them IR-
active by breaking the symmetry. In the present study we
will concentrate on a few key papers, each representative of a
particular type of microstructure of a-C films. As FTIR has his-
torically been a preferred tool for the characterization of a-C:H
and a-C:N films, extensive literature in the field can be obtained
by examining some of the references [17, 24, 25, 29, 44, 86,
168-177]. In our review we will examine in detail the FTIR
spectra in PAC [86], DAC [25, 178, 172], and TAC [ 174] films.
As there is considerable interest in examining nitrogenated a-C
films, some of the results in addition of N into the microstruc-
ture of a-C will also be discussed [29, 86, 175].
4.2.2. Experimental Method
Most modern infrared spectrometers almost always use FT
techniques for spectral detection. The FTIR spectrometer con-
sists of a Michelson interferometer and this method offers
greater sensitivity than moving diffraction grating spectrome-
ters, because the detector monitors the entire spectrum simulta-
neously, rather than one frequency at a time. The most common
way of obtaining the FTIR spectrum from films of a-C and its
436
9 ! 9 i 9 i 9 i 9 !
:l:a
"-E NH and sp' ~/ I ! !
tot-u~ CHstretch _ _ _ I ]~
CH sp'and ~J
bond stretch
,000' 0'00' 0'00'
Frequency (cm1)
Fig. 35. FTIRabsorption spectrum for a PAC and for a nitrogenated PAC film.
alloys is to grow a thick film of the material on a high resistivity
silicon wafer substrate. It is important that the silicon is highly
resistive, in order to obtain a clear spectra. The substrate is then
mounted inside the spectrometer in transmission mode, so that
the infrared beam trespasses the whole sample normally. The
spectrum is then taken, using the spectrum from a plain sub-
strate as the background signal.
A much enhanced signal-to-noise ratio is observed in the
spectra when the measurement is obtained using diffuse re-
flectance infrared Fourier transform spectroscopy. In order to
perform this type of measurement, the film must be deposited
on a highly reflecting substrate (in the 4000 to 400 cm -1 re-
gion of the electromagnetic spectrum). Such a substrate can be
either a highly doped silicon wafer or a metal-coated flat sub-
strate. Suitable metals for this application are titanium (resistant
to sputtering in the RF PECVD chamber) or aluminium (high
reflectivity in the infrared). In this measurement, the infrared
beam incident on the sample is transmitted through the film
and reflected from the substrate back to the spectrometer, af-
ter traversing through the film a second time. The advantage of
this method is that the infrared beam is not transmitted through
the substrate and hence the noise level in the spectra is ex-
tremely low. This type of measurement is essential if accurate
deconvolution of spectral absorption bands is required. Another
technique to enhance the sensitivity of the FTIR measurement
by avoiding the signal arising from the substrate is to dissolve
the substrate in a liquid solvent and leave the freestanding film,
which can be picked up using a silicon frame, as described by
Silva et al. [25]. An often-used substrate for this procedure is
single crystal NaC1, which is dissolved in water.
4.2.3. FTIR Studies o f PAC Films
PAC is a particularly viable material to investigate by FTIR as
films of PAC and PAC:N can be grown to up to 400 nm before
delamination occurs. The thicker films often provide a clear
FTIR spectrum. A typical spectrum from a PAC and PAC:N
SILVA ET AL.
9 i . !
films is shown in Figure 35. The figure also shows the assign-
ment of the most important absorption bands.
Figure 35 shows how the hydrogen stretching vibration
modes occur at the highest frequency, due to the small mass
of the hydrogen atoms. The frequency region of the spectra
where the stretching vibration modes occur is from 4000 to
W --" I
1485 cm -1 . The frequency region between 1485 and 400 cm-1
is known as the fingerprint region and is where the absorption
h\~ bands from bending modes occur. Bending modes in amor-
phous materials are difficult to examine due to the strained bond
CH bend angles, and also due to the many different infrared active modes
of oscillations that the solid network may have. The single va-
0'00 ' lence of hydrogen gives rise to sharp bending modes in the
spectra, which are useful for characterization.
4.2.3.1. Bending Modes
The symmetrical deformation mode of the methyl group (sp a
CH3) gives rise to the absorption band peaked at 1380 cm -1
[179]. The position of this band is relatively constant, and
it is of great analytical importance, because this region does
not contain other strong absorption bands. The asymmetric de-
formation vibration of the methyl group gives rise to a band
centered around 1460 cm -1. The proximity of this frequency
to that of the scissoring vibration of the methylene group (sp a
- C H 2 - ) gives rise to a convoluted absorption band peaked at
1457 cm -1. This convoluted peak also contains the absorp-
tion band from the =CH2 deformation, which occurs around
1420 cm -1 . The position of the deformation vibration of the
methylene group can vary in the case of strained cycloalkanes,
by up to 30 cm -1. This may give rise to band broadening in
PAC(:N). It may be possible that structures with sixfold rings
exist in a-C:H. The bending modes of the sixfold rings are char-
acteristic and show absorption bands at the lowest frequencies.
As an example, both cyclohexane and benzene show structural
C - C bending deformation vibration absorption bands centered
around 522 and around 450 cm -1 , respectively. The strong and
broad absorption band of a-C:H observed between 445 and
550 cm -1 may be due to bending modes of planes consisting
of hexagonal structures, although such a band could also arise
from the torsion of C = C double bonds [179]. Another C - C
bending deformation mode of cyclohexane has an absorption
band centered around 865 cm -1 . The spectra of a-C:H shows a
complex structure around this frequency.
The in-plane rocking vibration of the CH bonds of the
methylene group shows an absorption band centered around
720 cm -1 in straight chain alkanes. The infrared spectra of
these films shows a very broad band around this region. The
strong band centered around 890 cm -1 occurs in the spectra
from all the films from the nitrogen series. It is attributed to a
convolution of the absorption bands from the distortions of the
ethyl group and of the C - C double bonds of the R1RzC=CH2
group, where R1 and R2 are sp 3 carbon atoms. The absorption
band from the (CH3)2CH-R group occurs at slightly higher fre-
quencies, around 920 cm -1. Also, cyclohexane shows a CH2
 AMORPHOUS CARBON THIN FILMS
bending frequency at 903 cm -1. Again, the structure of this
band is complicated.
A point of interest is that the nitrogenation of the PAC films
gives rise to the absorption band centered at 1343 cm -1. The
assignment of this band is unclear, and it is attributed to the
nitrogenation of the films. It probably arises from band split-
ting of the CH bending vibrations from 1375 cm -1 to lower
wavenumbers. Films of PAC show a strong band peaked around
1050 cm-1. As these films are nitrogenated, this band gets con-
siderably weaker, and another band appears centered around
1140 cm -1. The assignment of these bands is also not clear,
but they may be related to the CH and C-C bending modes of
s p 3 quaternary carbon atoms in structures such as R1R2CH-R3
and a tetrahedrally bonded carbon to another four carbon atoms.
4.2.3.2. S t r e t c h i n g M o d e s
The absorption band found in the frequency range between
3570 and 3100 cm -1 is attributed to the convoluted absorption
bands of the NH and s p 1 CH stretching vibrations. The band
can be deconvolved into two Gaussians. The band for the a-C:H
spectra arises mainly due to the s p 1 CH absorption frequency,
due to the lack of nitrogen in the film. A small contribution
from the NH stretching vibration was also detected in the PAC
films, however, and it is speculated that this is due to the reac-
tion between nitrogen and surface dangling bonds that may take
place during the venting of the PECVD reaction chamber due
the high porosity after growth.
The single valence of hydrogen makes the investigation of its
bonding useful, since this will yield information about the atom
that it is attached to. The fact that the films have a high hydro-
gen content, of the order of 55 %, means that most of the carbon
atoms within the films are attached to at least one hydrogen
atom, and hence its hybridization state can be known (assum-
ing all the hydrogen is bound). The s p a and s p 3 CH stretching
band shows up clearly in the infrared spectra of all the sam-
pies, in the frequency region between 3070 and 2800 cm -1.
The band is composed of a convoluted series of different ab-
sorption bands that arise from the stretching vibrations of all
the different types of CH bonds present in the sample, and also
the individual bands from the different modes of the stretch-
ing vibrations for each type of CH bond containing group. The
different groups containing s p 3 CH bonds are the CH3, CH2,
and CH groups. The CH3 group has symmetrical and asymmet-
rical stretch frequencies at 2872 and 2962 cm -1, respectively.
The s p 3 CHe group has a symmetrical and asymmetrical stretch
centered at 2853 and 2926 cm -1, respectively. These frequen-
cies changed by one wavenumber for the case of cyclohexane.
The s p 3 CH stretch occurs at 2890 cm -1. These frequencies
were determined from spectroscopy of alkanes.
Another type of CH bond occurs when the hydrogen is
bonded to an s p a hybridized carbon atom. This bond has a
higher force constant than that of the s p 3 CH bond, and so
the infrared absorption bands will occur at higher frequencies,
above 3010 cm -1. The possible hydrogen containing groups
that can be formed are the s p e CHa or s p e CH groups. For
437
alkenes, the position of the absorption bands corresponding to
the stretching vibrations of these groups can change, accord-
ing to the position of the double bond in the alkene, but the
bands typically occur at 3070 and 3015 cm -1, respectively.
Another important infrared absorption band is that of aromatic
groups such as substituted benzene, which show an aromatic
CH stretching vibration centered around 3060 to 3100 cm-1.
The infrared spectra of PAC samples show no bands centered
around 3070 cm -1. The deconvolution of the CH stretching
band into Lorentzian functions also shows no strong bands
centered around 3015 cm -1, but this does not rule out the
possibility of a weak band existing at this frequency. It is gen-
erally accepted that in most PAC films, the number of s p 2
hybridized carbon atoms (including aromatic groups) that are
bonded to hydrogen is very small, compared to the number of
s p 3 hybridized carbon atoms bonded to hydrogen. Silva et al.
[29] used a magnetically confined RF PECVD system to grow
PAC:N films. Their analysis showed a much higher ratio of s p 2
hybridized carbon atoms, mainly in the form of aromatic rings.
Alkenes with conjugated double bonds (dienes) show char-
acteristic frequency shifts when compared to alkenes with a
single double bond. The interactions between the Jr electrons
of the conjugated system decrease the C = C double bond order
and increase the C-C single bond order. This means that the
absorption bands of individual double bonds cannot be identi-
fied separately, and the entire carbon framework behaves like a
single vibrational entity. Consequently, the C-C stretching vi-
brations occur in the 1600 cm-1 region. The strong absorption
band from the C - N bond in the PAC:N samples makes difficult
the observation of a possible band centered around 1600 cm -1 .
The C - C and C-=N triple bonds have a very similar stretch-
ing resonant frequency, and they occur between 2270 and
2130 cm -1. The band can hardly be observed in the PAC
films, but it is clearly observable (although weak) in all the
PAC:N samples. The weak signal-to-noise ratio for this absorp-
tion band made the deconvolution work of the band unfeasible.
The amorphous nature of the a-C:H(:N) films ought to make
the C=C triple bond infrared active. This gave rise to the idea
that there are few triple bonds in the a-C:H films but that this
number was increased in the a-C:H:N films, where most of the
triple bonds were C=-N bonds.
The stretching vibrations for the C--C and C = N double
bonds are found in the frequency region between 1815 and
1490 cm -1. Again, the similarity in the atomic masses of the
C and N atoms and the similar spring constant of the C = C and
C = N double bonds mean that the absorption bands occur at
similar frequencies, and they appear as one convoluted absorp-
tion band. The strong signal-to-noise ratio of this absorption
band made deconvolution possible, and the integrated intensi-
ties for the main components of the band were obtained. The
spectra from the PAC:N films showed two bands. One strong
band was centered around 1700 cm -1 and another weak one
was centered around 1555 cm -1. The 1700 cm -1 band is at-
tributed to the C = C double bond stretch (made optically active
due to symmetry breakdown due to the amorphous nature of
the material), and the 1555 cm -1 band is attributed to the
438 SILVA ET AL.
Fig. 36. IR absorption bands for various a-C:H films. 0-90 V represents PAC
films, and 200-1000 V resprents DAC films. A TAC:H film is also shown Re-
produced with permission from [178], 9 1996, Elsevier Science.
C--N double bonds. On nitrogenation of the films, the posi-
tion of the C = C double bond band shifts to 1670 c m - 1, and the
1555 cm -1 band shifts to 1590 cm -1 . The position of the bands
is the same for all the nitrogenated samples. The shifting of the
Fig. 37. IR absorption bands for a PAC (25 V), DAC (410 V), and TAC film in the CH bending and stretching modes.
Reproduced with permission from [178], 9 1996, Elsevier Science.
bands due to the nitrogenation of the samples is attributed to the
electronegativity of the nitrogen atom, compared to the carbon
atom.
An important point to stress is that the shape of absorption
bands is described by a Lorentzian lineshape. In PAC, the C - C
and C - N bonds found in the skeleton structure of the carbon
network suffer from distortions due to the amorphous nature of
the films. These distortions affect the position of the absorption
band. The energy distortions are distributed according to Gaus-
sian distribution functions, which are generally wider functions
than Lorentzian functions. This means that the resulting absorp-
tion band shape is going to be determined mainly by the random
distortions of the bonds, and their line shapes will be Gaussian
distributed. However, the CH bonds are short and do not suffer
from distortions or spatial confinements as much as the rest of
the network bonds. This means that the effect of bond distor-
tions on CH bonds is minimal, and the shape of the absorption
bands is often well defined by Lorentzian functions.
A whole series of films deposited as a function of DC self-
bias by Stief et al. [ 178] is shown in Figure 36. The PAC films
are the ones deposited below a DC negative self-bias of 90 V,
where the C - H stretching modes appearing between 2800 and
3100 cm-1 are well resolved. An expanded view of the modes
visible is shown in Figure 37, for the film deposited at a negative
bias of 25 V. Also shown in Figure 37 are the spectra for a DAC
film (self-bias of 410 V) and a TAC:H film deposited using a
plasma beam source for comparison. These will be discussed in
detail later. A well resolved set of C - H bending modes is evi-
dent. For the PAC films, the vibrational modes are distinct and
well defined due to the localized nature of the C - H vibrational
 AMORPHOUS CARBON THIN FILMS 439

Time (see) 0.8 , 0.20 , |

(a) (b)
0 I000 2000 3000 4000 "--! O
:5 0.6
lo-lO U b i a s = 2 5 V ~
0.15
sum v
10-11 t-- 0.4
'~ He(C~H4) (.-
c
~ 0.10 1
10-12 9 ....:L..."-..- ' ~ _ _ . . . . _ ~ C 3 H s
c", 0.2
I I
03 I I I 0(!)6 I
10-13 (d)
10-I4
x~(C) 9 X
t 0.2 ~ ~ o ~ d 0.4
104o ._z-
Ubias=350V 1,, t-
v • v x c

9 10-1~ ~r - 0.1 • • t-
0.2
• - ~
, ~ 10-t2 ! i I I
0.08 I I I
0 o 5 10 15
~t:~lO-13 -'"._.~...... C3H $ (e)
o,2 O O
~- 0.02
~ i044 O I~ O O
v
Nitrogen flow rate (sccm)

~' i04o ta-C:tt -~ 0.01 V ~7 ~7

/ ~ ~ c
(1) 3 0 As deposited
t- [ ] 100~ anneal
10-1t in
0 x x x x x-
I i i i
V 250~ anneal
x 400~ anneal
10-12 0 5 10 15
......... ~ C3Hs
10-13 Nitrogen flow rate (sccm)

10-14 t "....'

0 200 400 600 800 1000 1200 1400 Fig. 39. Normalized integrated absorption intensities of (a) s p 2 and s p 3
bonded CH stretch, (b) NH stretch and s p 1 bonded CH, (c) CC double bonds,
Temperature (*C) (d) CN double bonds, and (e) CC and CN triple bonds as a function of nitrogen
Fig. 38. Effusion transients for a PAC (25 V), DAC (350 V), and TAC films. flow and anneal temperature in nitrogenated PAC film.
Reproduced with permission from [ 178], (~) 1996, Elsevier Science.

"o
r" 2.5 - ' ~ ---
modes. The variation of the films when subject to annealing is
= }
shown in the effusion transients in Figure 38. It is clear that for 2.0
the PAC film deposited at - 2 5 V, 70% of the hydrogen is re-
leased as C3H8, 17% as H2, and 7% as C3H6 and CH4 each.
O
The films are stable up to 200~ while the hydrogen transients I 1
were still continuing at 1050~ Most of the hydrocarbon gases 0 5 10 15

were completely exhausted after 600~ for the PAC film.

Nitrogen flow rate (sccm)
In the case of the nitrogenated PAC (PAC:N), the varia-
tion of the normalized integrated absorption bands is shown
---O--- No a n n e a l
in Figure 39 as a function of anneal temperature. The s p 3 m --C)-- - - 100~ anneal
CH bands dominate the spectra, with the s p 2 CH bands con- __ _ - ~ - _ _ 250oC
- ~ - 400~
tributing weakly to the signal [86]. As the fingerprint region of
these spectra did not show any strong sharp absorption bands Fig. 40. The s p 3 CH2/CH 3 ratio for the nitrogenated PAC films as a function
in the window 950-650 cm -1, it was concluded that sixfold of nitrogen flow and temperature.
aromatic structures were not a major component of the poly-
meric films following the arguments of Williams and Fleming
[ 180]. In their work [ 180] it was shown that nonaromatic films lations Anguita et al. discussed the thermal stability of the films
that contain C--C double bonds have a peak at 1600 cm -1, but and its implications on the deposition of good quality semicon-
no features in the 3050 c m - ] or 950-650 cm-1 range. Anguita ducting PAC films.
et al. [86] concluded that most of the PAC films were composed
of polymer chains that had CH2 repeat units that were termi-
4.2.4. FTIR Studies of DAC Films
nated by CH3 ends (all s p 3 hybridized). Using this argument
they calculated the CH2/CH3 bond ratio as a function of nitro- The variation of the IR bands with increasing DC self-bias volt-
gen content and anneal temperature (see Fig. 40) and showed age is shown in Figs. 36 and 37. The DAC films are represented
that on average a carbon alkanelike chain length of 1 nm is ex- in the voltage range 200-1000 V. There is a major change in the
pected for these films. These chain structure values are much structural properties when moving from PAC to DAC films, and
smaller than the cluster sizes predicted by Robertson [79]. In this is represented in the IR spectra. It is clearly seen that both
the analysis that followed, using bond formation energy calcu- in the bending and stretching modes the intensity of the peaks
440 SILVA ET AL.

"-" 1.5
i "'I ' .... I '' I I I ' I ' I
(a) 9 I 9 ! -r ~ 9 I 9

< 9 O--iO.m 9 .....8~ O Io-C:HI 29?5-sp3CH2 lZ,S0- spZ/sp3

sp3CH3-29~3 2870- sp3CH
t9 tO
sp?CH-302S
,.J

/
u_ 0.5
F-
{a) " " O
o \
I , l , I , l l I ~0 l C
o
/
w c3c
i-- 11' L..
z o
"I- 1.0 o ~ ~ " O~o
u}
.o
<C
}
P_
tLl
r

~ 0.5 /
% 50
"I" " (b) I
..

6 ,
I , I ~ I m I m Ixel "
t
75
/ 9 1

32OO 3(X)0 2800 1600 %00 1200

sp3 ~.~ 9 /
Wovenumbor [crfill
7. 60-
r _
7
o
ol
l,O
(b)
o 2o
w 9 2925-sp3CH~
n spl sp"CH-2960b 87 "

100 200 300 AO0 500 600

sp2CH-3C50 / I ~ 1610-,~CC/,~s
ANNEAL T E H P . (oC}

Fig. 41. Variation in the (a) bandgap, (b) CH stretch intensity, and (c) type o
of bonding for DAC films as a function of annealing temperature. Reproduced
with permission from [24], 9 1989, Trans Tech Publications Ltd. o

0
decreases significantly. Also the s p 3 CH3 vibrational peak at
1370 cm-1 disappears. Most of the bonding that was s p 3 CH3
is now being gradually replaced by s p a olefinic and aromatic
bonds. A majority (40%) of the H is bonded as s p 3 CHa. Signif-
icant percentages of olefinic (22%) and aromatic (23%) bonds
in a s p a CH configuration are also found [178]. Bands usu- 9 1 9 1 i .r il . 1 ! 1 .

ally associated with C-C single bonds below 1300 cm -1 now 3zoo 3ooo z~ 16oo 1r 1zoo
become more prevalent, together with the C = C double bond Wavenumber [crfi 11
associated with the aromatic clusters close to 1600 cm -1 . The Fig. 42. Variation in the [R absorption spectra as a function of (a) A r percent-
porosity of the microstructure in the films is clearly decreasing age of C H 4 - A r mixture for DAC films deposited at - 3 5 0 V, and (b) microwave
by the reduced uptake of water vapor by the films presumably power (DC self-bias) for DAC films in a hybrid microwave-RF deposition sys-
when exposed to the atmosphere. In the effusion experiments tem. Reproduced with permission from [ 181 ], (~) 1992, Elsevier Science.

shown in Figure 38 a large percentage of the hydrogen (75%)

is molecular, with a gradual effusion of methyl C3H8 groups at
around 200~ The main release of hydrogen occurs at 550~
in the form of CH4 and Ha. What remains beyond this is usually
graphitic due to the collapse of the amorphous structure. A very
similar picture is observed in the results of Koidl [24] shown in
Figure 41, where variations in the bandgap, CH stretch inten-
sity, and type of bonding are shown.
Essentially a similar variation can be observed in all DAC
films independent of the deposition system used. This is beauti-
fully highlighted when we consider DAC films deposited using
a hybrid microwave-RF system constructed by Martinu et al.
[ 181 ] shown in Figure 42 as a function of both Ar percentage
and microwave power. Even the reduction of the 1375 s p 3 CH
peak is shown reproduced as the DC self-bias increases. At the
highest bias voltages, it can be seen that there is a loss of hy-
drogen by the decrease in the intensity of the stretching and
bending modes together with a spreading or diffusive effect of
the peak shape. This is partly due to amorphization at the higher
bias and partly due to graphitization.
A thorough analysis of the FTIR spectrum of DAC films de-
posited by RF magnetron sputtering has been reported by Clin
et al. [182]. In their work, they sputtered a graphite target us-
ing an argon plasma containing 10% hydrogen as the reactant
gas. Their analysis of the deconvolution of the CH stretching
band showed a decrease of the s p 3 C H / s p 2 CH bond ratio as
 AMORPHOUS CARBON THIN FILMS
the negative target bias (i.e., RF power) increases. This was ac-
companied by an increase of the refractive index and a decrease
of the E04 optical bandgap, suggesting a densification of the
films with increasing RF power. The behavior was attributed to
a decrease of the total H content, as well as a decrease in the
porosity of the samples.
4.2.5. F T I R Studies o f TAC Films
It should be noted that in order to produce TAC:H films using
the plasma beam source whose properties in the IR are shown
in Figures 36, 37, and 38, very specific conditions should be
used [ 17]. When these optimized parameters are used extremely
well defined IR bands are observed. The IR measurements sug-
gest that the sp 2 C-H stretch modes are olefinic in nature as is
shown to be the case in the neutron diffraction work of Wai-
ters et al. [83]. The sharpness of the stretching modes in the
IR bands usually signifies polymeric soft films. In contrast, the
effusion results clearly show the main threshold for hydrogen
is at 700~ which is much higher than the 200-400~ seen
for the PAC films. This clearly shows that the structure of these
films as well as the hydrogen uptake is significantly different.
Chen et al. [ 174] observed the variation of the FTIR with in-
creasing nitrogen content in their TAC films. They showed that
in the case of the undoped films there were no IR bands visible,
and in order to observe any bands nitrogen contents in excess
of 15% were needed. When such a high alloying was used the
nitrogen appeared to prefer to sit in a trigonal configuration and
thus promote sp 2 bonding.
4.2.6. F T I R Studies o f G A C Films
Some work on GAC films has been reported by Schwan et al.
[77] when they used a plasma beam source to deposit a-C films.
In the conditions used by them a s p 3 contents (by EELS) of less
than 20% were obtained for all the bias voltages used. Stretch-
ing modes close to 3000 cm-1 were observed due to the use of
C2H2 as the source gas for the plasma beam together with Ar,
and an sp 3 content obtained from the ratio of sp 3 to sp 2 C-H
bonds of 75% is predicted. This clearly illustrates the problems
associated in using FTIR to obtain quantitative information on
bond hybridizations. Effusion studies showed the hydrogen to
be stable until above 500~ Very interestingly, the bandgaps
of these films were close to 2 eV, and so the microstructure of
these films could not be explained using the simple cluster mod-
els developed by Robertson. It was thought that in these films
the aliphatic (olefinic) bonding was more likely.
4.3. Photoluminescence Spectroscopy
4.3.1. Introduction
The classical description of photoluminescence (PL) is usually
discussed in terms of the initial excitation of an electron from
the valence band to the conduction band by the absorption of
a photon of a particular wavelength. The resulting electron-
hole (e-h) pair may form a quasi-particle, the exciton, but they
441
will eventually annihilate each other with a subsequent emis-
sion of light. During its lifetime, the exciton can move within
the semiconductor (free exciton) or form a bound exciton. The
energy levels of the exciton are given by hydrogenlike Rydberg
states with an effective Bohr radius which often extends over
several 10's of atomic sites. If light of energies significantly
larger than the bandgap of the material is used for excitation,
then the electron and hole are pumped high into the bands after
which the carriers rapidly (typically femtoseconds) relax to the
bottom (top) of the conduction (valence) band. Carriers lose en-
ergy to the lattice in the form of phonons. As an alternative to
radiative recombination in which the emission of light results,
nonradiative recombination energy may also be transferred to
the lattice at specific sites, in the form lattice vibrations, thus
not involving the creation of a photon. This type of recombi-
nation is termed nonradiative recombination (NRR). In a-Si:H
paramagnetic defect sites are believed to act as sites for NRR.
The role of paramagnetic sites as NRR sites in amorphous car-
bon films is discussed in Section 5.
Among all the useful properties of PAC thin films, that
of strong, room temperature PL in the visible region of the
electromagnetic spectrum is significant [ 183-186]. This makes
amorphous carbon a potentially useful material for use in lu-
minescent devices, being especially well suited as the active
material in fiat-panel displays, due to its ease of deposition over
large areas using inexpensive RF PECVD techniques. There
is a strong need for a thorough understanding of the PL pro-
cess in amorphous carbon, to enable industrial exploitation of
its full potential. The useful luminescence properties of other
forms of carbon, such as carbon-fiber reinforced plastics, are al-
ready extensively used by material scientists to investigate the
mechanical failure of these materials [ 187, 188]. In this case,
luminescence is related to the relaxation that occurs after the
destruction of an atomic/molecular single bond by the applica-
tion of mechanical stress. The effect of field-emission-induced
luminescence from carbon nanotubes has also been reported
[ 189]. This part of the review, however, will place its empha-
sis on the PL properties of PAC and PAC:N thin films deposited
by PECVD from hydrocarbon gas sources.
4.3.2. P h o t o l u m i n e s c e n c e in PAC Films
A search through the literature clearly shows that there is still a
considerable amount of confusion about the origin of the PL in
amorphous carbon. Most of the research in this area has been
performed on the polymeric hydrogenated amorphous carbon
(PAC) films. It is widely accepted that it is only the soft form
of a-C that exhibits the strongest PL at room temperature [ 186,
190-192]. For this reason, this material has been the focus of
many efforts in developing viable electroluminescent devices
[193, 194]. PAC is also used as a dielectric in metal-insulator-
metal switches in active matrix displays [195, 196]. The PL
signal obtained from PAC films shows no sharp features like
those observed in the PL spectra from crystalline materials.
Rather, the PL spectra from PAC consist of broad bands, typ-
ical of amorphous semiconductors [163]. On excitation above
442 S ILVA ET AL.

1.00 -1 le I L-- 2.8 I I I I I I

E04 ( e V ) -

2.6 ~ 4.33_
0.75
v

...I
Q.
"1o
~ _ ~ ~ j ~ 3.73__
. m
0.50
r

0
Z ,~lo----o4.~ev K~, _~ e 22
0.25 I ----- 3.73eV ~,',,
I mF..... 9 3.28eV ~
I .......... 2.92 eV ~-'i~-~.
l e- ..... -e 2.69 eV I l" 2.0

1.7 2.0 2.3 2.6 2.9 3.2

I I I I I I
2.4 2.6 2.8 3.0 3.2 3.4 3.6

Energy (eV) Excitation energy (eV)

Fig. 43. PL spectra obtained from a set of PAC films with different optical Fig. 44. Position of the PL peak maximum as a function of excitation energy
bandgap values, as indicated. Adapted from [201]. for films with different E04 bandgaps.

I I I I u I I I I
the optical bandgap, the broad band PL spectrum occurs over a 1000
broad region, several eV's wide. A similar broad band spectrum
is observed from the PL signal obtained from polycrystalline di-
amond films grown by CVD [ 197], which suggests that PAC is
present in this material, mainly at the grain boundaries. :i 100
Early workers [183, 198] investigated the effect of sub-
strate DC self-bias during growth of PAC/DAC films on the C
ID
PL prepared by RF PECVD using methane. They observed a
significant decrease in the intensity of the PL signal with in- 10 ~li~ "e
creasing substrate DC self-bias. This observation is consistent
with the widely accepted model, since reducing the DC self-
bias during growth leads to growth conditions that favor the
formation of the highly luminescent PAC phase of a-C:H, due 1 i I i
to the low defect density material being deposited Surprisingly, -2 0 2 4 6 8

they also reported an invariance in the PL peak position with

Tauc optical bandgap for a given excitation wavelength [198].
They used an excitation source of higher energy than the opti-
cal bandgap of their PL measurements. It is important to note
that they obtained films with different optical bandgap values
by using a different substrate DC self-biases to grow the differ-
ent types of PAC films. Similar experiments repeated by other
groups [88, 199-202] also show the very weak dependence of
the peak position of the PL band with the optical bandgap for a
given PL excitation wavelength. This invariance is shown as a
small red-shift in the peak position of the PL spectra obtained
from a set of films with different optical bandgap values, shown
in Figure 43, by Rusli et al. [201,202].
PL measurements performed by Silva [88] and later Rusli
[201,202] on similar films showed that the most influential pa-
rameter on the peak position of the PL signal was the excitation
energy at which the PL measurement is performed. The posi-
tion of the PL maximum as a function of excitation energy for
films with different E04 optical bandgap values is shown in Fig-
ure 44.
Time (ns)
Fig. 45. Time-resolved room temperature PL decay from a PAC film possess-
ing an E04 gap of 3.4 eV. Reproduced with permission from [206], 9 1998,
Elsevier Science.
Ko6s et al. [203] performed a very careful analysis of the
PL spectra as a function of excitation energy for films grown
by RF PECVD from pure methane. Their results were in good
agreement with those reported in Figure 44. Both groups did not
observe a significant change in the PL peak energy as a func-
tion of excitation energy in the range between 2.95 and 3.93 eV
for a film with an E04 optical bandgap value of 3.1 eV. Ko6s
et al. observed that excitation energies of 5.9 eV did not excite
the characteristic PL band of PAC. A well defined PL spectrum
was only when the excitation energy was decreased to a maxi-
mum value of 5.63 eV. Decreasing the excitation energy further
lead to an increase in the PL efficiency, which peaked when the
excitation energy was 3 eV.
 AMORPHOUS CARBON THIN FILMS 443

11.0
4.3.3. Lifetime Studies of PAC Films
. ~ 1 ..... :...... I
The PL decay processes in PAC films have been consistently
reported to be about four orders of magnitude faster than in
m

m
"1o
10.5
=============================
amorphous silicon [204-206]. The time-resolved room temper- [~ 10.0
o)
ature PL decay of a PAC film (E04 optical bandgap of 3.4 eV) is
shown in Figure 45, reproduced from [206]. The PL measure- _J
~ 9.5
ment was taken with a 1 ps pulsed laser at an excitation energy e-

_1 &
of 2.93 eV, monitoring the time evolution of the peak inten- 9.0
sity at 2.36 eV. Figure 45 shows the initial rise of the signal,
followed by a decay in intensity after t - 0, the time cor- 1000/T (K 1)
responding to the arrival of the laser pulse. The decay is not Fig. 46. Variation of the log of the PL intensity versus 1 0 0 0 / T for two sam-
exponential, since it cannot be approximated by a linear func- pies, PL bands at 562 and 612 nm. A and B are integrated intensity of the 562
tion in the semilogarithmic plot. The peak at t ~ 2 ns was band from a PAC:N film with 2.5 and 15 sccm N2, respectively. Points C and D
refer to the integrated intensity of a band centered at 612 nm from PAC:N with
attributed to an artifact created by the electronics of the mea-
2.5 and 15 sccm N2.
suring system. Lormes et al. [206] noted that the decay of the
PL intensity, I (t), could be fitted to a stretched exponential de- 5 9 I 9 I I ' I 9

,..7,.
cay according to 9 .... 9
4
I1~11 "''"-
I (t) (x exp(-[t/reff] ~) (4.9)
3
They obtained values of fl of 0.44 and reff of the order of
0.07 -1- 0.02 ns. On this basis, a reasonable manner in which 2
to define the average decay time constant (Ts) involving only
I'..-A --A~=v~...e
l--e-B - A ..... .......~ , ,
one variable is given by [206] I---c ...................-"Av
_.1 l--I---D
o. 0
1 f l(t)dt
Ts-- /total
(4.10) 8 10 ;2 ;4 ;6 18
T lt2 (K lt2)
where/total is the total time integrated PL intensity. Using this
Fig. 47. PL integrated intensity as a function of the square root of the temper-
expression, three important trends in the decay time of the PL
ature. The bands are labelled as in Figure 46.
signal were observed:

(1) It was observed that Ts increases almost linearly, from

0.5 to 1.5 ns for samples grown by RF PECVD with
increasing substrate negative DC self-bias, from 0 to
1 0 0 0 V.
(2) Ts is independent of the laser excitation power used to
obtain the PL signal, but its value decreases by about a
factor of 3 to 0.2 ns, after 50 minutes of laser
illumination. It was also noted that increasing the
illumination time has no further effect on Ts.
(3) Ts increases with increasing energy AE, where A E is
the difference between the laser excitation energy,
Eexc, and PL detection energy, EpL
(AE = Eexc - EpL). Ts increases by a factor of about
2, to 0.4 ns, as A E increases from 0.1 to 1.2 eV. The
stretching to the exponential decay curve is a common
feature in a-Si:H and a-C:H. This stretching was
attributed to a decreasing decay rate which develops as
recombination proceeds after pulsed excitation. In
a-Si:H, this was explained by the increasing separation
of e-h pairs as their density is reduced by the
recombination process. This was used to explain how
the PL decay became faster at larger e-h generation
rates in a-Si:H. The constant decay time observed for
a-C:H is in contrast with these observations. This fact,
together with the short lifetime, suggest that the e-h
pairs are much more spatially localized in PAC than in
a-Si:H.
4.3.4. TemperatureDependence of PL Intensity
The dependence of the PL intensity as a function of sample tem-
perature is an area that has not attracted much attention in the
literature and there are few reports. It is important to investigate
the influence of temperature on the PL in PAC because this will
give information about the quenching mechanisms in PAC films
and the nature of the PL quenching sites. Experimental observa-
tions from most groups show that the temperature dependence
of the integrated intensity for PL bands does not show an Arrhe-
nius behavior. A typical example of this is shown in Figure 46,
where a plot of the log of PL intensity versus 1000/T does not
yield a straight line. The non-Arrhenius nature of the PL signal
as a function of the temperature is widely accepted in the litera-
ture [ 190]. Points A and B are integrated intensity of the 562 nm
band from PAC:N films with 2.5 and 15 sccm N2, respectively.
Points C and D refer to the integrated intensity of a band cen-
tered at 612 nm from PAC:N with 2.5 and 15 sccm N2. It is also
generally accepted that there is an increase in the PL intensity
associated with decreasing the temperature of the sample during
the PL measurement. Our experimental observations show that
444 SILVA ET AL.
a good fit exists when the PL integrated intensity is plotted as a
function of the temperature to the power 1/2, as shown in Fig-
ure 47. The measurement taken at 80 K was made by exposing
the sample to the excitation laser beam for more than 30 min-
utes for all the samples and hence caused a decrease in the PL
intensity due to PL fatigue. The samples were grown by placing
silicon substrates on the earthed electrode of a RF PECVD sys-
tem using methane, nitrogen, and helium. The flow rates were
20 and 75 sccm for methane and helium, and the flow rate of
nitrogen was varied from 0 to 15 sccm for different films.
4.3.5. PL Fatigue
PL fatigue has been reported in a-C based materials [ 173,207-
212]. It consists of a decrease in the PL intensity of the films
after prolonged exposure to the excitation source. There is some
doubt as to whether the decrease in the PL intensity is followed
by a shift of the PL peak position. A reduction in the PL de-
cay time by nearly a factor of 5 has been reported to follow the
PL fatigue process for PAC films deposited by RF PECVD. In-
terestingly, a self-recovery of fatigued PL samples in the dark
has also been observed [207]. PL fatigued samples placed in
the dark for 10 minutes showed a recovery of the PL intensity
of nearly 40%. The samples showed a 55% decrease in PL in-
tensity due to initial fatigue, which lasted 2 minutes. Although
most workers agree with the existence of PL fatigue in car-
bon films, some scientists report the observation of a significant
enhancement in the PL signal intensity after exposure to the ex-
citation source. This process was first reported by Ko6s et al.
[211] for RF PECVD grown PAC films. The prolonged expo-
sure to the excitation source was reported as "laser-soaking."
A threefold increase in the PL intensity was observed after
laser-soaking the samples for 1 hour, using the 488 nm line of an
argon ion laser. A small blue-shifting of the PL intensity maxi-
mum was reported to follow the laser-soaking process. Similar
results are reported for films grown by pulsed laser ablation,
which result in a high quality form of a-C:H (DAC/TAC) film
[210].
PL fatigue has been attributed to the creation of light-
induced defects, created by the excitation source, which act
as nonradiative recombination centers in the vicinity of a lu-
minescent dipole. Such additional defects will both reduce the
PL intensity and the PL decay rate, as confirmed by experi-
mental results. The PL efficiency enhancement by laser-soaking
has been attributed to the splitting of large clusters into many
smaller ones, induced by the effect of the excitation source on
the larger clusters. This explains the observed blue-shift of the
PL peak observed after prolonged exposure. However, it must
be stressed that sputtered a-C is a low bandgap material (hence
high density of larger clusters), but it does not exhibit a PL effi-
ciency enhancement by laser-soaking. Although PL fatigue and
PL efficiency enhancement processes have both been reported
to occur during prolonged exposure of films to the excitation
light source, different reports on similar experiments discuss
different combinations of these processes. For example, PL fa-
tigue has been reported to occur immediately after exposure
to the excitation source by some groups, while other groups
suggest an initial increase in the PL efficiency followed by a
decrease. The effect of prolonged exposure to the excitation
source is thus still a matter of research, and a more rigorous
analysis is needed.
It is well known that hydrocarbons exhibit photodecompo-
sition by ultraviolet (UV) radiation [173], with the evolution
of hydrogen containing molecules. It is likely that UV ex-
citation sources used during PL measurements will have an
effect on the microstructure of softer PAC films, which show
the most promising PL characteristics. The decomposition of
the polymerlike phase of PAC films is likely to reduce the
PL efficiency, either by introducing defects or by increasing
the size and/or density of the zr-bonded clusters. This would
result in a compromise, where the creation of defects would en-
hance the rate of nonradiative recombination, thus decreasing
the PL efficiency, while the generation of clusters will increase
the absorption coefficient of the films, thus increasing the e-h
generation rate. One of the key areas of research focuses on
determining the nature of the defects where nonradiative re-
combination takes place. It has been reported that these sites
may not necessarily be paramagnetic defects. Experimental ob-
servations point to the fact that the creation of defects has a
stronger effect.
Another macroscopic effect that decreases the PL efficiency
is the mechanical application of high pressure to the films
[212]. The investigations were carried out on reactively sput-
tered a-C:N films, which showed a very similar PL signal to RF
PECVD grown films, when excited with 488 nm wavelength
radiation. The results showed an exponential decrease in the in-
tegrated PL intensity with increasing pressure from 0 to 25 GPa.
The PL integrated intensity was reduced to about 15% of its
original value by the application of 8 GPa of mechanical pres-
sure. It was observed that the PL intensity was recovered after
decompression to ambient atmosphere.
4.3.6. Polarization Memory
The polarization memory that PECVD grown PAC exhibits
was first reported by Ko6s et al. [206, 213] and has been ob-
served and investigated by other groups [ 190, 202, 214-216].
The polarization memory consists of a considerable amount of
the PL intensity having the same polarization as the excitation
source. The intensity of the PL with polarization parallel (Is)
and perpendicular (Iv) is measured using a polarizer between
the sample and the monochromator. The degree of polarization
(DP) has been defined as [ 188]
Is-I v
DP = (4.11)
Is+Iv
It is noted that the intensity of the PL that has its polariza-
tion vector parallel to that of the excitation source is light that
has the same polarization as the excitation source. The effect of
PL polarization memory in an RF PECVD grown film with an
E04 bandgap of 4.33 eV, when excited using a 2.41 eV source,
is clearly observed in Figure 48a. In this figure, the solid and
 AMORPHOUS CARBON THIN FILMS 445

i I I I I I I I
(a) increasing PL energy above the excitation source. The depen-
dence of the PL DP on the film's properties shows interesting
results. The DP gives a measure of the degree of localization of
the carriers. Figure 49 shows the variation of the DP as a func-
r
C tion of the PL energy for a set of films with different E04 optical
r-
bandgap values reproduced from [214].
_.J
n In Figure 49, it is observed that as the PL energy decreases
from the value of the excitation source, the DP decreases almost
I I I I I I I
0.45 I I I I I I I I linearly. The trend is observed consistently on films with differ-
_(b) 9 9 ent optical bandgap values. This result may be expected, since
0.40 9 9 9 -
0 0 0 0 lower PL energies involve e-h pair thermalization for longer pe-
-- 00 -
0.35 riods of time. This extended lifetime of the e-h pairs increases
0.30 -- 9
00
9 - their probability of reorientation after their creation, thus losing
O 00 their original orientation. Also, the e-h pair-lattice interactions
0.25
involved during thermalization may contribute to changing the
0.20 I I I I I I I orientation of the e-h pairs. Another crucial trend that Figure 49
1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5
shows is that the DP is affected by the optical bandgap of the
films, the general trend being that the DP increases with in-
Energy (eV)
creasing optical bandgap of the films. The DP increases by
Fig. 48. (a) Effects of PL polarization memory on a PAC film (E04 gap of about 0.1 for films with bandgap values ranging from 2.69 to
4.33 eV) under 2.41 eV excitation. The polarizations refer to the polarization of
4.33 eV. This evidence suggests that carriers are more localized
the excitation source. (b) Degree of polarization (DP) for the PL spectra seen
in (a). Reproduced with permission from [214], 9 1996, American Physical in high bandgap material.
Society.

4.3. 7. Nitrogenated PAC Films

I i I i I I I i
0 The better electronic and mechanical properties of PAC:N over
0
0.4 0 PAC have led many scientists to diverge their research toward
0 0 1 ~ 9 the nitrogenated material over the last decade. The PL prop-
0 A
0 o
0 0 0 II~ 1 A 0 v1 ~3
erties of the nitrogenated material have been no exception in
o 9 showing a significant improvement in performance. The exact
0 1 1 B A ~ (ill 9
9 0 0
0 9 ll
9 role that nitrogen plays in PAC:N is yet not clear, but most agree
13.
E3 0.3 A 9 A 9 [] that the nitrogenated alloy outperforms PAC in nearly all as-
9 pects.
A 9 00 [] 2.69 eV The shape of the PL broad band observed from films of
9 2.92 eV PAC:N is similar to ones obtained from PAC films. Only care-
z~ 3.28 eV
0.2
9 3.73 eV ful deconvolution of the PL signal into its constituent bands
o 4.33 eV
shows that nitrogenation gives rise to the appearance of a new
I = I I I i I i
PL band [86]. The reason it is difficult to distinguish PAC from
~9 2~ 23 2.s 2.7 PAC:N films from their PL band shapes is that the intensity
of the contribution to the PL signal from the nitrogenation is
Energy (eV) small compared to the total PL signal from the material. An-
Fig. 49. Variation of the DP as a function of the PL energy for a series of PAC other aspect that clouds the issues on the difference in the PL
films with different E04 optical bandgap values. Reproduced with permission band shape between these two materials is the fact that there is
from [214], (g) 1996, American Physical Society. often a small amount of nitrogen found within the softer, more
porous PAC films.
It is widely observed that the PL efficiency of PAC:N films
broken lines correspond to polarization parallel and perpendic- increases as the concentration of nitrogen in the PECVD cham-
ular to that of the excitation, respectively. Figure 48b shows the ber increases. This trend is observed for nitrogen/methane gas
degree of polarization for the PL spectra seen in Figure 48a, mixture concentrations in the range between 0 and around 0.3.
from [214]. For PL events where the polarization is not con- Increasing further the nitrogen concentration in the plasma has
served, Is -- Ip, and DP tends to 0. For a random distribution an adverse effect on the PL efficiency, and it starts to decrease
of dipoles, the theoretical limit for DP is 0.5 [216]. Figure 49 once again. This trend is clearly observed in Figure 50 obtained
shows that DP for a-C:H can be as high as 0.4, which shows from [244]. It is important to note from Figure 50, that there
a strong PL polarization memory. Note that the peak in the is not a significant change in the position of the PL band for
polarization memory occurs for PL energies close to the excita- the PAC:N films grown using different nitrogen concentrations
tion energy. Also note that the DP decreases very rapidly with in the gas mixture. However, there exists a significant change
446
1.0 I I I I I I 13 I . . i . . I . . I
-
>., -gap
-
| /',
0.6 /'~ ~ ='-='~" PL intensity
o-
lD
O0
.c_
_.,I 0.4 / ~,.._-~_~as
ft.
\4o%
t 20%'~__._~__
0 I I i I i I t I ~
300 400 500 600 700
Wavelength (nm)
Fig. 50. PL spectra from PAC:N films for various N contents. The inset shows
the dependencies of the main energy peak position (EPL), optical gap (Egap),
and the relative PL intensity with N content in the gas mixture. Reproduced
with permission from [244], 9 19??, ???.
in the PL peak position of the PAC and PAC:N films. Another
point to state is that there is no apparent simple relation between
the PL peak position and the optical bandgap. All these obser-
vations have been confirmed by various workers and are still not
well understood. Early workers attributed the decrease in the PL
intensity at the higher nitrogen concentrations to the formation
of graphitelike bonding within the PAC:N films. Graphitelike
bonding is most likely to occur when growing at high nitrogen
concentrations.
Annealing PAC:N films at moderate temperatures (around
200-250~ has a very similar effect on the PL signal to
growing the films at high nitrogen concentrations. It is well
known that annealing these films at such temperatures induces
graphitelike bonding. The decrease in the PL efficiency with
annealing has been attributed to the formation of this type
of bonding. These two observations indicate that graphitelike
bonding sites are nonradiative recombination centers.
Recently [217], EPR measurements performed on PAC:N
films and discussed in Section 5 have shown that the density of
paramagnetic defects is invariant as a function of nitrogen con-
=entrations (ranging between 0 and 8 at.%). PL measurements
performed on these films show, however, a dramatic increase in
their PL efficiency upon nitrogenation [86]. These experimental
9bservations put into question once more the nature of the non-
:adiative recombination sites in PAC and PAC:N materials and
ire further evidence against these sites being paramagnetic cen-
:ers, as is the case for a-Si:H. To date there have been no reports
hat investigate the polarization memory of PAC:N films.
~.3.8. Possible PL Mechanisms
['he polarization memory and the short lifetime of the PL pro-
:ess suggest that the e-h pair created during excitation remains
:losely correlated until luminescence and does not diffuse or
SILVA ET AL.
I. - ,
i tunnel apart very easily. The close correlation between the elec-
tron and the hole renders their name as a geminate e-h pair.
An early mechanism for the PL process in PAC was sug-
gested by Robertson et al. [ 190]. Their calculations explained
the feasibility of a model based on the idea of geminate re-
combination within s p 2 carbon clusters embedded in an s p 3
amorphous matrix. This model was widely accepted, and most
15 30 45 workers explained their observations in terms of this model.
content (%) From the definition of the cluster model, the PL mechanism
_
meant that the exciton created was confined to a particular
_ cluster, which in most cases extends over many atomic sites.
Subsequent discoveries, such as the very short lifetime of exci-
tons in a-C:H and evidence for polarization memory, suggested
I i I i that the degree of localization of the geminate pair was stronger
800 900 1000
than previously thought and was applicable to only a few atomic
sites.
The strong localization of the e-h pair in wide bandgap PAC
would mean that the Bohr radius of the exciton must be smaller
than the dimensions of the cluster where the PL is believed
to originate. The high possibility of a carbon s p 3 phase sur-
rounding the cluster means that the amplitude of the exciton
wavefunction decreases strongly in this material, and tunnelling
to neighboring clusters is not expected to be a common process.
This contradicts current understanding and questions the nature
of the exciton that is being created.
Recently Piryatinskii et al. [218] investigated novel ways of
postgrowth treatment of PAC and PAC:N films in order to en-
hance the intensity of their PL signal. The films were gown
using a 13.56 MHz RF PECVD system using a CH4:H2:N2
gas mixture. Their investigations were focused on the effect
of H + ion implantation into PAC and PAC:N films. They con-
cluded that in all cases implantation resulted in some decreasing
of PL intensity because of ion beam induced film disordering
and appearance of nonradiative recombination centers. How-
ever, strong UV irradiation of preliminary implanted films led
to a marked increasing of PL intensity. In this case, the im-
planted hydrogen under the action of UV treatment can saturate
dangling bonds, leading to PL intensity increasing. They also
reported that the effect of strong UV irradiation alone, with-
out implantation, has the effect of reducing the PL intensity
of low nitrogen content a-C:H:N films but has no significant
effect on the PL intensity of high nitrogen content a-C:H:N
films. They attributed this to the strength of the carbon-nitrogen
bonds [219].
4.4. Raman Spectroscopy
4.4.1. I n t r o d u c t i o n
There have been a large number of papers published on the use
of Raman spectroscopy to obtain structural information about
the different types of amorphous carbon. The study by Ta-
mor and Vassell [220] published in 1994 is the one of the first
comprehensive studies to examine the Raman spectra of both
hydrogenated and unhydrogenated a-C thin films over a wide
range of deposition conditions. In this part of the review the
 AMORPHOUS CARBON THIN FILMS 447

fundamentals required to understand the results from Raman I i I

measurements will be presented along with some representa-
tive results which demonstrate the current understanding of the
topic. 0
-10 - -
Raman spectroscopy is a nondestructive optical technique o
that involves inelastic scattering from the vibrational modes in %
a sample. Raman scattering differs from infrared spectroscopy t"
-20 - -
in that the former is concerned with the changes in the bond []
o
polarizability whereas the latter is concerned with the presence 0
LI..
of a dipole in the vibration. For a single crystal, the intensity of
a spectrum is determined by the particular geometry, polariza- -30 []
tion of the incident beam, and the k conservation rule. As the
[] Xu (488 nm) []
Lifshitz (514 nm)
wavelength of the incident light is longer than the phonon wave-
length only those phonons with wavevectors at the Brillouin -40 i I i 1 i
zone center (k ~ 0) usually take part. In this way the Ra- 0 0.2 0.4 0.6 0.8 1.0

man spectra from single crystals will display sharp peaks. This sp3/(sp2+ sp 3)
is referred to as first order scattering. Second order effects, in
which two phonons of equal but opposite crystal momenta, may Fig. 51. Variation of the B W F parameter Q series of different prepared TAC
films as a function of s p 3 content. Reproduced with permission from [222], 9
also effectively satisfy this condition and give Raman shifts that 2000, American Institute of Physics.
will have peaks at roughly twice those of the first order Ra-
man shifts. The peaks tend to be broadened as a distribution of
phonons can take part. In an amorphous material a greater num-
\ !
ber of phonons can take part in the Raman scattering process as
the k = 0 conservation rule no longer holds and in this way the
intensity of the Raman signal is reflected in the vibrational den- -,q v

sity of states (VDOS) of the material. The intensity is usually

expressed in the Shuker-Gammon formula [221]
(a) G mode - relative motion of (b) D mode - breathing
n(w) + 1 two sp 2 C atoms mode of 6-fold ring
I (co) = ~ C (w)G(w) (4.12)
09 Fig. 52. Structures indicating the C s p 2 stretch vibrations (a) E2g vibration of
where n(w) + 1 is the boson occupation factor, C(w) is the two s p 2 C atoms and (b) A l g breathing mode found in a sixfold ring.

Raman coupling coefficient, and C(w) is the VDOS of the

amorphous material. The cross-section for Raman scattering
also dictates the strength of a particular Raman peak. At visi-
ble wavelengths scattering from s p 2 C sites is much higher than
that from s p 3 C sites. This is partly due to the fact that the local
s p 2 C energy gap of ('-~2 eV) is comparable with the energy of
the incident photons. In this way the contribution from the s p 3
sites is overshadowed by the contribution from the s p 2 sites.
In order to examine the s p 3 sites it is necessary to use lower
wavelength excitations (UV Raman scattering).
not at w0 but at wo + F / 2 Q . In this way Q measures the skew-
ness of the peak and for the BWF curves the tail increases to
lower frequencies for lower values of Q. Figure 51 shows the
values of Q used for a series of TAC films as a function of s p 3
content [222]. Films with a high s p 3 content tend to have large
negative values of Q and these tend to produce highly symmet-
rical Raman peaks. In such a situation Lorentzian lineshapes
can also be used.

4.4.3. Fundamentals of Raman Spectroscopy in Graphite

4.4.2. Raman Lineshapes
Raman lineshapes have been fitted using a combination of
Gaussian lineshapes as well as Lorentzian lineshapes. One of
the more common lineshapes is the Breit-Wigner-Fano (BWF)
lineshape which has the form
I0[1 -t- 2(o9 -- c o o ) / Q F ] 2
l(w) = (4.13)
1 -t- [2(w - c o o ) / F ] 2
where I0 and coo are the peak intensity and position respectively
and F is the full width half maximum. 1/ Q is the BWF coupling
coefficient and in the limit of 1/Q --+ 0 a Lorentzian lineshape
is recovered. The maximum of the BWF lineshape function is
and Disordered Graphite
Many of the characteristics present in the visible Raman spec-
tra of amorphous carbon thin films are discussed in terms of
similar peaks observed in graphite and disordered graphite. It
is therefore important to examine what is already known about
the Raman spectra from these two materials. Graphite is com-
posed of a series of stacked parallel layers of hexagonal planes
with trigonal planar s p 2 bonding. Each s p 2 C atom bonds with
three other s p 2 hybridized atoms to form a bonds. The bond an-
gle between the s p 2 hybridized orbitals is 120 ~ giving rise to
threefold rotational symmetry, and this results in a continuous
2D arrangement of hexagons, as shown in Figure 1. The fourth
448 SILVA ET AL.
valence electron is oriented perpendicular to this plane and is
delocalized into a Jr orbital. The cr bond length is 0.142 nm,
the spacing between the layers is 0.335 nm, and the layers
are stacked in a hexagonal arrangement in which neighboring
atoms in adjacent planes lie above and below (-ABABA-). The
space group of graphite is therefore D46h (P63/mmc). The de-
composition of the zone center optic modes can be obtained
using standard group theory and results in the following irre-
ducible representations
F = A2u + 2B2g + E lu + 2E2g (4.14)
The A2u and Elu modes are infrared active and have been ob-
served at 867 and 1588 cm -1, respectively [223]. The B2g
mode is optically inactive but has been observed using neu-
tron scattering at 127 and near 867 cm -1 [224]. Group theory
analysis predicts that only the 2Eeg modes will be Raman ac-
tive. The symmetry of the E2g modes restricts the motion of
the atoms to the plane and involves the in-plane bond stretching
motion of pairs of sp 2 C atoms as shown in Figure 52a. Two
different E2g modes occur because adjacent planes can vibrate
in phase or with the opposite phase; however, the energy separa-
tion between the two modes is small due to the weak interlayer
coupling. The Raman spectrum measured from single crystal
graphite by Tuinstra and Koenig (TK) [225] showed a single
line at 1575 cm -1 and on the basis of group theory, as well as
tentative calculations, this mode was assigned to the E2g mode
and is now universally referred to as the G peak. Second or-
der Raman peaks, associated with two-phonon states, have also
been observed in both single crystal graphite (SCG) as well as
in highly oriented pyrolytic graphite (HOPG) by Nemanich and
Solin [226] and by Wilhelm et al. [227]. A strong resonance is
observed from HOPG at around 2725 cm - l with weaker sig-
nals at ~2450 and ~3250 cm -1 . Wilhelm et al. showed that the
strong second order resonance has a shoulder at 2697 c m - l in
SCG and at 2690 cm -1 in HOPG. The overall spectrum from
2300 to 3300 cm -1 was observed to be uniform and strongly
polarized from which Nemanich and Solin concluded that the
second order spectrum was due to overtones not to combina-
tions of peaks.
In the case of microcrystalline graphite two peaks at
1575 cm -1 (G peak) and at 1355 cm -1 (later referred to as the
D peak) were observed [225]. TK noted a linear behavior of the
ratio of the intensities of the peaks ID/IG with the crystallite
size, La, obtained from X-ray diffraction. This linear relation-
ship indicates that the Raman intensity is proportional to the
amount of boundary edge present and proposed the relationship
ID C
= (4.15)
IG La
where C "-, 4.4 nm measured at 514.5 nm. TK interpreted the
presence of the D peak as being due to a relaxation of the se-
lection rules for an Alg breathing mode at the K zone edge
(Figure 52b). This mode is normally forbidden but in the pres-
ence of disorder if can appear; it is for this reason that it is often
referred to as the disorder peak. Some care must be exercised
with this description, as the term "disorder" can be misleading.
Table II. In-Plane Correlation Lengths as Measured by XRD and Ratio of
ID/IG for Different Types of Disordered Graphite
Sample La (/xm) ID/IG
SCG > 100 0
HOPG ~1 0
Flat micronic graphite 1-10 0.20
Ground natural graphite <5 0.36
High temperature pyrocarbon "~0.02 0.16
Wilhelm et al. studied the ratio of the areas in the D and G peak
and the measured values of La using X-ray diffraction (XRD)
for a range of different graphite based materials. Table II shows
that the ratio of ID/Ic is similar for a flat micronic graphite
sample and a pyrocarbon grown sample but the measured val-
ues of La differ by between 50 and 500. This implies that c-axis
disorder is not the dominating factor and there must be smaller
domains that are not observed by XRD and these play a signif-
icant role in the Raman process.
In addition to the D peak at 1355 cm -1, a number of
other peaks can appear depending on the level of imperfec-
tions in the graphite. In slightly damaged graphite (such as by
layer-edge facets producing by fractures, etc.) the D peak can
appear as a doublet at 1350 cm -1 (labelled D1) and 1370 cm -1
(D2). Vidano et al. [228] noted that the Raman shift in dis-
ordered graphite materials was dispersivemi.e., depends upon
the wavelength of the excitation. They investigated samples of
pyrolytic carbon deposited at 1800~ from methane, a glassy
carbon (GC), a highly oriented large crystallite graphite pre-
pared by compression annealing (CA), and a CA sample which
had been subject to Ar ion beam damage (ion-CA). Using an
excitation wavelength of 488 nm, they observed in the CA
graphite sample peaks at 1580 cm -1 (G peak) as well as sec-
ond order lines at 2695 cm -1 (G'1) and 2735 cm -I (G~). In
the disordered samples additional lines appeared at 1360 cm-1
(D peak) and 1620 cm -1 (D' peak) as well as a second order
peak at around --~2950 cm -1 (D"). They further noted that the
!
G~I and G 2 appeared to merge into one band, labelled G ~, as the
disorder increased.
As the wavelength of excitation increased, Vidano et al.
noted that the D, G ~, and D" bands red-shifted but that the G
and D t bands did not. Figure 53 shows the wavelength depen-
dence of the various peaks present. The D peak decreases from
~1360 cm -1 (488 nm) to ~1325 cm -1 (647.1 nm) whereas
over the same range of excitation the G t peak shifts from
2725 cm -1 to 2645 cm -1 . This is almost twice the shift of the
D peak and is consistent with the assignment that the G ~ peak
is an overtone of the G peak. It is interesting to note that the D
peak is absent from the highly oriented CA sample even though
the G ~ peak is present and also moves. In the ion-CA sample
the D peak is present and is observed to shift with excitation.
This red-shift was observed to be independent of the orienta-
tion of the excitation. As noted by Vidano et al. the magnitudes
of the band shifts are relatively small with a shift of the D band
 AMORPHOUS CARBON THIN FILMS
2750 b PC
V 9 GC
[]
9 CAPC
[] ~7 Ion
2700
"7
E
o 2650
e- J
p
= 1600 8 with the 2D graphite crystallite (the graphene layer). The Tu-
E
1500
1400
g ond order peaks are also present. This analysis is applicable to
I , I , I ,
1300 500 550 600
Excitation wavlength (nm)
Fig. 53. Variation of the position of (a) first order and (b) second order peaks
as a function of excitation wavelength.
of only 35 cm -1 and a shift of "~75 cm -1 for the overtone G'
band compared to a change of over 5000 cm -1 in excitation
frequency. From this the authors concluded that the red-shifts
of the Raman spectra could not be attributed to the large lon-
gitudinal acoustic dispersion from the zone center to the zone
edge.
A number of groups have proposed possible explanations
for the dispersive nature of some of the Raman peaks. Bara-
nov et al. [229] proposed that the dispersion was a result of
selective coupling between phonon and electronic states that
have the same magnitude of wavevectors (Ak -- Aq) and as
the photon energy rises (wavelength decreases) the number of
phonons modes around the K point increases. Matthews et al.
[230] have proposed that the peak shift is a result of the cou-
pling between the high frequency optical modes near the K
point with the transverse acoustic branch. They concluded that
all the optic phonons on this branch that have the same mag-
nitude Aq around the K point will contribute to the D and G'
bands. This is in contrast to Baranov et al. who proposed that
only those phonons in the K-M direction will take part. Ferrari
and Robertson [231] have addressed possible discrepancies be-
tween these different interpretations and have shown that the
precise shape and symmetry of the dispersion curves around
the K point are important. They noted that since the Alg mode
is singly degenerate that it is necessary to have a single degen-
erate band at the K point that is upward dispersing away from
K. The branch chosen by Matthews et al. is doubly degenerate
at the K point.
In summary, the first order Raman spectrum of ordered
graphite consists a single peak (G peak) at about 1580 cm -1.
Second order doublet peaks (G'1 and G~) also occur at about
449
2697 and 2725 cm -1 though their position depends upon the
incident wavelength. The G peak is associated with the in-plane
movements of sp 2 C atoms. The G peak is not dispersive though
its second order peaks are dispersive. In disordered graphitic
materials the extent of disorder present will determine the in-
tensity and position of the D peak. First the G peak will appear
to increase from 1580 to above 1600 cm -1 . This is, in fact, due
to the presence of an additional dispersive peak (D') at around
J 1610 cm -1 . The D peak, which is dispersive, appears at about
J
1350 cm -1 and increases in intensity as boundary associated
instra and Koenig relationship (at a given wavelength) is often
used to evaluate the in-plane correlation length, La, though this
can differ from the size of crystallite domain as measured by
.
XRD. The D peak is associated with the Alg breathing mode
and this is associated with the presence of sixfold tings. Sec-
I graphite as well as to disordered graphite all which have sp 2
650 contents ,~ 100%. In the next section the transition from disor-
dered graphite to amorphous carbon with sp 2 contents of less
than 100% will be presented.
4.4.4. Visible Raman Spectroscopy o f Amorphous Carbon
Tamor et al. [232] studied the visible Raman spectra and optical
properties of a wide range of amorphous carbon films deposited
using RF PECVD as a function of self-bias using feed gases of
CH4 and C6H6. The optical gap was observed to decrease with
bias voltage ranging from about 1.8 eV ( - 2 0 0 V bias) to less
than 0.8 eV ( - 1 2 0 0 V). Above about - 1 2 0 0 V the optical gap
begins to increase slightly. They used the original expression
from Robertson and O'Reilly [78] relating the optical gap (in
eV) to the cluster size. On this basis they concluded that cluster
sizes varied from 1 nm at the lowest bias to 2 nm at -1-200 V
bias. Visible Raman spectra were performed and 459, 515, and
628 nm. Two bands were observed around 1500 cm-1 (G peak)
and 1350 cm -1 (D peak). The Raman peak positions and the
ratio of the intensities of the D peak to the G peak are shown in
Figure 54 for the three different wavelengths. First, for a sample
deposited at a particular bias the G peak shifts to lower frequen-
cies as the excitation wavelength increases. This is in contrast
to the situation found in disordered graphite where no disper-
sion of the G band is observed. Second, as the deposition bias
is increased the G peak increases in frequency, eventually con-
verging on 1582 cm -1. Above a bias of about - 1 0 0 0 V the
peak position remains approximately constant. The ratio the D
peak to the G peak increases approximately linearly with bias,
as shown in Figure 54b, and for a given sample deposited at a
particular bias it is higher with longer wavelength excitation.
At that time the conventional interpretation of the ID/IG ratio
was based on the effects in disordered graphite. An increase
in the ID/IG ratio implied that the cluster size was decreasing
in contrast to what was inferred from the optical data. Tamor
et al. concluded that "either the assumption of small graphitic
domains and the associated optical gap calculations are inappli-
cable to amorphous carbon or else the ID/IG ratio is determined
450 SILVA ET AL.

1590 I 1600
(a)
I I .~. I I I
O
1570
"7 (a)
"7 0 9 ~ V V E 1580 00 I-
E O 0 9 V vO 9 I
t-
1550 O
O l .1
t-
O
.u}
i 1560
1530 O
r
O
Q.
m 1540
(D
(.9 1510 r
V
V (.9 1520
1490 - I I I I I- ..... I I
l I I I I I
-(b) V 1-- ,7 80 (b) I * *
V E
V 9
.ol 3 99 ao - "tll 70
9 O q,)
i O Ex
~Q 2 V O (.9 60
9 9 O
V 9 O
O O t-
V "r
50 00
9 o
0 I I I I I I 4o I I I I
250 500 750 1000 1250 1500 250 500 750 1000 1250 1500

Bias voltage (V) Negative self bias (V)

Fig. 54. (a) Position of the Raman G peak and (b) ID/IG ratio as a function Fig. 55. (a) Position of the Raman G peak and (b) G peak width as a function
of bias voltage at 459 nm (o), 515 nm ( I ) , and 628 nm (V). of bias voltage for DAC film deposited using RF PECVD using CH4 as feed
gas.

by factors other than the graphitic cluster size." They ruled 5

40nm 4nm lnm

out the former as the likely source of the discrepancy as the ' ' , , _

EELS spectra of their films indicated a strong graphitic struc-

4
ture present, and they concluded that the relative intensity of
the D peak (to the G peak intensity) in amorphous carbon is not _ i : AA
3
a useful indicator of graphitic cluster size. They interpreted the
o
laser wavelength and bias voltage dependence of the G peak in
terms of the amount of H termination in the clusters. For low : ~ 121

bias samples the clusters are terminated with H and the vibra-
O 2
%~
!i 'V *N A ~.
tional modes associated with the reduction in the number of 1 . . . . . . ~. . . . . J ~ ~t'-~ ~ A o
C edges and a weakening of the C - C bonds near the edge of
a clusters. In a later comprehensive study Tamor and Vassell _..... ~.: #1 : "
0
[220] studied a number of different DAC films and proposed
I I I I I I I
that the Raman shift observed at 600 c m - l is due to the pres- 0 20 40 60 80 100 120 140 160

ence of H. The incorporation of H leads to the greater presence
of sp 3 sites so that a-C film can be viewed as an alloy mixture
of the different sp2-based and sp3-based materials.
Tamor and Vassell also observed that for films deposited
from CH4 that the G peak moved up in frequency from 1520
to 1580 cm -1 as the self-bias increased to - 1 5 0 0 V and at the
same time the G width decreased from about 80 to 50 cm -1,
as shown in Figure 55. The G peak linewidth is affected by
cluster size, their distribution, as well as the stress in the film.
Nemanich et al. [233] and Shroder et al. [234] found that the
relative concentration and crystallite size are important in the
analysis of spectra. They showed that the vibration modes of
small crystallites can be described as phonons with an uncer-
tainty in the wavevectors Ak "-~ 2zc/d, where d is the size of
the crystallite. Schwan et al. [109] showed that for a range of
films deposited by different methods that the ratio of the ID/IG
peak depended on the G linewidth as reproduced in Figure 56.
The films examined were PECVD grown DAC:H [220], sput-
tered GAC [220], TAC deposited using laser ablation [220],
G linewidth (cm -1)
Fig. 56. ID/IG ratio vs G linewidth for DAC ([]), MEPD deposited DAC
(/x), magnetically confined DAC films (V), DAC films by Mariotto (o), sput-
tered a-C (e), TAC films ( I ) and TAC films using m a g n e t r o n sputtering with
Ar ion plating (A), and various graphites and other carbons by K n i g h t [245]
(0). Reproduced with permission from [109], 9 1996, A m e r i c a n Institute of
Physics.
TAC films deposited by magnetron sputtering [109], magnet-
ically confined PECVD [88], as well as graphite and disordered
graphite. All the films were examined using 514.5 nm excita-
tion. In the case of microcrystalline graphite the small linewidth
and low ID/IG ratio indicate high quality material. As the G
linewidth becomes broader there is a maximum in the observed
ID/IG ratio. Above a G linewidth of about 50 cm -1 the ra-
tio begins to decrease and under the TK relationship given in
Eq. (4.15) would indicate a crystallite size of less than 1 nm.
Davis et al. [81] did not observe clusters bigger than 0.5 nm
 AMORPHOUS CARBON THIN FILMS 451

1600 I I
in RF plasma deposited DAC films. The low value of ID/IG
and large linewidth for the TAC films indicate a very low con- E 1585
centration of sixfold rings. The deviation from the solid line r

._o
in Figure 56 of the TAC films deposited by unbalanced mag- .~ 1570
o
netron sputtering was attributed to the high stress in these films.
Finally it is worth noting that the position of the G peak also (.9 1555 I ! 9 9

depends on the amount of H present in the films. The peak was

"~Eo 300 (b~o
observed to shift to lower frequencies as the H concentration
250
increased. The loss of H helps to promote the formation of s p 2 .'I2_
bonds rather than s p 3 bonded C. 200
These results of the Raman measurements by Tamor et al. tll
19
n 150 J l i r
and Schwan et al. can be viewed in terms of an decrease in the I I I I
sp 2 content (with an increase of the s p 3 content) as the bias .o 1.2 (C
voltage is reduced. In summary, for an increase in the sp 3 con- ,- 0.8
tent, ~ 0.4
(i) the G peak becomes dispersive, 0 I I I I
0 1 O0 200 300 400
(ii) the G peak position decreases, and
(iii) the TK relationship for the ratio of the D peak to the G
Deposition temperature (~
peak breaks down and no longer reflects the in-plane
correlation length. At this point cluster sizes are Fig. 57. Variation of (a) G peak position, (b) G peak width, and (c) ID/I G
ratio as a function of deposition temperature for TAC films deposited using the
typically a couple of nm and ID/IG approaches 0.
FCVA technique.
Since the D peak is associated with the presence of sixfold
clusters, at higher levels of disorder greater cluster distortion
occurs and the number of such sixfold clusters will decrease. In
this way Chhowalla et al. [235] and later Ferrari and Robertson
[231 ] proposed that for small values of La, the intensity of the
D peak is indicative of finding a six-fold ring in the cluster and
is therefore proportional to the cluster area and therefore
._o
ID 2 (.9
m ~ La ~ M (4.16) m
Ic
Chhowalla et al. studied the effects of deposition temper-
ature on the Raman spectra of FCVA deposited TAC. The G
peak at ~ 1560 cm -1 was clearly observed in films deposited
at 30~ but at higher temperatures a D peak at 1350 cm -1 was
also observed and indicated the formation of sixfold graphitic
0
rings. The variations of the G peak position, G peak width, and 0 0.5 1.0 1.5 2.0
ID/IG ratio are shown in Figure 57. In conjunction with the
Tauc gap, EELS measurements, and resistivity they concluded 1/E~ (eV -2)
that films deposited at near room temperature consist of a small Fig. 58. The Raman ID/I o ratio against 1/E2 for a series of TAC films
number of short olefinic chains which keep the bandgap wide deposited at different substrate temperatures (o) and for series of films as a
and the resistivity low. As the deposition temperature rises the function of substrate bias (11).
sp 2 sites begin to condense into clusters of increasing size (re-
suiting in a reduction of the Tauc gap). Sixfold tings begin to
form, resulting in an increase of the ID/IG ratio. According to [107] and GC [236, 237]. GC, produced by the decomposi-
the Robertson and O'Reilly model, discussed in the section (op- tion of highly crosslinked polymers, is a nongraphitizing form
tical) for undistorted sixfold tings, the bandgap varies as the of carbon as the tangled graphite ribbons prevent the forma-
1 / M 1/2, where M is the number of sixfold rings. In this way tion of a proper 3D structure even at high temperatures [237].
the ratio of ID/IG should be inversely proportional to the square The visible Raman scattering from a GC samples can been
of the bandgap Eg, if the gap is determined by sixfold rings. seen in Figure 59 [237]. It can be seen that the spectrum con-
Figure 58 shows a linear relationship for the films studied by sists of two dominant peaks at 1360 cm -1 (D peak) and at
Chhowalla and also by using the data of Tamor et al. [232]. 1588 cm -1 (G peak). This latter peak has a broad shoulder at
There have also been a number of studies using Raman about 1615 cm -1, assigned to the D t peak. In the case of TAC
spectroscopy of the effects of ion implantation in both TAC films produced by the FCVA method only a broad band lying
452 SILVA ET AL.
, ! , , , i , , , i , , , i , , , i , ,
300
I I I I
B

gla 0.3
200
=3
A

v
. m
>,
e-
lxl
t"-
(D
t,-
m
..o t_
100
2xl
v

> ,
.8
c-
ID
lxl

2x1013 0
750 1000 1250 1500 1750 2000
I x 1013

R a m a n shift (cm -1)

undamagedta-C
1000 1200 1400
Wavenumber (cm "1)
Fig. 59. The effects of 200 keV Xe ion implantation on the Raman spectrum
of TAC implanted to the doses shown. Also shown for comparison is the Raman
spectrum of glassy carbon.
between the G and D peaks is observed. The Raman spectra
of the films implanted with 200 keV Xe ions are also shown
in Figure 59. It is evident that as the dose is increased above
1014 cm -1 the two broad bands become clearly visible and their
appearance is attributed to the formation of a high concentration
of s p 2 bonded C with good in-plane ordering. It is interesting
to note that in the study of 320 keV Xe implantation into GC
[236], the increased dose resulted in the initial broadening of
the G and D peaks at a dose of up to 2 • 1014 cm -2 and then
their subsequent merger into a single broad band at a dose of
6 • 1016 cm -2.
4.4.5. Ultraviolet Raman Spectroscopymprobing
Content
The cross-section for Raman scattering determines the strength
of a particular Raman peak. As discussed in the introduction
to Raman scattering, at visible wavelengths the contribution
from the s p 3 sites is overshadowed by the contribution from
the s p 2 sites. In order to examine the s p 3 sites it is neces-
sary to use lower wavelength excitations. One of the first uses
of UV Raman spectroscopy to examine the influence of s p 3
content was by Wagner et al. in their study of polycrystalline
diamond [238]. They showed that the Raman spectra from poly-
crystalline diamond films depended upon the grain size and also
the laser excitation energy. For a diamond film with grain sizes
in the region of 5 0 - 1 0 0 / z m , the Raman spectrum consisted
of a single sharp line at 1332 cm -1 when excited with light
of 2.33 eV energy. This line is the signature of the T2g mode
in diamond and is associated with s p 3 C - C stretching modes.
Fig. 60. Visible Raman spectra from TAC films with different sp 3 fractions.
The spectrum from the sample with the highest sp 3 content was taken by Xu
et al. using 488 nm excitation [54] and the remainder by Lifshitz et al. using
1600 1800
514 nm excitation [246]. The data have been fitted by a single BWF lineshape.
Only very weak scattering was observed in the 1500 cm -1
region, indicating very little scattering from the s p 2 regions.
However, as the laser energy was decreased a broad shoulder
appeared at lower frequency. For a polycrystalline film with
grains sizes of 15-100 nm, the vibration associated with the T2g
modes was only clearly visible with an excitation of 4.82 eV, a
broad but weaker peak around 1580 cm-1 was also observed at
this wavelength. As the laser energy decreased to 3.53 eV the
1332 cm - l was only just visible and the band at 1580 cm -1
had increased in size significantly. In addition a weaker band
around 1150 cm-1 began to appear. For successively lower en-
ergies this 1150 cm-1 band increased in intensity whereas the
two other bands began to merge. The band at 1150 cm -1 was
attributed to the s p 3 content in the film.
Gilkes et al. studied the presence of the s p 3 bonding in
FCVA grown TAC films using UV Raman (244 nm) spec-
the s p 3 troscopy [239]. In a more recent study the Raman spectra for
several TAC films with known s p 3 contents have been studied
[222]. Figures 60 and 61 show the visible (514/488 nm) and
UV (244 nm) Raman spectra for three TAC films with differ-
ent s p 3 contents. The visible spectra were all fitted with a BWF
lineshape along with a linear background subtraction. The vis-
ible Raman spectra from each of the films consists of a broad
peak centered around 1550 cm -1 associated with the G peak.
(The square shaped peak in the sample with the highest s p 3
fraction is the second order mode from the underlying Si sub-
strate. This sample has the highest optical gap and is the most
transparent.) No evidence of the D peak is observed, indicat-
ing that no sixfold rings are present. The UV Raman spectra
of the same samples shown in Figure 61 have two broad peaks
at 1100 and 1600 cm -1. It is evident from Figure 61 that as
the s p 3 fraction increases (or conversely as the s p 2 content de-
creases) the position of the peak of the G band shifts to higher
 AMORPHOUS CARBON THIN FILMS 453

I I I I I I I 1675 I I I I I I I I
[]
200 [] [] (a)_
1650 - D []
[]
[]
[] [] D

a::
._o 1625

150 o.
O 1600
:3
@l 0 o 9 ~i-1
~. 1575
(9
oSg 9 oOO 9 g l e
e- 100 n
1550
c,- 1 I I I I I I I
1 I I I [ I I I
300
"7, 9 S (b)-
50
g - 9 9
250
0.88 m
9 o ~ o9
g ID O O O Do i ~ I O D
200
(9 |
I I I I I 1
500 750 1000 1250 1500 1750 2000 150 -
t~ 9
100 - I I I I I I I [2 1-
R a m a n shift (cm "1)
0 200 400 600 800 1000 1200 1400
Fig. 61. Corresponding U V Raman (244 nm) spectra of the films shown in
Figure 60. The data have been fitted by two Lorentzian lineshapes. Annealing temperature (~

Fig. 63. (a) Position of the G peak and (b) width of the G peak as a function
1680 (a) u u u I J I of annealing temperature measured under visible (e) and UV (D) excitation.
[] _
~uE 1650 9
C
._o 9
"~ 1620 9 9
g v clusters as the s p 2 sites increase is possible. As the cluster size
1590 9 increases the bond order decreases with a resultant decrease in
1 I I I I I I the Raman frequency as s p 2 content increases. The other possi-
"~
~Eo 1120 (b) 9 I I I I I 1
ble explanation proposed by Gilkes et al. concerns whether an
c
.o
1095 v increase in the compressive strain will shift the Raman peak.
r The downward shift in the peak at 1100 cm -1 with increas-
R 1070 O Q 9 9 []
ing s p 3 fraction was attributed to the replacement of mixed
@
a.
1045
I I I I I I I
s p Z - s p 3 bonds with more s p 3 - s p 3 bonds. However, since these
s p 3 - s p 3 bonds are longer than the corresponding bond lengths
V
"b 0.32 - [] in diamond, the Raman shift is lower than reported in the UV
Raman spectrum of pure diamondmnamely 1150 cm -1. The
0.28 9
tight-binding molecular dynamic calculations by Wang et al.
0.24 9 9 9
[87] also suggest that in TAC in excess of 90% of the vibrational
0.20 t ~ I I I L I amplitude above 1600 cm -1 was localized on s p 2 sites. In ad-
0.3 0.4 0.5 0.6 0.7 0.8 0.9
dition the s p 3 stretching modes were found to be at 1100 cm -1 .
sp3/(sp2+sp3) Similar results were found by Drabold et al. [85].
Two more studies demonstrate the usefulness of UV Raman
Fig. 62. Peak position of (a) the 1650 cm -1 band and (b) the 1100 cm -1
band; (c) ratio of the intensity of the 1100 cm -1 and 1650 cm -1 band as a spectroscopy in studying the effect of annealing and also the
function of s p 3 fraction. Adapted from [222]. addition of N. Ferrari et al. [ 125] used UV and visible Raman
spectroscopy to study the effects of annealing of TAC films.
Using UV Raman the as-deposited TAC films consisted of two
frequency; the peak at 1100 cm -1 (T peak) decreases in fre- broad peaks at 1050 cm -1 and a peak at 1660 cm -1. They
quency and finally the intensity of the T peak increases. This ascribed the band at 1660 cm -1 to s p 2 olefinic C - C stretch-
behavior is more clearly seen in Figure 62a-c for samples de- ing modes (G modes) and the band at 1100 cm -1 to s p 3 C-C
posited by different groups using either FCVA or mass selected bond vibrations (T peak). They proposed that the shorted s p 2
ion deposition [222]. Note that in Figure 62c the peak inten- olefinic bands will produce Raman peaks at higher frequen-
sities rather than peak areas have been plotted. Gilkes et al. cies. By contrast the visible Raman spectra of the as-deposited
proposed that the peak at ~1600 cm -1 is most likely due to film consisted of a single broad peak at 1567 cm -1. Anneal-
the presence of paired s p 2 sites which are enhanced by UV ex- ing of the films resulted in a shift of the G peak (1560 cm -1
citation. This peak position is larger than the usual s p 2 G peak in the visible spectrum) to higher frequencies as shown in Fig-
at ~1550 cm -1 found using visible Raman spectroscopy, and ure 63a. However, the 1650 cm -1 peak in the UV spectrum
the change in this band's position was attributed to two possi- remains at about the same frequency up to an annealing tem-
ble reasons. First, the relative proportion of s p 2 pairs to large perature of 1000~ There was also a change in the width of
454 SILVA ET AL.
Im
I I OI 1670 - I
1.00 E] (a)
(a) "7,
1640 -
,.,,,
0.75
t/J .m
[] []
> t-

1610 -
0.50
r.-
o r

m _ 9 u _ E
0.25 fie
t~
1580 -
9 9 9

0 1" 9 ~176 el I I I - I i ! I I I
1550 I
I I ! i I I I I I I I I
0.5 oo
_
[] []
[]
[] [] []
[]
[] [] (b) - 1400 -
_
O
_
0.4 []
v
1300 - []
:D 0.3 r"-
v _ _

t,9 t/) 0
n
0.2
c-
[]
m
t~ 1200 -
E _ _
0.1 n,'
[] [] - 1100 - o
0 I I I I ! I I
/- I I I 1 I
0 250 500 750 1000 1250 0 2 4 6 8 10 12

A n n e a l i n g t e m p e r a t u r e (Oc) N content (at. %)

Fig. 64. (a) Ratio o f I D / I G under visible excitation and (b) ratio o f I T / I G
Fig. 65. Effect of nitrogenation on the positions of (a) G peaks and (b) D peak
and T peak under visible (e) and UV (D) excitation as appropriate.
under UV excitation.

180 I I I I I I I
(a) Q
9
9
9
the G peak observed in the visible Raman spectrum, as shown
i-. 160 - Q
in Figure 63b, from a width of ,~260 to less than 175 cm -] at
1000~ In the study by Merkulov et al. of a-C films with s p 3 v

.'g 140 -
contents which ranged from 20 to 75%, an increase in the G
position was also observed (from "~ 1580 to 1620 c m - ] ). How- W
0 120 73
ever, there was an increase in width of this peak. By contrast, D [] []
in the study by Ferrari et al. the width of the 1650 cm-1 peak O []
100 - I i I I I I i
remains at approximately 220 cm-1 up to 1000~ from where I I I I I I
it then falls. If the width of the G peak is taken as a measure of 0.9 -'(b) 9

_
the size of the domain the reduction in the G width indicates an
increase in the size of the s p 2 cluster. Changes in the relative 0
O.7-
peak intensities of the both pairs of peaks (ID/IG) in the visi- _

ble and (IT/IG) in the UV are also accompanied by changes in 0.5-

the positions and linewidths as shown in Figure 64. Some care
must be exercised with the interpretations of these peaks. How- I I I I I I
0.3 ?
ever, the increase in the intensity of the D peak in the visible 0 2 4 6 8 10 12

indicates the formation of sixfold rings. The ratio of the T band

N content (at. %)
to the G band (1650 cm -1) band is constant up to annealing
temperatures of 1000~ indicating that the s p 3 content in the Fig. 66. Effect of nitrogenation on (a) the widths of G peaks under visible (o)
films remained constant to 1000~ This interpretation was also and UV (R) excitation and (b) the ratio of ID/IG under visible excitation.

confirmed by EELS measurements and indicates the ratio of the

ID/IG cannot be related to the s p 3 content. Finally, it should be
noted that for annealing temperatures above 1000~ grains of spectrum from a non-nitrogenated film had a peak at 1548 c m - 1
/~-SiC were formed. The results of the Raman measurements (G peak) and a barely visible peak at 1377 cm-1 ( O peak). The
made using the two different wavelengths allowed Ferrari et al. UV (244 nm) spectrum from the same non-nitrogenated sample
to conclude that although s p 3 sites begin to convert to s p 2 sites consisted of two peaks at 1665 cm-1 and a peak at 1095 cm-1
at an annealing temperature of around 600-700~ these are not (T peak). The effect of nitrogenation on the peak position for all
detected by UV Raman. these four peaks can be seen in Figure 65. As the N content in-
Shi et al. [240] used both UV and visible Raman to explore creases the visible G peak only varies slightly in frequency and
the effects of nitrogenation of FCVA grown TAC films. The remains in the range 1568-1572 cm -], as shown in Figure 65a,
N content was determined by Rutherford backscattering spec- whereas the peak at 1665 cm -1 decreases by 55 cm -1, reach-
troscopy and by Auger electron spectroscopy and was 11.2 at.% ing 1610 cm -1 for the sample with 10.8 at.% N. The position
for the maximum concentration. The visible (514 nm) Raman of the D peak increases slowly from 1377 to 1412 cm -1. The
 AMORPHOUS CARBON THIN FILMS
position of the T peak shifts upward by 219 cm -1 from 1095
to 1314 cm -1 (10.8 at.% N). Shi et al. also reported changes in
the linewidths of the four peaks. The D peak increases from 149
(0 N) to 170 cm -1 at about 4.2 at.% and then remained approxi-
mately constant. The G peak under visible excitation decreased
only from 113 (0 N) to 106 cm -1 (10.8 at.% N). A small re-
duction was also reported in the G peak under UV excitation
from 110 to 105 cm -1. The behaviors of both G peaks under
visible and UV excitation are shown in Figure 66a. Shi et al.
reported that no clear trend was evident for the width of the T
peak with N. Finally it is evident in Figure 66b, that Io/IG in-
creased with N content but that no trend was reported for the
ratio of I T ~ I t . The increase in I D / I G increased and the re-
duction in width of the G peak with N was attributed to the
generation of larger clusters. The lowering of the position of
the G peak under visible and UV excitation could be attributed
to s p 2 clusters with larger s p 2 aromatic rings as opposed to
shorter s p 2 olefinic chains. The increase in the position of the T
peak with N incorporation can be explained by the replacement
of s p 3 - s p 3 bonds with s p 3 - s p 2 bonds, which are shorter and
therefore appeared at higher energies.
Both Shi et al. [240] and Ferrari et al. [125] addressed the
issue of strain and its possible implications for the position of
the G peak. It was noted by Ager et al. [241] that the posi-
tion of the G peak in TAC depends on the stress in the film. If
a highly strained TAC film relaxes though delamination, Ager
et al. showed that the position of the G peak changes by as
much as 20 cm -1. They found a shift of 1.9 cm -I GPa - l for
biaxial-plane stress in TAC. Shi et al. noted that the difference
in compressive stress between a non-nitrogenated film and one
with 10.8 at.% N is 5.6 GPa which would manifest itself as a
shift of 10.6 cm - l . However, the G peak under visible excita-
tion does not shift appreciably from which Shi et al. concluded
that stress was not significant as the source of shift in the G
peak. In the study by Ferrari et al. they showed near com-
plete stress relaxation of their samples by annealing at 600~
The stability of the G peak position and width in both UV
and visible excitation indicate that only minor modifications in
structure of the film have occurred. Finally it is worth noting
that although the s p 2 content in both the films of Shi et al. and
Ferrari et al. is increasing, the study by Shi et al. did not observe
a major shift in the position in the G peak whereas in the study
by Ferrari et al. the G peak increased by 33 cm -1 . The reason
for this discrepancy is not known.
In summary using UV Raman allows the s p 3 content of
amorphous carbon films to be examined. The s p 3 peaks are
found at 1100 c m - 1 and are referred to as the T peaks. The peak
associated with s p 2 vibrations appears at higher wavenumbers
under UV excitation than the corresponding peak under visi-
ble excitation. Visible Raman scattering allows probing of the
s p 2 content as these are resonantly enhanced. The D peak is the
signature of sixfold rings and the G peak is indicative of s p 2
bonding and can be seen in both in aromatic rings as well as in
olefinic chains.
455
4.5. Conclusions
A considerable amount of information has been amassed con-
cerning the study the optical properties of amorphous carbon.
It is therefore useful to bring some of the main conclusion to-
gether. First, while the exact nature of the relationship between
the energy gap and the size of clusters is not fully established,
the general view persists that the larger the size of the cluster the
small the energy gap. The role, if any, of distorted clusters, in
particular, is not fully understood. Early models for the DOS as-
sumed symmetric Gaussian bands but more recent experiments
have cast into question whether this is the case. FTIR and Ra-
man spectroscopy are powerful complimentary techniques and
the development of UV Raman has helped to probe the role s p 3
sites play.
5. DEFECT STUDIES OF A M O R P H O U S CARBON
5.1. Introduction
In order to gain further understanding of the role played by :r
states lying within the bandgap of a-C films, there has been a
considerable body of research performed to look at the "defect"
states especially those near the Fermi level. As noted previ-
ously s p 2 clusters may form into aromatic ringlike structures
or olefinic chains which may or may not become distorted. The
extent to which these clusters remain undistorted or become
distorted is largely determined by the disorder within the a-C
network with disorder tending to oppose clustering. Isolated
s p 2 sites from an individual C atom may also form and give rise
to a "dangling bond" (DB). The DB in a-Si:H has been charac-
terised by a number of different techniques, one of which has
been electron spin/paramagnetic resonance [ 163]. The DB in
a-C is analogous to the CH3 radical, and low temperature EPR
measurements made by Fessender and Schuler [247] showed
that the CH3 radical can be considered as three C-H fragments
oriented 120 ~ apart in a plane. In this way the DB in amorphous
carbon is planar rather than pyramidal-like as in a-Si.
From the discussion of Section 4, the density of states in the
energy gap is principally determined by the zr states made up of
(i) isolated s p 2 sites, (ii) undistorted s p 2 clusters (in the form
of chains or rings), and (iii) distorted s p 2 clusters. Whether any
of these different possible structures will be paramagnetically
active depends on whether there is a new unpaired electron spin
available or not. Undistorted odd membered rings, such as five-
and seven-membered rings, will produce a state which is near
the Fermi level and will be EPR active. Doubly occupied states
will not be EPR active.
The basic theory behind EPR is now well established and the
interested reader is referred to the book by Wertz and Bolton
[248] for further information and to the book by Poole [249]
for more experimental information. In its most simplistic form,
EPR occurs when there is a resonant absorption of microwave
power, of frequency v, between energy two levels. These energy
levels induced by a magnetic field, of strength B, are known
as the Zeeman levels [248]. The relative population of these
456 SILVA ET AL.
energy levels is given by the standard Boltzman factor. For a
defect with a net unpaired electron, giving a spin S of 89 the
resonance condition for absorption of electromagnetic radiation
is
hv = glzBB (5.1)
where h is Planck's constant and #B is the Bohr magnetron.
The remaining parameter in Eq. (5.1) is known as the g value
and is specific to each type of defect present. EPR experiments
are carried out by placing the sample under investigation at
the center of a resonant microwave cavity (typically X band
-~9.9 GHz) and monitoring the reflected microwave power. At
resonance the absorption of microwaves alters the reflected mi-
crowave power. Usually, since the amount of reflected power is
small, modulation techniques are used in which a slowing vary-
ing magnetic field (usually 100 kHz) is superimposed upon the
Zeeman field. In this way the spectrum that is usually recorded
is the first derivative of the absorbed microwave power. The g
value for a particular resonance is calculated from Eq. (5.1) us-
ing the microwave frequency and the magnetic field at which
the derivative of the microwave absorption is zero. This is often
referred to as the zero crossing g value, go. For a free elec-
tron, the g value would be 2.0023 and any deviations from this
value are determined by the extent of the spin-orbit interaction,
which in turn is related to the localization of the electron. By
performing a double integration of the EPR signal and by com-
parison with a known standard, a value of the concentration of
the paramagnetically active species can be determined. Much
of the early work on a-C based materials [250, 251 ] using EPR
has concentrated on determining how the g value and spin den-
sity vary as a function of either deposition or postdeposition
conditions but ignoring other important information such as the
variation in the linewidth, lineshape, and relaxation times, all of
which are now discussed in detail.
5.2. Lineshape Analysis and Relaxation Effects
Since EPR spectra are usually recorded in derivative mode, the
linewidth is usually taken as the peak-to-peak linewidth (ABpp)
and is usually expressed in Gauss or mT. This can be related to
the full width half maximum (AB1/2) of the absorption pro-
file if the lineshape of the resonance is known. The lineshape
is usually determined by whether the broadening of the sig-
nal is either homogeneous or inhomogeneous. Homogeneous
line broadening processes are usually described as those pro-
cesses that affect every defect identically, so that each defect
center in the sample is capable of absorption of microwave en-
ergy over a (narrow) range of frequencies, but this range of
frequencies is identical for each defect in the sample. Impor-
tant sources of homogeneous broadening include the dipolar
interaction between like spins and motienal effects arising from
fluctuating magnetic fields arising from exchange or hopping
of spins; such broadening mechanisms will tend to produce a
Lorentzian lineshape with AB1/2 -- 1.7321ABpp [249]. Inho-
mogeneous line broadening is the overall effect of an ensemble
of defects, each of which has its own unique range of frequen-
cies for absorption. Inhomogeneous broadening results from the
defect experiencing different magnetic fields and the principal
source in amorphous materials discussed here is from the hy-
perfine interaction with nuclear spins and high levels of atomic
disorder. Inhomogeneous broadening tends to produce a more
Gaussian lineshape with AB1/2 = 1.1776ABpp [249]. A more
useful way to look at the different types of broadening, and one
that reflects the dynamic nature of the spin system, is to regard
homogenous broadening as arising from a particular broaden-
ing mechanism that is fluctuating rapidly compared with the
time associated with a spin transition. If an EPR resonance is
being broadened independently by two different mechanisms a
convolution of the two lineshapes will result. A convolution of
two Lorentzian lineshapes will produce a Lorentzian lineshape
and the convolution of two Gaussian lineshapes will produce a
Gaussian lineshape. In the case of a line that is independently
broadened by both Lorentzian and Gaussian effects a Voigt pro-
file will result.
Since EPR is based upon transitions between discrete energy
levels it is important to understand how the absorbed microwave
energy is dissipated. This is often discussed in terms of the
spin-lattice relaxation time, T1, and the spin-spin relaxation
time T2. The spin-lattice relaxation time is a measure of the
how well energy can be dissipated from the spin system to
the lattice; T2 is a measure of the spin-to-spin effects. The
relaxation times can be determined from the behavior of the
peak-to-peak amplitude of the (derivative) spectrum hpp and
A Bpp with increasing microwave power as described in [249].
The spin-spin relaxation time can be determined directly from
the spectrum before the onset of saturation from the equation
2
T2 -- ~/-~y ABpp (5.2)
where V is the gyromagnetic ratio. This approach is only strictly
correct for homogeneously broadened (Lorentzian lineshape)
lines but has been generalized for other lineshapes [249]. Since
7"1 and T2 are sensitive to the presence of time averaged fields
which can be produced by the motion of spins through ex-
change or hopping, their variation from sample to sample can
give important information about the interaction of the spins
within the defects.
In summary:
(i) g value: Each defect center has a particular g value and
as such EPR is able to distinguish between different
centers. In the absence of the spin-orbit interaction the
g value would be that of the free electron 2.0023 and
the deviation of the observed g value from this value is
related to the degree of localization of the center.
(ii) Spin concentration: The concentration or density of a
defect center can be determined if the spectrum is
compared with that of a known standard such as Varian
pitch in KC1 or DPPH (1,1-dyphenil-1-2-picryl-
hydrazil). Care must be taken to account for differences
in the conductivity of the underlying substrate so that
 AMORPHOUS CARBON THIN FILMS
1 I I I I i
,,,,,=
t..-
~
n,"
LU
I I I I I o
0.3450 0.3475 0.3500 0.3525 0.3550
Magnetic field (Tesla)
Fig. 67. Room temperature EPR spectrum from an PAC/Si film of 138 nm
thickness. The spectrum has been fitted with two lines, one associated with C
unpaired electrons and the other associated with defects at or near the filrn/Si
interface. The individual lineshapes of the two defects are also shown.
that Q-factor of the cavity is not significantly reduced.
High resistivity substrates are usually used.
(iii) Linewidth and lineshape: The peak-to-peak linewidth
( A Bpp) and the lineshape can give information about
the dynamics of the spin system. Homogeneous
broadening arises if the static plus time averaged
magnetic fields are the same and will tend to lead to a
Lorentzian lineshape. Inhomogeneous broadening will
tend to produce a more Gaussian lineshape. A Voigt
profile will result from the convolution of a Lorentzian
with a Gaussian lineshape.
(iv) The spin-lattice relaxation time TI and the spin-spin
relaxation time T2 are sensitive to the fluctuations of
fields which can arise from hopping or exchange. Long
values of T1 (> 10 -4 s) indicate that the unpaired
electron has a weak interaction with the lattice.
5.3. g Values
Table III shows the measured zero crossing g values, linewidths
and shape, spin densities, and hydrogen content for a range of
a-C samples. The first point to note is that the smallest de-
fect concentrations (<1018 cm -3) are found in PAC films and
it is from these samples that the greatest variation in g value
from 2.0029 to 2.0045 is observed. In the samples measured by
Sadki et al. [252], the large g value of 2.0045 was attributed
to the interaction of the unpaired spins with nearby O atoms.
The presence of O was confirmed by FTIR analysis of their
films. By contrast no evidence of O contamination was ob-
served in the films deposited by PECVD [86] and examined by
Collins et al. [217]. They reported high zero crossing g values,
go, and that go, A Bpp, and lineshape as well as the areal spin
concentration, NA, were dependent upon the film thickness.
457
I I I I I i I
1.2
eo0
o.9 J
2 /
0.6
t,--
0.3
/
~" I I I I
0 100 200 300 400 500
Film thickness (nm)
Fig. 68. Variation of the areal spin density with film thickness for the Si re-
lated defect (o) and for the carbon related center ( I ) .
Figure 67 shows the observed EPR spectrum from an PAC/Si
film of 138 nm thickness. Collins et al. reported that as the film
thickness increased the EPR signal became less symmetric and
the linewidth larger. They observed that for films below 60 nm
thickness go remained constant at about 2.0050(3), ABpp at
about 0.56 mT, and NA at about (5 4- 2) x 1012 cm -2. How-
ever, for films greater than about 60 nm thickness go tended to
decrease, reaching a value of 2.0046(2) for a film with a thick-
ness of 481 nm. They also showed increases with thickness of
A Bpp and NA, but in the case of NA the increase was slower
than the increase in the film thickness.
This behavior of the spin density and go on the thickness
of film was explained on the assumption that the signal is
the superposition of two lines of different g values. The first
defect has g ~ 2.0053 and has a areal concentration indepen-
dent of film thickness, and the second has g value --~ 2.0029
whose areal concentration increases linearly as the film thick-
ness increases. The g value of the former center is typical of
that found ion implanted Si which is usually attributed to Si
related defects [253] and could originate from the film interfa-
cial region and/or the silicon substrate. Spectra recorded from
the Si substrate alone produced a weak, symmetric line with
g -- 2.0053(4) and an average value of NA -- 2 • 1012 cm -2.
It was reported that all of the spectra from the PAC/Si samples
could be fitted to the superposition of two Lorentzian lines: one
with g ----- 2.0053(3), A B p p = 0.56 mT and the second with
g -- 2.0029(3), A B p p - - 0.83 mT. The best fit to the mea-
sured spectrum using the above parameters for the PAC/Si film
of 138 nm thickness is shown in Figure 67. Also shown there are
the lineshapes of the two individual defect centers. The values
of NA for both lines as a function of film thickness are shown in
Figure 68. The areal spin population of the g ~ 2.0029 line is
proportional, within error, to the film thickness and implies that
it is associated with C unpaired spins in the bulk of the film.
From the slope of NA versus thickness (dashed line) a volume
458 SILVA ET AL.

Table III. Zero Crossing g Values, Peak-to-Peak Linewidths, Spin Densities, and H Content for Different Amorphous Carbon Films

Zero crossing A Bpp (mT), Spin density H content

Type of carbon g value (error) lineshape (cm - 3 ) (at.%) Reference

PAC 2.0045 0.8 L+G 1.5 x 1017 45-50 [252]

2.0040 0.8 -- 7.3 x 1017 57 [255]
2.0035 0.76 L 6.0 x 10 TM >22 [257]
2.0029(3) 0.83 L 2.3 x 1017 45-50 [217]
2.0029(2) -- L ~1018 64 [263]
2.0029(1) 1.5 -- 5 x 1017 [277]
DAC 2.0031 (2) -- L 1021 0.26 [263]
2.003 0.3 L " 2.9 x 1019 -- [273]
2.0028 0.4 L 4.5 x 1020 0.25 [252]
2.0027 0.27 L 2.0 x 1020 -- [278]
-- 0.3 -- 1.6 x 1020 [279]
2.0036 0.73 L 1.3 x 1020 [255]
TAC 2.0024 0.44 L 1020 -- [260]
TAC 2.0024 0.36 G 1020 -- [260]
TAC 2.0023 0.34 1.4 x 1020 g - 1 __ [267]
TAC:H -- 0.18 0.8 x 1020 0.23 [259]
TAC:H -- 0.25 1.5 x 1020 0.25 [259]
TAC:H -- 0.40 3.0 x 1020 0.28 [259]
GAC 2.0024(2) 0.31 L 1020 -- [262]
2.0027(2) 0.42 L 1019 [263]

L = Lorentzian, G = Gaussian.

1 0 21 ___I-. I I I I I I
concentration, Nv, of (2.3 -t-0.3) x 1017 cm -3 is obtained. Fig- (a)3
r _

ure 68 also shows that the area concentration of the g -- 2.0053 E oc~ 9 v
_

10 20 V
line is independent of the film thickness and the average value v
O V _
_

of NA for this line is (5 4-2) z 1012 cm -2. These results indicate V 9 _

1019
t-
V _
_

that for low defect density polymeric PAC/Si films of thickness ,lo
[]
less than 200 nm, up to 50% of the paramagnetic defects present .m
t- 10 TM
~D
Q.

are not associated with the C related centers but with Si related
1017
centers which originate from the PAC/Si interface region and/or -i 9 I I l I I
i I i I ] 1 I
the underlying substrate. 1.6 (b)-
9 []
In a study of RF sputtered a-C:H:Si films, DeMartino et al.
I-
[254] showed that the observed g value varied from 2.0057, for v
E 1.2
r
[]
samples deposited at high Sill4 flow rates, to 2.0027 for low
0.8 -1:3[-1
"O

Sill4 flow rates. They also reported that a wide range of phys- V
V
r
ical properties could be obtained from the films by changing 9 9 V V -
.--I
0.4 9 9 9
the Sill4 flow rates. Films that had graphiticlike characteris-
tics in the absence of Sill4 took more diamondlike properties 0 I 1 I i 1 1 I
0 100 200 300 400 500 600
(high Knoop hardness, low energy gap, and high spin density
3 • 102o cm -3) with the addition of silane. They noted that
Negative self bias (V)
the spin density was larger for films possessing the lower g
value and attributed this to the fact that addition of silane will Fig. 69. Variation of the (a) volume spin density and (b) peak-to-peak
linewidth with DC negative self-bias for three sets of films from Barklie et al.
tend to form more s p 3 C due to the much larger H presence in
(e) [256], Ristein et al. (r~) [255], and Zeinert et al. (V) [257].
the plasma.

5.4. Spin Densities Ristein et al. [255] and Barklie et al. [256] both sets of films
The volume spin densities, Ns, and A Bpp for three series of were deposited by RF plasma decomposition of either only CH4
hydrogenated a-C films as a function of negative self-bias [255- or a mix of CH4 (10%) and Ar (90%), respectively. Films were
257] are shown in Figure 69. In the case of the two studies by deposited on the powered electrode in each case and the RF
 AMORPHOUS CARBON THIN FILMS
I I I I 1. 7
1021
[]
r %
E 1020
to [] []
v
u~
t-
(9
-o
r
. m
1019
Q,.
O0 -~7~V 00
V
10 TM V varied from 0.38 to 0.69 mT, though no clear trend was ob-
1 I-=
0 100 200 300 400 500
Energy (eV)
Fig. 70. Variation of volume spin density for three sets of TAC films grown
by the FCVA method (,) [258], magnetron sputtering (MS) with Ar-ion plating
(~7) [280] and plasma beam source (O) [259].
power was adjusted which resulted in different values of the
negative DC self-bias. In the study of Zeinert et al. [257] the
films were produced by RF magnetron sputtering of a graphite
target in an argon plasma containing 10% H. The results from
both sets of PECVD grown films show a similar rapid increase
in spin density with bias up to a bias o f - 100 V and the spin
density remains constant at about a value of 1020 cm -3. The
films produced by magnetron sputtering also show an increase
in the spin density but only reach a density of 1020 cm -3 at
a negative self bias of 490 V, much higher than the PECVD
grown material. The peak-to-peak linewidth initially increases,
reaching a maximum also at about - 1 0 0 V bias, and then
decreases for the PECVD samples whereas the linewidth is ini-
tially smaller and then decreases. A detailed discussion of the
behavior of the linewidth will be given in the next section.
The spin densities for three sets of TAC(:H) films deposited
under different ion energies are shown in Figure 70. In the case
of the TAC films grown from the FCVA method by Amaratunga
et al. [258] the spin density decreases from about 1020 cm -3 for
C ion energies below 25 eV to about 5 x 1018 cm-3 and remains
below 1019 cm -3 for ion energies below 300 eV. The spin den-
sity then rises again at higher ion energies. It was reported in
this study that Ns was lowest when the s p 3 content was about
60-70%. In the case of the films deposited using DC-biased un-
balanced magnetron sputtering in the presence of Ar-ion plating
described by Schwan et al. [109], spin densities of less than
5 x 1018 cm -3 were measured for a range of Ar ion plating
energies. The lowest spin concentration of 1.2 x 1018 cm -3
was measured for energy of 85 eV. In the case of TAC:H films
deposited using a plasma beam source derived from acetylene
[259], the spin density decreased from a value of 3 x 1020 cm -3
at a C ion energy of 92 eV to 8 x 1019 cm -3 at 266 eV. In these
films the H content varied only from 27 at.% (92 eV) to 23 at.%
(266 eV).
459
Gerstner et al. [110] have also used the FCVA technique
to prepare TAC and deposited films with substrate biased in
the range of 0 to - 1 7 5 0 V. Films deposited on Si substrates
with biases between 0 and - 5 0 0 V readily delaminated due to
the high internal stress. Films deposited at higher biases had
greater adhesion to the substrate. These films together with
their substrates were ground into a power and EPR measure-
ments were made on the mixture. Gerstner et al. reported that
the EPR spectrum consisted of two Lorentzian lines, one with
g -- 2.0028(1), while the other was associated with the Si dan-
gling bonds which was attributed to the substrate being ground
into a powder. The linewidth associated with C related defects
served as a function of deposition of bias. For samples which
delaminated from the substrate a small reduction in the spin
density with bias (5 x 102~ cm -3 at zero bias to 2 x 102~ cm -3
at - 4 0 0 V bias) was reported. In contrast to the results of Ama-
ratunga et al. [258] and Schwan et al. [ 109] no minimum in the
EPR signal with bias was reported.
Fusco et al. [260] reported that the EPR signal from TAC
grown by FCVA consisted of two centers both, with g =
2.0024, but one having a Lorentzian lineshape and the other
having a Gaussian lineshape. They interpreted the Lorentzian
line as being due to clustered C centers and the Gaussian line as
being due to disorder. Since TAC is known to have a spZ-rich
surface layer it is possible that some of the observed EPR sig-
nal originates from this layer and not from the bulk of the film.
Finally Palinginis et al. [261] have measured defect densities
using drive level capacitance profiling. They found in undoped
TAC a uniform defect density of (3.5 + 1.0) x 1017 cm -3
measured at room temperatures. From measurements at dif-
ferent temperatures they were able to account for thermally
activate defects and the found that the total defect density is
(6 • 1.5) • 1017 cm -3. For TAC:N (n-type) they observed
an order of magnitude higher defect concentration. Since the
EPR density is typically 10 20 cm -3 in TAC they accounted for
the difference between the two defect density measurements by
noting that EPR measures the neutral centers. Drive level capac-
itance profiling measurements examined transitions of the type
D + --+ D O + h and D O --+ D - + h, though the latter transition
is unlikely to occur due to the high correlation energy. Ad-
mittance measurements revealed an areal density greater than
2 x 1012 cm -2 at the film/Si interface.
Finally Demichelis et al. [262] reported that in sputtered a-C
(GAC) that a g value of 2.0024 is obtained. This is much closer
to the free electron g value and would imply a high degree of
electron delocalization. Fancilulli et al. [263] reported that the
best fit to the EPR spectrum came from a superposition of a sin-
gle Lorentzian and a single Gaussian line. Clearly the different
deposition conditions and whether H is present or absent have
a major influence on the spin density. By suitable choice of de-
position conditions, however, it is possible to reduce this value
and yet retain the semiconducting properties of the films.
The results of the EPR measurements show that the lowest
spin densities are found in PAC films which usually contain the
highest concentration of H. As the deposition energy increases
460 SILVA ET AL.
, , ,
540
. ,
3450 3470 3490 3510 3530 3550
Magnetic Field [G]
Fig. 71. Room temperature EPR spectra showing the effect of changing the
negative self-bias from 50 to 540 V. The smooth lines are computer fits. Only
Lorentzian fits are shown for Vb = 100, 190, and 540 V. For Vb = 50 V,
Lorentzian (L) and Gaussian (G) fits are shown but the best fit has a Voigt
(V) lineshape. The peak-to-peak linewidths have been normalized. Reproduced
with permission from [256], 9 2000, American Physical Society.
C - H bonds begin to break and are replaced with C - C and C = C
bonds. The lower concentrations of H present and the higher ion
energy result in unpaired electron and an increase in the spin
density. It is also worth noting that the spin density from TAC
films may mainly arise from the spZ-rich surface layer. Even at
these high spin densities ( ~ 1020 cm -3) only a tiny fraction of
the sp 2 states are paramagnetic. If a typical hydrogenated film
has a density of 1.8 g cm -3, 40 at.% H, and an sp 2 content of
0.2, then there are over 10 22 ~ states cm -3. In the PAC:H films
the spin concentration is 1 spin per 105 zr states. In this way the
EPR active centers are the exception rather than the norm.
5.5. Linewidths, Lineshapes, and Relaxation Effects
5.5.1. Motional Effects
As discussed previously while the g values and spin densities
arise from "static" properties of the defect centers, the linewidth
and shape together with the relaxation times give important
information about the "dynamic" response of the defects. Fig-
ure 71 shows the spectra from DAC:H/Si samples deposited at
room temperature on the driven electrode of capacitively cou-
pled PECVD system described previously [88]. Feed gases of
CH4 (10%) and Ar (90%) at a constant pressure of 300 mTorr
were used and the RF power was varied such that the negative
self-bias was varied from - 5 0 to - 5 4 0 V [256]. The variations
of the spin densities and linewidths with bias have already been
shown in Figure 69. As can be seen from Figure 71 increas-
ing the self-bias results in a narrowing of A Bpp from 1.42 mT
( - 5 0 V) to 0.29 mT ( - 5 4 0 V). In addition it was reported that
the lineshape changes to one that can be fitted to a Voigt pro-
file for a self-bias of - 5 0 V to one that is close to a Lorentzian
lineshape at - 1 0 0 V. At higher biases all of the lineshapes ob-
served could be fitted to a Lorentzian lineshape. In order to
analyze the changes in the linewidth and lineshape with bias it
is worth recalling that a Lorentzian lineshape will result from
either dipolar broadening between like spins or from the ef-
fects of spin motion such as hopping or exchange. For dipolar
broadening in magnetically dilute materials, Abragam [264] has
shown that the half-width at half height of the integrated spec-
trum AB1/2 (measured in Gauss) can be related to spin density
of Ns measured in cm -3 via
1 27r 2
-AB1/2- glz]3Ns (5 1)
2
Recalling that for a Lorentzian line ABpp = AB1/2/~/c3 gives
ABpp = 8.12 • 10-2~ (5.2)
For the three series of samples deposited at different biases
Vb discussed in the previous section, Barklie et al., observed
a Lorentzian lineshape was for biases of - 1 0 0 V and greater
[256]. At Vb -- --100 V and the measured values of A B p p =
1.22 mT and Ns = 1.5 • 102~ cm -3, Eq. (5.2) gives a predicted
linewidth 1.22 mT and indicates that no other factor is required
to explain either the linewidth or lineshape for this film. Ris-
tein et al. [255] report that in their DAC:H films a Lorentzian
lineshape is observed at a bias o f - 5 0 V and greater. At a bias
o f - 100 V, the value of A Bpp is 1.46 mT and the spin den-
sity was measured to be only 1.3 x 1020 cm -3. Equation (5.2)
would predict a linewidth of 1.1 mT, slightly smaller than that
measured.
For the films measured by Zeinert et al. [257], at a bias
o f - 4 0 9 V, Ns -- 7.5 • 1019 cm -3 and the measured value
of A Bpp is 0.66 mT. Dipolar broadening alone would con-
tribute 0.61 mT. At higher biases in both the sets of samples
measured by Barklie et al. and Ristein et al. the spin density
increases to about 1.5 • 1020 cm -3. Since the value of Ns
does not change significantly in the bias range from - 1 0 0 to
- 3 0 0 V, Eq. (5.2) would predict that it should remain close
to 1.12 mT. However, as seen in Figure 69 there is a continu-
ous decrease in the linewidth in this range of biases and also in
the RF sputtered samples at even higher biases. This is indica-
tive that another mechanism is present which is determining
the observed linewidth and so such reductions in linewidths are
consistent with the presence of motional effects resulting from
exchange or electron hopping.
In order to test the hypothesis that motional effects are occur-
ring Barklie et al. measured the spin-lattice T1 and spin-spin T2
relaxation times for their samples as a function of bias using the
power saturation method [249]. They observed T1 to decrease
from about 1.5 x 10 - 6 S at gb = -- 100 V to 3.0 • 10 - 7 S at the
highest bias they investigated ( - 5 4 0 V). Simultaneously there
was an increase in T2 from 4.5 • 10 -9 s to 2.0 x 10 -8 s over
the same bias range, as shown in Figure 72. Using the approach
described elsewhere [265], it can be shown that if the dipolar
interaction is characterized by a frequency COp and a fluctuating
magnetic field is characterized by a correlation time re, then
narrowing will occur if Ogp < 1/re. In terms of re, TI and T2
 AMORPHOUS C A R B O N THIN FILMS 461

' ' ' ' C'a~- Table IV. Variation of Spin-Lattice T 1 and Spin-Spin T2 Relaxation Times
car) 10 "5 r
for Different Forms of Amorphous Carbon
_
_

: 9
_
_

E 10 -6 r Type Lorentzian Temperature

_

_
9 9 9 9 -
r

._o
_

of component behavior
10 .7
carbon T 1 (s) T2 (s) ABpp (mT) of ABpp Reference
_
_
_
_

x _ [] [] [] -
10 -8 O -~
PAC 3 • 10 - 4 6 • 10 - 9 1.50 -- [256]
_

n," _

10 -9 2 x 10 - 4 -- -- decreases [263]
I I 1 I
I I , , I i k/'bk- DAC 2 x 10 - 7 -- -- decreases [263]
100
o 2.5 • 10 - 6 5 • 10 - 9 1.42 [256]
90 O
r TAC < 10 - 7 1.8 • 10 - 8 -- -- [263]
8O O
r DAC 2 • 10 - 7 2.5 • 10 - 8 -- -- [256]
o O
o 70 -- 4.2 • 10 -7
0
60 - - 0

o
50
I I I 1
0 100 200
Bias voltage (V)
Fig. 72. Variation of the (a) spin lattice 7"1 (m) and spin-spin T2 (E3) relaxation
times and (b) sp 2 content measured by EELS as a function of negative self-bias.
can be expressed as
1 2),2B 2
and 1
r, 1 r2
where B 2 is the magnitude of the magnetic field associated with
fluctuation, g is the gyromagnetic ratio of the electron and COp --
),2B 2, and COo is the Larmor frequency. In the case of COp <
COc < COoEq. (5.3) reduces to
1 2COcCO2p
and
7'1 COo
2 T2
so that the correlation frequency of the fluctuation can be deter-
mined from the relaxation times via
IT2]
~Oc ~ oJo ~
For the sample deposited at - 5 4 0 V the measured relaxation
times are T1 -- 3.0 • 10 -7 s and T2 = 2.0 • 10 -8 s, resulting in
a correlation frequency of 1.1 • 101~ rad s -1 . The frequency of
the dipolar field cop is given by (COc/ T2) ]/2 and comes to 7.4 •
108 rad s -1 . The correlation frequency can thus be seen to be
higher than the dipolar frequency with the result that the dipolar
line is being averaged out by the effects of the fluctuating field.
Using Eq. (5.3) the magnitude of the fluctuating magnetic
field (Be) 1/2 is estimated to be about 4.2 mT. If no fluctuations
were occurring t h e n 1ABpp should be equal t o (B2) 1/2, for a
value of 4.2 mT a spin density in excess of 3 x 10 20 cm -3
would be required. Since the measured spin density is only
3.5 • 1019 cm -3 it was argued that this is evidence of clustering
of spins at this bias and that the observed linewidth narrowing
I I t
300 400 500 600
was a result of the increasing strength of the exchange interac-
tion, rather than electron hopping. This increase in the exchange
in interaction is due to greater delocalization of the spin wave
functions associated with the increase in the sp 2 content of the
films as shown in Figure 72b. The sp 2 content, as measured by
EELS, increased from about 60% to close to 100% at the high-
est biases.
Additional evidence for exchange interaction as the reason
for the linewidth narrowing comes from the similar behavior
2B2
= F 2 B 2 re + )' of T] (becoming shorter) and T2 (becoming longer) in solid
1 + o02 c2 solutions of DPPH dissolved to different concentrations in
(5.3) polystyrene [266]. This is due to the increasing strength of the
exchange interaction though in this case it is as a result of the
higher density of paramagnetic centers rather than greater delo-
calization of the spin [266]. The calculation just discussed can
also be used to explain why the static dipolar field can be used
for the sample deposited at - 100 V. In this sample the measured
2
relaxation times are T1 -- 1.5 x 10 -6 s and T2 -- 4.5 x 10 -9 s.
1 COp This results in coc -- 2.4 x 109 rad s-l and COp -- 7.3 x 108 rad
~ (5.4)
coc s -1 . In this case coc is just fractionally larger than COp, so that
the fluctuating frequency is not fast enough to average out the
static linewidth. In this sample little exchange is occurring and
the linewidth is determined by the static linewidth from dipo-
1/2 lar broadening. Studies of relaxation times in types of film are
(5.5) one clear way to establish the presence of exchange effects. Ta-
ble IV lists of the other studies of relaxation times and from the
limited number of measurements there is some good agreement
between different research groups for similar types of a-C.
5.5.2. Variation o f Linewidth with Temperature
Additional information concerning dynamic effects can be
found in the dependence of the linewidth with temperature.
Figure 73 shows the variation of ABpp with temperature for
five series of different a-C related films [262, 267]. In the case
of DAC, PAC, P doped TAC, and GAC:H, the linewidth de-
creases with increasing temperature. For example Demichelis
et al. [262] showed that in highly sp 2 GAC films, ABpp de-
creased from 0.54 mT at 10 K to 0.30 mT at 470 K. In P
doped TAC, which is H free, Golzan et al. showed that A Bpp
462
2.0
Io 9 I I I I
9 OOoo ~ 9
F-.-
E 1.5 OO
t-
"ID
C While a reduction in A Bpp is usually associated with motional
"- 1.0
D
6
to 0.5 _Oo o mF3[]E]DE 3 []
o o o
OOoio
w ~vvwi~~ mmm ~ 0
Vv
I I I 1 I Lorentzian and a single Gaussian. Ristein et al. reported that
0 100 200 300 400 500
Temperature (~
Fig. 73. Variation of the peak-to-peak linewidth A Bpp as a function of tem-
perature for DAC (V), polymeric PAC (o), P doped TAC (El), graphiticlike
carbon (o), and sputtered a-C ( I ) [262, 267]. Only in the case sputtered films
does A Bpp increase with increasing temperature.
decreased from 0.63 mT at 100 K to 0.52 mT at 300 K [267].
By contrast, in sputtered a-C films Demichelis et al. showed
that A Bpp increased with temperature from 0.24 mT (10 K) to
0.35 mT (370 K). They observed that temperature dependence
of the linewidth could be related to the conductivity cr (T) via
ABpp(T) -- ABpp(O) + C[o(T)] n
where C is a constant and A Bpp(0) is the linewidth at 0 K. For
the sputtered a-C films the best fit gave ABpp(0) = 0.23 mT
and n = 0.32. Some care must be used in the use of Eq. (5.6).
It was originally used by Voget-Grote et al. [268] to study the
effects of temperature on the linewidth of the dangling bond
center (D center, g = 2.0055) in evaporated a-Si and to relate
it to the DC conductivity; they observed a decrease in the ex-
ponent n from 1 to 0.5 with increasing conductivity. Movagher
et al. [269] interpreted these results as being due to effects of
locally fluctuating magnetic fields which originated from the
hopping motion of the electrons and are equivalent to field fluc-
tuation with time at the site of the electrons.
By contrast, in the study of B and P doped a-Si:H, Dersch
et al. [270] observed that the exponent n increased with doping.
They interpreted their results as due to enhanced spin-lattice
relaxation of the localized electrons due to exchange coupling
with rapidly relaxing carriers in extended states. The values of
T1 have been measured at both room temperature (RT) and 77
K for GAC and for DAC'H. It was found that T1 shortened from
1.6 x 10 -6 s at 77 K to 4.2 x 10 -7 s at RT for GAC [262]. In
the case of the DAC:H film T1 reduced from 2.0 x 10 -5 s to
4.0 x 10 -6 s at the two measuring temperatures. A reduction in
T1 in GAC as the temperature was increased and would result
in the linewidth increasing in temperature, which was observed.
However, T1 also decreased in the DAC film and yet this was
accompanied by a decrease of A Bpp with temperature. The tea-
SILVA ET AL.
son for this different behavior is not yet clear but may be a result
of the fact that in DAC, T1 is still significantly longer than T2
such that the linewidth is still determined solely by T2.
5.5.3. Variation of Linewidth for PAC Films
effects, in particular the rapid exchange of spins, a reduction in
the linewidth reported by Barklie et al. [256] and Ristein et al.
[255] (Fig. 70) for films deposited at low biases was accompa-
nied by a change in the lineshape. Barklie et al. reported that
for the film deposited at - 5 0 V bias, the lineshape could be
fitted with either a Voigt profile or a superposition of a single
for biases greater than - 5 0 V the lineshape is fully Lorentzian
but did not report on the lineshapes for films they grew at lower
biases.
Table V shows some of the measured parameters (spin den-
sity, linewidth, and H content) of two series of PAC films
deposited with lower negative self-biases. It can be immedi-
ately seen that by raising the self-bias the spin density increases
from 7.3 x 1017 cm -3 at zero bias to over 1.3 x l02~ cm -3
at - 9 0 V bias. There is also a general increase in the mea-
sured value of A Bpp as the bias is raised. Table V also shows
the predicted value of the linewidth, using Eq. (5.2), assum-
ing that the only source of broadening was dipolar broadening.
As can be seen the calculated values differ considerably from
the measured values except at the higher biases of - 9 0 V
(5.6) and above. Furthermore, dipolar broadening would produce a
Lorentzian lineshape whereas both Voigt and/or Lorentzian and
Gaussian lines have been reported for some of these low bias
samples. The fact that non-Lorentzian lineshape may be present
points to a source of inhomogeneous broadening. One of the
principal sources of such broadening may come from the (unre-
solved) hyperfine interaction from the H 1 nucleus. In this way
the lineshape is determined by the relative contribution from
the (Gaussian) unresolved hyperfine interaction (UHI) to the
(Lorentzian) dipolar contribution. The UHI will increase with
H content and the dipolar contribution will reduce at lower spin
concentrations. Barklie et al. have proposed that the Gaussian
contribution from the UHI can be related to the H atomic con-
centration via the empirical relationship
A Bpp
UHI ( G ) - (0.18 4-0.05) x H (at.%) (5.7)
Values for linewidth predicted by Eq. (5.7) are shown in Ta-
ble V. Some care must be taken in the use of this equation as it
is based upon just three measurements so there may be a distri-
bution of hyperfine coupling constants which would affect the
hyperfine fields. However, Eq. (5.7) does show that it is quanti-
tatively possible to discuss the measured linewidth at low biases
in terms of the contribution from the hyperfine interaction from
H.
The effects of the unresolved hyperfine interaction have also
been attributed to the linewidth behavior with H content in the
DC magnetron sputtered DAC:H film studied by Hoinkis et al.
[271 ]. The EPR spectra, measured under vacuum, consisted of a
 AMORPHOUS CARBON THIN FILMS
Table V. Measured Spin Density and Peak-to-Peak Linewidth, Predicted Linewidths Assuming Dipolar and Unresolved Hyperfine Interactions for Low Bias
Vbias Spin density AB~peasured
/x/~pp
(V) (cm - 3 ) (mT)
0 7.3 • 1017 0.82
-10 3.0 • 1017 1.13
-25 5.5 • 1017 0.82
-50 2.9 x 1018 1.00
4.9 x 1019 1.54
-90 1.3 • 1020 1.46
-200 1.33 • 1020 0.73
single Lorentzian line with g = 2.002 with no hyperfine struc-
ture present. They observed a decrease in A Bpp with H content
from over 7 mT at H contents of less than 6 at.% to 0.28 mT
at 24 at.%. Experiments performed on a sample with a 20 at.%
H content at different microwave frequencies revealed that the
linewidth is independent of frequency. This result indicates that
the linewidth is not significantly affected by a distribution of
g values or any g value anisotropy. At higher H contents the
linewidth increased to 0.8 mT (36 at.%) and to 1.0 mT (39
at. %). The measured spin density decreased monotonically with
H content and ranged from 8 • 1020 cm -3 at low H contents to
0.5 • 1020 cm -3 at 39 at.%. They interpreted the increase in
A Bpp for a H content greater than 24 at. % as being due to UHI.
An alternative explanation has been proposed in which the
observed linewidth of 0.28 mT at 24 at.% H is a result of
exchange narrowing due to a high s p 2 content found in sput-
tered a-C [256]. The dipolar contribution to the linewidth for
this sample, for which Ns = 4.5 • 1020 cm -3, would be, via
Eq. (5.2), 3.7 mT and the UHI would produce a linewidth of
0.43 mT, the combination of which, assuming a Voigt profile,
far exceeds the observed value of 0.28 mT. Similar analysis for
the film with 36 at.% H for which the measured ABpp -- 0.8 mT
9 //dipolar
and Ns = 1 5 • 1020 cm -3 reveals that A,_,pp = 1.22 mT
and A --pp
B UnI = 0.65 mT and would result in a Voigt linewidth of
1.5 mT, which is still in excess of the observed value. Barklie
et al. argue that the effects of exchange are still occurring but are
reduced since the higher H content reduces the s p 2 content. At
39 at.% H, the measured values of ABpp and Ns are 1.0 mT and
1.5 • 1020 cm -3 respectively. The predicted values of A n,-,pp
dip~
and AB~pHI are 0.41 and 0.70 mT and the corresponding total
Voigt linewidth would then be 0.9 + 0.2 mT, which is close
to the observed value. In this way the linewidth would be de-
termined by a mixtures of exchange narrowing and unresolved
hyperfine interactions and would produce a Voigt profile. As the
H content is reduced to about 24 at.% contributions to the width
and shape are dipolar and exchange interactions both of which
will produce a Lorentzian lineshape. For lower H contents 2-
20 at.% of the linewidth increases as the H content reduces.
Hoinkis et al. argue that the simultaneous reduction in the film
resistivity by about two orders of magnitude to a value under
463
Films
. ..dipolar
H content A B UHI
(mT) (at.%) (mT) Reference
0.006 57 1.03 [255]
0.0025 50 0.90 [256]
0.0045 m -- [255]
0.024 -- -- [255]
0.40 25 0.45 [256]
1.06 m -- [255]
1.08 40 0.72 [255]
10 f2 cm results in reductions in the spin relaxation times and
consequent broadening of the lineshape.
Most of the measurements made by Hoinkis et al. were made
under vacuum (10 -6 Torr). Samples which were measured in
air had slightly narrower linewidths and higher signal intensi-
ties. In order to examine the effects of the presence of 02 gas,
Hoinkis et al. backfilled their cavity with 02. They observed
an increase in linewidth but a decrease in the signal intensity
such that the spin density was constant. This broadening effect
was found to be reversible in that after the 02 in the chamber
was removed the lineshape narrowed to approximately the same
linewidth that was observed in vacuum before the introduction
of 02. Other gases such as N2, Ar, or a N2/H2 mixtures (all
of which are diamagnetic) did not produce a significant change
to when the sample was in vacuum. The reversible O2-related
linewidth broadening was attributed to 02 permeating into film
but without the formation of strong chemical bonds. Since the
diamagnetic gases do not affect the linewidth, the line broad-
ening was attributed the interaction of C unpaired electrons
with the unpaired spins of 0 2 . No report of a variation in the
g value was made and the EPR spectrum from the sample with
25 at.% H and exposed to 2 atmospheres of 02 reveals a nearly
Lorentzian lineshape. No change in g value was reported.
5.6. Effects of Nitrogenation
Figure 74 show the spin density for four different types of amor-
phous carbon film as a function of N content. The N content
in each case was determined by either Rutherford backscatter-
ing spectrometry and/or elastic recoil detection analysis. The
series of films examined included three sets of DAC:H films
by Amir et al. [272], Silva et al. [29], and Bhattacharyya et al.
[273] and one set of PAC films by Collins et al. [217]. In the
case of the DAC:H films examined by Silva et al., the spin
density decreases immediately with the inclusion of N from
4 x 1020 cm -3 (0 at.% N) to 9 x 1017 cm -3 (15 at.% N).
They also reported a decrease in the linewidth from 0.50 to
0.15 mT over the same N concentration range. In the absence
of exchange the dipolar contribution to the linewidth for a spin
concentration of 4 x 1020 cm -3 would, via Eq. (5.2), predict a
linewidth of 3.3 mT. Since this is considerably larger than the
464 SILVA ET AL.

1021 1021 [
-I ~v I I I i I I ~O I I I u I
DV V
-V
1020
1020
,? ,,,?, - oo o Ell~ 0
E
r,.> -O
E
rO
- oomo ~
v
>,,
1019 %
r 10 TM r,~
r- c
Q) [] 000
ID
'10 [] V [] [] '10 =n
r c-
~ 0
o.. el. 0
o"3 O9 10 TM 0
10 is
-0
m m
1017 9 --=
1017 I i I J I l I J ~ I I i I l I I --
0 4 8 12 16 0 200 400 600 800

Nitrogen content (at. %) Annealing temperature (~

Fig. 74. Variation of spin density with N content for DAC films by Amir et al. Fig. 75. Variation of spin density with annealing temperature for TAC:H de-
(V) [272], Silva et al. ([3) [29], and Bhattacharyya et al. (.) [273], and one set posited using a plasma beam source using methane (.), DAC films deposited at
of polymeric type by Collins et al. ( n ) [217]. - 6 0 V bias using a magnetically confined plasma containing 1 at.% N (D), and
a set of polymeric films grown by RF PECVD (o).

measured linewidth, some exchange narrowing is believed to be

occurring in these samples. Since the addition of N in this film
has also shown to increase the s p 2 content, which would result
in greater wavefunction overlap, the reduction in the linewidth
due to N is most likely an exchange effect.
In both the series of DAC samples measured by Amir et al.
and by Bhattacharyya et al. reductions in the spin density also
occurred but in the case of Amir et al., reduction in the defect
density below 1020 cm -3 only occurred when the N content
reached about 8.6 at.% N. The N content in the films studied
by Bhattacharyya et al. never exceeded about 4.6 at.% but even
in this limited range a reduction of spin density occurred from
about 1.75 • 1020 cm -3 (0 at.% N) to 0.6 • 1020 cm -3 (4.6 at.%
N). They recorded a single Lorentzian line for N-free and low
N containing films with a g value of about 2.003 but from the
film with 4.6 at.% N some hyperfine structure was observed. It
was proposed that "~ 1% of the spins are in the vicinity of the N
atoms but are not localized upon them. They also observed that
the addition of N resulted in an increase in A Bpp from 0.03 mT
(0 at.% N) rising slowly to 0.06 mT (4.1 at.% N) then rising
sharply to 0.16 mT at the highest N content. They attributed the
increase in the linewidth as due to a reduction in the relaxation
time. However, they did not indicate whether this the T1 or T2
relaxation time; nor did they give values for these two quan-
tities. Finally, in the case of the PAC films, the addition of N
appears to have no effect of the C related defect density which
stays around 3.4 • 1017 cm -3. This behavior is probably at-
tributed to little defect passivation occurring in these low defect
films. For GAC:N films produced by RF sputtering of a graphite
target in an Ar/N2 atmosphere, Demichelis et al. [274] reported
that as the N partial pressure was increased from 1.0 to 4.7 Pa,
the spin density decreased from 1.0 • 1019 to 1.1 • 1018 cm-3.
This was accompanied by an increase in the optical gap from
0.58 to 1.0 eV. (At a partial pressure of 4.7 Pa, the N content was
estimated to be about 30 at.%.) The measured g values were in
the range of 2.0027-2.0032; no values for the linewidths were
given. They argued that the reduction in the spin density is due
to reduction in the disorder in the s p 2 phase of the material.
In addition to the incorporation of N as a n-type dopant,
Golzan et al. [267] have studied the effects of P as a dopant
source in FCVA grown TAC. They observed a single Lorentzian
line with g -- 2.0023 and A B p p = 0.52 mT at room tempera-
ture. The measured spin density was 3.3 • 1018 g - l , nearly two
orders of magnitude lower than undoped TAC. They interpreted
the reduction of the spin density as being partly due to the pair-
ing of the 7r orbital of the s p 2 C with the Jr orbital of P and due
to passivation of dangling bonds.
The addition of N in most types of film results in a reduction
of the spin density and would normally be interpreted in terms
of the passivation of dangling bonds. This is almost certainly
the case in the high defect density samples where the reduction
of the spin density was accompanied by an initial increase in
the Tauc gap (removal of gap states) followed by a reduction in
the Tauc gap possibly due to graphization [29]. However, the
effects of N may also be due to movement of the Fermi level
with the result that that some paramagnetic states become dia-
magnetic. The fact that the spin concentration remains constant
for the PAC films indicates that this may be the lower limit of
the defect density.
5.7. Effects of Annealing
The effects of annealing on the spin density of three different
series of films are shown in Figure 75. The four sets of films
examined were TAC:H deposited using a plasma beam source
with methane as feed gas, measured by Conway et al. [167],
DAC:N deposited at - 6 0 V bias using a magnetically confined
 AMORPHOUS CARBON THIN FILMS 465

i I '
2.0045 d o
(a) I -

2.0040
_

-
_
_

_
T
>
2.0035

2.0030
-
_

-
[]
o
[]
[]
o o
_
[]
2.0025 I O
, I
I ' I
o o
1.0- o []
o
I---
g []
,-- 0.8- []
[]
~ - []
.r 0.6 -
0.4 I I , I
0 200 400
Annealing temperature (~
Fig. 76. Variationof (a) g value and (b) peak-to-peak linewidth for a DAC
(D) and a polymeric (o) film with annealing temperature.
plasma [88] which contained 1 at.% N, measured by Barklie
et al. [275], and a set of PAC films grown by RF PECVD, mea-
sured by Collins et al. [217]. In the case of the TAC:H films the
defect density reduces from 6.4 • 1020 cm -3 in as-deposited
films to 2.6 x 1019 cm -3 for films annealed at 250~ for 30 min.
Above this anneal temperature the spin density remains approx-
imately constant. They did not give either g values or linewidths
and whether there was any variation in these quantities with
annealing. In the case of the DAC:N films, the samples were
step annealed in flowing Ar at 10 min intervals. As can be seen
from Figure 75, Ns increases continuously, reaching a maxi-
mum of 5 • 1019 cm -3 at around 450~ above which it drops
sharply to 8 x 1018 cm -3 at 600~ A similar trend was also
observed in the PAC films which in which the spin density in-
creased from 3.5 • 1017 cm -3 in as-deposited films to a value
of 4 x 1018 cm -3 also at about 450~ At higher anneal temper-
atures the spin density decreased and at 700~ was measured to
be 9 x 1016 cm -3.
Figure 76 shows that for both the DAC and PAC films the
g value and the linewidth depend upon the anneal tempera-
ture. For both sets of films, a similar trend is observed in that
the g value converges to around 2.0025 at anneal temperatures
around 500-550~ In addition the linewidth initially increases,
reaching a maximum at about 200-300~ and then continu-
ously rises to an anneal temperature of 550~ These reported
trends of the spin density, g value, and linewidth can be ex-
plained by the loss of H and a subsequent increase in the amount
of s p 2 C present. For temperatures above 400~ delocalization
of the Jr electrons can occur with a subsequent shift of the g
value to the free g value of 2.0023.
The rapid decrease in the spin density above 550-600~ is
attributed to the removal of unpaired electrons through the for-
mation of large graphitic sheets and a rise in the linewidth of
[]
[]
_
T T
[]
O -
Positive U Negative U
l 1
' (bi Fig. 77. The arrangement of electrons in orbitals for both positive and nega-
tively correlation energies U for singly and doubly occupied orbitals.
0
O
o the DAC:H:N film at 600~ to a shortening of the spin lattice
[]
[] o relaxation time due to interaction with the conduction elec-
D trons which are present if the graphitic sheets become parallel.
, I
Sadki et al. [252] reported a similar behavior in their anneal-
600
ing study of PAC films. As-deposited films had a spin density
of 1.5 x 1017 cm -3. Above an annealing temperature of 250~
they were unable to observe the EPR signal which implied that
the spin density was below 1016 cm -3. It was interpreted that
the FTIR signal from these films annealed above 400~ shows
the presence of aromatic rings and the C = C absorption band
becomes very intense. They argued that the polymeric films
consist of a small number of rr delocalized clusters.
5.8. Correlation Energies and Photoyield M e a s u r e m e n t s
Apart from EPR, there are a number of other techniques that
can give information about defects in a-C based materials but
they may not be confined to just paramagnetically active states.
EPR measurements give information concerning the density of
singly occupied states. In the single electron approximation the
density of states will be filled pairwise by electrons in order of
the orbital energy. Within this approximation no EPR signals
should be visible. In order to explain the presence of the EPR
signal observed in many different firms of a-C, correlation ef-
fects which prevent the spin pairing from occurring need to be
considered. The correlation energy U is regarded as the differ-
ence between the Coulomb repulsion energy of two electrons in
the same orbital and the energy gained by lattice relaxation at
the defect site when the second electron is added to the orbital.
Positive and negative U centers have different properties. In the
notation adopted from a-Si technology, consider a defect which
is neutral when it contains a single electron, labelled D ~ The
other two charge states occur when it is empty, D +, and doubly
occupied, D - . Figure 77 shows the arrangement of electrons in
orbitals for both positive and negatively U. If U is positive all
the defect states will be single occupied and the sample will ex-
hibit paramagnetism. By contrast no EPR will be visible from a
negative U system and the Fermi level will be heavily pinned.
Negative U centers are believed to be responsible for the ab-
sence of any EPR signal from amorphous chalcogenides [ 163].
Only the regime from EF -- U to EF will be singly occupied.
Below EF -- U the states are doubly occupied and above EF the
states will be empty.
466 SILVA ET AL.

I I t used photoelectron yield spectroscopy to determine the occu-

EF ~ 200 V
30 pied density of states (ODOS) for a series of a-C:H samples
as a function of bias as illustrated in Figure 78. In the case
of the sample deposited at 0 V bias, which produced a PAC
/ / /5ov_ film, two defect bands labelled D1 and D2 and the Jr band
centered at 3.0 eV have been fitted. All three bands were fit-
E , v_
0 ted using Gaussian functions. The peak DOS was measured to
0 be 1.2 x 10 22 c m - 3 e V - 1 with a full width at half maximum of
121
0 1.2 eV. According to Ristein et al. the two defect bands should
0
be considered as a pure parameterization of the observed DOS.
Extrapolating to the Fermi level the measured DOS, D(EF), is
1 x 1018 cm -3 eV -1 . As the bias voltage is increased the spectra
can be seen to change and for the sample deposited at - 2 0 0 V
14 bias (a DAC film) the D(EF) is of the order of only 1016 cm -3
-'1 4 eV -1 . The variations of the band positions and electron den-
sities for the three Gaussians fitted to the ODOS are shown in
Binding energy (eV)
Figure 79. Also included are the EPR spin densities discussed
Fig. 78. ODOS with respect to the Fermi level for a series of a-C:H samples previously. Recalling that states will remain singly occupied,
as a function of bias as determined from photoelectron yield spectroscopy. The
and therefore paramagnetic, in the energy range from EF -- U
curves are labelled with the self-bias which were prepared and are offset for
clarity. For the polymerlike 0 V sample the fit of the three Gaussian bands D2,
to EF it is possible to estimate the correlation energy using the
D 1, and 7r to the density of states is also shown. The vertical bars in the spectra data in Figure 79 and the defect density. Integrating the DOS
indicate which binding energy states have to be singly occupied to account for over an energy interval equivalent to U, to give the measured
the measured spin densities. The labels at the bars are the corresponding lower spin densities, will provide a lower limit on the value of U. Ris-
limits for the correlation energies (in eV). Reproduced with permission from
tein et al. infer a value of 0.2 eV for the PAC sample. For the
[255], 9 1995, ???.
DAC sample deposited at - 2 0 0 V bias the higher spin densities
of 1020 cm -3, coupled with the fairly low DOS near the Fermi
, I , I , l , 1
4 level, mean that value of U must be at least 1.5 eV. Such a large
11;
correlation energy may either point to a high degree of local-
vr 3
ization of the gap states and/or to a strong suppression of lattice
o D1
~ 2 relaxation. Finally, it should be noted that surface band bending
0 o ~a-- ,-. - e - - - . ~ o
D2 may also contribute to the value of U though its exact role has
"0
c 1 _ _

yet to be determined.
V ~ V ~ V V
II)
0
An attempt to estimate the correlation energy by examining
I ~ I I I i I i I the density of states inferred from optical absorption mea-
' ' i I i I _
23 surements and spin density measurements has been reported
=- 71;
by Zeinert et al. [257]. Photothermal deflection spectroscopy
E D1
0
v 21 (PDS), transmission spectroscopy in the visible and UV re-
.# o E]
r o
gions, and EPR measurements were made on RF magnetron
Spin density sputtered films using a graphite target in an Ar plasma (90%)
containing hydrogen (10%). The spin densities for these films
8' D2
are reported in Figure79. By assuming that the DOS can be ap-
17 I I I I I proximated by a Gaussian function of the form
0 50 100 150 200

Negative self bias (V) G(EF) -- 2Gmax exp ~ (5.8)

Fig. 79. (a) Band positions and (b) total integrated electron density for the
three Gaussian bands fitted to the ODOS spectra in Figure 78. In addition, the
values of EG and s could be determined from the absorption
EPR densities of the of samples are shown in (b). Reproduced with permission spectra. The value of Gmax was approximated from the number
from [255], 9 1995, ???. of Jr states via

Nrr = sGmax (5.9)

One of the key parameters is the location of the DOS at Zeinert et al. assumed that for a density of 1.5 g cm -3 and
the Fermi level EF. This can be measured in a number of 50% s p 2 coordination that Njr "~ 4 x 1022 cm -3 and showed
ways using photoelectron yield spectroscopy [255] and by elec- that as the optical gap increased from 1.6 to 2.5 eV the DOS
trical techniques such as by space charge limited current as decreased from 3 x 1020 to 3.5 x 1019 cm -3 eV -1. These val-
discussed previously and by junction capacitance techniques ues are higher than those Ristein et al. quoted previously. Using
such a drive level capacitance profiling [261 ]. Ristein et al. have the measured spin densities, values of U for the PAC films were
 AMORPHOUS CARBON THIN FILMS 467

10 6
found to 0.14 eV, similar to that reported by [255]. In the case I I I
113
of the DAC films deposited at higher bias film a value of U of
[]
0.25 eV was reported. This is considerably less than that re- o []

ported in the DAC films of Ristein et al. Zeinert et al., however, 10 5 v o 9

comment that the analysis of the optical absorption may over- "'3".
estimate the DOS. v
~ R =lnm
10 4 - -
c:
c:
5.9. Defects and Nonradiative Recombination _.1 Rc=1.5 nm
Q. o
Many of the features of the photoluminescence from a-C have E =2.54eV v v o
Ex = 3.41 eV
103 t S~hutte (anodic)
been discussed in Section 4.3. In this part of the review we Schutte (cathodic)
shall concentrate solely on those factors which influence the PL
efficiency from different types of films. In a-Si:H photon ab- I I ~ I'
10 2
sorption above the optical gap results in an electron-hole pair 10 TM 1019 1020 1021 1022
that can fall into the tail states via thermalization. This may
result in the carriers diffusing apart from one another. It is gen- N d / ( 1 -Z) (cm "3)

erally accepted that in a-Si:H the dangling bond (D-center) acts
as a nonradiative center and if a carrier meets such a defect non-
radiative recombination will occur. However, due to the more
complicated defect structures that are present in the different
types of amorphous carbon, in particular the different amount
of s p 2 to s p 3 C as well as different sizes of the band tails in
a-C:H, the PL mechanism may be more complicated. In the
model proposed by Robertson [276] the PL is believed to orig-
inate from s p 2 clusters and the PL efficiency depends upon the
defect density, so nonradiative recombination will occur if the
e-h pair is generated within the tunnelling capture radius Rc of
a nonradiative center. The relative quantum efficiency can be
expressed as
rl- rio
[--47r 3 1
3 RcNs (5.10)
where Ns is the spin density. This is the same expression used
by Street for the case of a-Si:H in which the value of Rc ranged
from 100 to 120 ]k. In this description quenching occurs if a
carrier tunnels out of the excited cluster to a defect center where
it recombines. The decay of a tail state from any cluster will
only occur in the s p 3 matrix, which is a fraction (1 - z) of the
total volume. Silva et al. [88] have modified Eq. (5.10) to take
account of the relative amount of s p 2 bonding in the films such
that
Fig. 80. Photoluminescenceefficiency as a function of non radiative density.
The solid lines are fits using Eq. (5.11) for different carrier capture radii as
indicated. Reproduced with permission from [88], 9 1996, ???.
5.10. Summary
In conclusion EPR has been used to examine a wide variety of
amorphous carbon films. Measured values for C related centers
are usually in 2.0026-2.0030 range, though in the case of GAC
values closer to 2.0024 have also been reported. This is almost
certainly due to a high degree of electron delocalization in a
s p 2 graphitic phase. The spin density varies from 1017 cm -3
for soft PAC films up to 1020 cm -3 for harder DAC and TAC
films. Addition of H or N can, for some films, reduce the spin
density but usually by no more than one order of magnitude.
Films deposited at higher bias or ion energy conditions tend to
exhibit Lorentzian lineshapes which can be attributed to dipolar
broadening, and a reduction in the peak-to-peak linewidth is in-
dicative of exchange narrowing. Evidence for this comes from
measured spin-lattice and spin-spin relaxation times. Films de-
posited at lower biases tend to have non-Lorentzian lineshapes
and this is due to unresolved hyperfine interactions from H 1.
Annealing of samples does result in reduction of the spin den-
sity but at extreme temperatures (650~ may result in the
formation of large graphitic layers.

[ - 4 z r 3 Ns I (5.11) 6. ELECTRICAL PROPERTIES OF AMORPHOUS

= 00 3 Rc 1 - z
The fraction of s p 2 bonding in the film is represented by z.
Higher values of z indicate a greater s p 2 content which would
result in an increase in the s p 2 cluster size. Figure 80 shows the
fit of relative PL intensity from a number of films against the re-
duced defect density. From fitting the data to Eq. (5.11) capture
radii of 10 and 15 ~: have been determined. This much reduced
capture radius in comparison to a-Si:H was explained on the
grounds that the reduced Bohr radius is a result of a higher
Coulombic attraction of the e-h pairs.
CARBON
6.1. Conduction and Amorphous Semiconductors
Amorphous carbon possesses many attractive benefits as a
large-area semiconducting material. The deposition is gener-
ally carried out at room temperature, which allows the use of
plastic substrates. Furthermore, the films possess a controllable
optical bandgap in the range of 1-4 eV [281], high electri-
cal breakdown strength of the order of 106 V cm -1 [35], and
low dielectric constant which makes a-C attractive as a high
468
ENERGY
, ,
U However, these states are a consequence Of the amorphous na-
CRYSTALLINE AMORPHOUS
Fig. 81. Andersonmodel for the variation of the energy of potential wells in
an amorphous material.
power semiconductor material. In this part of this review, first
the generalized theory of conduction in amorphous materials
will be described. Second, the electronic properties of the var-
ious types of a-C thin film will be discussed, with properties
subdivided into two broad areas, the electronic structure of the
intrinsic material, and n- and p-type "doping" using in-situ ad-
dition of precursors during deposition. Furthermore, these areas
may be further subdivided into the various types of amorphous
carbon which are commonly grown, namely PAC, DAC, TAC,
and GAC. The electronic properties of each type of a-C will be
commented upon and contrasted.
6.2. Electronic Band Structure of Amorphous Materials
Several texts describe the electronic structure and properties
of amorphous semiconductors. The original models introduced
by Mott and Davis [282] showed that amorphous materials
exhibited short and medium range order but no long range or-
der. Free electron theory shows that the bandgap of a material
is caused by its crystalline order, as shown by the Anderson
model of the potential wells for an amorphous semiconductor
in Figure 81. In the case of a crystalline semiconductor there
is a periodic potential of the ordered crystal. This leads to a
constant phase relation between the wavefunction at different
lattice sites. Therefore, the wavefunction has a well-defined k
value defined by the E - k relationship. In the case of an amor-
phous material this relationship breaks down, as the potential of
the lattice is nonperiodic.
For a crystalline semiconductor, there exists a bandgap,
caused by the broadening of the individual electronic states
into well-defined bands, i.e., an occupied valence band that is
separated from an empty conduction band by a gap that is usu-
ally less than 3 eV. This is due to the formation of standing
waves being set up in the periodic lattice as a result of Bragg's
diffraction theory, which results in the formation of allowed and
forbidden bands in the E - k diagram. However, in the case of an
amorphous material, variations in the periodic potential caused
by changes in bond angle and length result in the sharp band
edges found in crystalline semiconductors to be replaced by
band tails. Amorphous materials do possess a bandgap, though,
as these bands are mostly influenced by short range order.
SILVA ET AL.
In amorphous films there are states within the crystalline
bandgap, i.e., between Ev and Ec as shown in Figure 82.
ture of the solid and hence are not extended throughout the
solid. Therefore, states in the crystalline valence and conduc-
tion bands are known as extended states and states found within
Ec and Ev in the amorphous material are known as tail states
that may or may not be localized. The mobility of carriers in
localized states is much lower than in extended states. The Ec
and Ev lines shown in Figure 82 are known as the mobility
edges. Also, the existence of trapping centers and defects in-
troduce states at the middle of the bandgap that tend to pin the
Fermi level. The tail states are crucial in the conduction process
as even a small concentration can have significant influence on
the electronic properties. In general for a semiconductor the so-
lution to Schrrdinger's equation gives rise to a wavefunction for
electronic states that is solved using the Bloch theorem. There is
a constant phase difference between wavefunctions at different
lattice sites due to the periodicity in crystalline semiconductors
which have a k-space that extends throughout the crystal.
In an amorphous material the Bloch theorem can only be
used with a varying nonperiodic potential function V (r), whose
disorder potential 6 V, though small, will tend to scatter elec-
trons from one atom to another. Therefore, phase coherence is
lost due to the disorder and as a result of the uncertainty prin-
ciple there is a loss of momentum or k-conservation (Ak -~
h / A x ~ h/ao) in electronic transitions due to the uncertainty
in the interatomic (Ax) or scattering length a0. The loss of k-
conservation due to disorder gives rise to a number of very
important properties in amorphous materials and emphasizes
the importance of the spatial location of the carriers which gives
rise to the density of states. Electron and hole effective masses
must be redefined as either tunnelling masses [283] obtained
empirically or by simulation, as the usual curvature of the E - k
diagram cannot be used. Also, due to the disorder the carrier
mobilities are decreased significantly due to frequent scattering.
Most importantly due to the lack of momentum conservation
there is no distinction between direct and indirect bandgaps in
amorphous materials, with transitions allowed to occur when-
ever there is an overlap of states in real space.
6.3. Comparison with Amorphous Silicon
Amorphous silicon was first produced using evaporation or
sputtering, and it was found that the DOS in the mobility gap
was very high, resulting in the pinning of the Fermi level which
prevented the doping of the material [163]. It was then found
that amorphous silicon produced by the RF glow discharge of
silane (Sill4) had a reduced midgap DOS, allowing effective
electronic doping by Group III or Group V elements. It was
suggested that hydrogen had the ability to bond to the dangling
bonds and hence reduce the density of states in the middle of
the gap. However, the optimum atomic percentage of hydrogen
was experimentally found to be 10%, which was at least two
orders of magnitude higher than the amount required to satisfy
all of the dangling bonds. Therefore, hydrogen also remained
 AMORPHOUS CARBON THIN FILMS
Fig. 82. Schematic representations of the density of states for an amorphous material.
in molecular form in a-Si:H and the material was in fact an
alloy. Disadvantages included instability problems due to the
presence of hydrogen.
Intrinsic a-Si:H was found to be slightly n-type [ 163]. There-
fore, the addition of boron to the film had the effect of initially
lowering and then increasing the conductivity as the Fermi level
moved through the middle of the band gap. Activation energy
measurements showed an increase followed by a decrease for
the same reason. The doping mechanism was not thought to be
able to be simply substitutional because of the 8-N rule [282],
which states that all atoms (including dopants) in an amorphous
network bond with their optimal valency. However, experimen-
tal evidence did show that substitutional doping was occurring
for a-Si:H. Furthermore, the DOS was shown experimentally to
increase with doping. This was not shown by EPR as the move-
ment of the Fermi level by doping caused defects to become
doubly occupied and hence nonparamagnetic, but it was shown
in light-induced EPR.
6.4. Generalized Conduction in Amorphous Materials:
Low Field Conduction
Most authors cite the measurements of conductivity and acti-
vation energy as being paramount in describing the electrical
characteristics of amorphous carbon. These are commonly
taken by measuring the resistance of the film by applying a
voltage which results in a field strength of around 103 V cm -1 .
Generally, at this field the current is shown to vary linearly with
voltage. Also, this degree of electric field is applicable for pla-
nar (gap-cell) contacts onto a thin film, as amorphous carbon is
typically grown in the thickness range of 50-300 nm, which re-
sults in a high electrical field if the electrical characteristics are
measured in a sandwich structure with any appreciable voltage.
Due to the presence of localized states around the Fermi
level and the band tails, electronic transport may occur in differ-
ent regions of the DOS, as described below [282, 284]. These
correspond to conduction in four different regimes.
(a) Transport by carriers excited beyond the mobility edges
into extended states at Ec or Ev, leading to a straight-line de-
pendence in the In 0" versus 1 / T characteristic,
I Ec - EF] (6.1)
0" - - 0"minexp -- kT
469
where 0"min is related to the extended state mobility and the
density of states at the conduction band edge by 0"min - -
lZexteN ( Ec )k T.
(b) Transport by carriers excited to localized states at the
band edges and then hopping at the band tail, also leading to a
straight-line In 0" versus 1/ T dependence,
0" -- 0"1 exp -
[ EA--EF-k-Wl]
kT (6.2)
where wl is the hopping activation energy and E A is the band-
tail energy of conduction. 0"1 is found to be considerably lower
than 0"min, due to the reduced density of states and also the much
reduced mobility. Although the mobility term for the hopping
process has been shown by Mott [282] to possess a temperature
dependence as shown in (d), the thermally activated tempera-
ture dependence of the excitation of carriers to the band tail
will dominate this, resulting in the observed dependence.
(c) Transport by the hopping of carriers excited between
localized sites at around EF,
0- = 0"2 exp - (6.3)
where w2 is the hopping energy of activation. This also leads to
a In 0- versus 1/ T dependence.
(d) Finally, at lower temperatures, variable-range hopping
(VRH) dominates for most materials with
0- --0-~exp[-B/T 1/4] (6.4)
The constant B = 2(ot3/kN(Ev)) 1/4, where ot is a measure of
the decay of the wavefunction on a single potential well, and
0-~ - vphe2N(EF)-R 2 where R is the average hopping distance
and Vph depends on the phonon frequencies. The curved nature
of the In J versus 1 / T characteristic in the case of most forms
of a-C has led many authors to believe that VRH predominates
up to room temperature and above [285]. However, others have
refuted this by showing that the localization factor derived in
the case of a-C is often unrealistic [286]. Finally, another form
of hopping, known as nearest-neighbor hopping, is possible if
the localization is very strong, such that the electron jumps to
the state nearest in space because the term exp(-2otR) falls
off rapidly. This leads to an exp(-W/kT) dependence [282],
where W is approximately 1/ R03N (EF), R 0 being the nearest
neighbor hopping distance. See Figure 83.
470
Fig. 83. Schematicof the temperature dependence of conductivity expected
for an amorphous semiconductor.
Fig. 84. Energydiagram showing two ohmic contacts on a trap-free semicon-
ductor, demonstrating space-charge.
6.5. High Field Conduction
This applies in the electric field range of 105-106 V cm -1.
This would be achieved by performing electrical measurements
through a thin film, using for example a metal-semiconductor-
metal or metal-semiconductor-silicon structure. Normally, in
this voltage region the current no longer varies linearly with
voltage. The following mechanisms that describe these char-
acteristics have been observed in a-C: space-charge-limited
current (SCLC) [287, 288], Poole-Frenkel effect [289, 290],
Schottky effect [291-293], and tunnelling [283,294].
6.5.1. Space-Charge-Limited Current
This applies in MIM- and MIS-type structures where two ohmic
contacts are separated by a space charge, as shown in Figure 84.
This can first be analyzed assuming a trap-free undoped semi-
conductor [288]. The ohmic contacts are shown at the same
potential. It can be seen that the accumulation regions are over-
lapping, and as a result the bottom of the conduction band is
curved throughout its length. Therefore, space charge must ex-
tend through the length the semiconductor to allow for band
bending. The result of this is that the conduction process is con-
trolled by the space charge rather than the bulk properties of the
material. In other words, the conduction is space charge limited.
The derivations of the equations governing SCLC are well out-
SILVA ET AL.
lined by Lamb [295], and in the most simple case model the
system as a parallel-plate capacitor with a transit time of car-
riers between the plates. It suffices to state that for a trap-free
semiconductor with single carriers the J / E characteristic is
9#EOEr 2
J cx ~ E (6.5)
8d
where # is the carrier mobility, Er is the relative permittivity,
E0 is the permittivity of free space, and d is the film thickness.
When the semiconductor contains shallow traps, a large fraction
of injected space charge is condensed, resulting in a reduced
density of free charge. The free charge to trapped charge ratio
(Q) can be calculated by applying a simple Arrhenius depen-
dence,
Ncexp( Et )
O = Nt ~ (6.6)
where Nt is the number of shallow traps, and Et is the energy
distance between the trap and the conduction band edge [287].
For deep traps, Q is no longer a constant but depends on the
depth and distribution of traps in the density of states. There-
fore, it is possible, using a careful analysis, to extract some
measure of the density of states at the Fermi level, from the cur-
rent versus voltage data. This has been carried out in the case of
DAC [296] and TAC [297]. The following scaling law has been
predicted [298], assuming field-independent mobility:
= f ~ (6.7)
6.5.2. Poole-FrenkelEffect
This mechanism is bulk-controlled, i.e., it occurs due to the
intrinsic properties of the semiconductor and is not a contact-
limited effect, and is therefore detrimental to device perfor-
mance. Conduction in the bulk is governed by the manner in
which the carrier leaves its originally occupied state at the
Fermi level. As stated, these states are caused by defects due
to the amorphous nature of the material. Some of these defects
will be charged and hence contain carriers held by the electro-
static potential due to the charge. Hence, these trapping centers
can be modelled by a coulombic potential well. The carrier can
leave this well by a reduction of the well height caused by the
application of an electric field, namely the Poole-Frenkel ef-
fect, which was first discussed in the 1930s [289] and modified
in the 1970s by Hill [290]. Figure 85 shows the model diagra-
matically.
The resulting J versus E characteristic, as shown by Hill
[290], is given by
J--Ee#Ncexp ~ exp[flVrE] (6.8)
where
~--~
, e3 ~r~O~r
(6.9)

C O N D U C T I O N BAND
%**
" " " " " " .. 0
: ....'"; ......
~
. . . .
-;:................... Poole-Frenkel Effect
Applied electric field
Trapping center
Fig. 85. Energy diagram showing the modification of the coulombic potential
according to the single center Poole-Frenkel effect.
METAL SEMICONDUCTOR
Ideal barrier
EF
'Ji
I
Fig. 86. Schematic diagram showing barrier lowering due to image charges,
according to the Schottky effect.
and A** is Richardson's constant, k is Boltzmann's constant, T
is the absolute temperature, e is 1.6 • 10-19C, E0 is the permit-
tivity of free space, and Er is the relative permittivity. Therefore,
by plotting In J/E versus E 1/z, values of relative permittivity
can be calculated, along with the trap density Nc.
6.5.3. Schottky Effect
At intermediate electric fields (104-105 V cm-1), this is the
dominant process controlling the current versus voltage charac-
teristic in several materials, for example silicon nitride. This
is known as the Schottky effect [291,292] but must be dis-
tinguished from the standard Schottky barrier equations as it
only occurs at fields at which the metal-to-semiconductor bar-
rier height is reduced due to image forces attracting the electron
to the surface of the metal, which is shown in Figure 86. The re-
suiting current density is given by
J -- A**T 2 exp [ ~~0 + ~-
fl~]
where /3 has the same meaning as in Section 6.5.2. The di-
electric constant and barrier height at zero voltage, ~0, can
therefore be calculated from the above equation by plotting In J
AMORPHOUS CARBON THIN FILMS 471
X THERMIONIC
~c
TUNNELLING
EF FOWLER-NORDHEIM
~TUNNELLING
METAL SEMICONDUCTOR
Fig. 87. Thermionic and Fowler-Nordheim tunnelling through a potential bar-
tier.
versus E 1/2. In the case of a-C, this type of analysis is relatively
cB rare, and there has been no proof as yet of a Schottky barrier on
this material by applying to a fit to barrier lowering.
6.5.4. Tunnelling
At higher fields the electron can tunnel through the barrier, with
or without thermionic assistance, as shown in Figure 87.
The derivation of thermionic tunnelling assuming thermionic
field emission is outlined by Shannon [283]. For small carrier
effective masses the total current is described by the equation
j = A**T2 exp [ -(~~kT
+~ ] (6.11)
where Es is the surface electric field and c~ -- (kT)6 In J/,~Es
is the tunnelling constant. Generally, this type of tunnelling
only occurs at electric fields of higher than 106 V cm -1 and
is characterized by a straight line in the In J versus E char-
acteristic. The Fowler-Nordheim [294] process assumes an
approximately triangular potential barrier and obeys the depen-
dence
V2 [_~3/2]
exp (6 12)
J o~ d~O fl V
where ~0 is the barrier height and fl is a constant which de-
pends on the localized field enhancement. It must be noted that
this model applies to tunnelling at the Fermi level. A straight-
line In J / V 2 versus 1/ V dependence is observed. In particular,
though, this analysis has greater relevance in the case of sur-
face electron field emission, as Fowler-Nordheim tunneling has
often been cited as the process controlling the emission of elec-
trons through the barrier to the vacuum level.
6.6. Electronic Structure and Properties of Amorphous
(6.10)
Carbon
Amorphous carbon has been studied as an electronic material
for about 30 years. However, the electronic structure of a-C,
and hence the electronic properties, are complicated by the fact
472 SILVA ET AL.
' " ' ' ' ' '
) I ' I ' I 9 I
that both zr and cr states exist within the bandgap, which con-
10 s 10 5
tribute differently to the conduction properties. Therefore, the
10 4 10 4
electronic properties of a-C are relatively poorly explained. In
the first section, the electronic properties of amorphous carbon 103 10 3 r

in its undoped state will be described. This will be subdivided 10 2 10 2 3

into its two most commonly researched forms: a-C:H in its
~" 10' ~. lO ~
forms DAC, PAC, and GAC, and TAC. o cb .
~' I oO
As documented in Section 7, the gap states of a-C are highly - - 100
localized. The eventual outcome of this is that in any form of 10 -1 101 i
amorphous carbon, conduction will always occur by some hop- 1 0 .2 r
1 0 .2
ping process between localized states. Higher temperatures are 1 0 .3 r 9 a-C \
therefore required for conduction in the extended states to be 10 .3
o a-C:H \ o a-C:H "%
1 0 .`= .
realized. In a later study, Robertson discusses the p-type con- 10 .4 l ' I 9 I 9 I . I , . i . i . 11

2 3 4 5 6 0.22 0.24 0.26 0.28

ductivity of a-C as being due to the nature of the dangling bond
defect. This is shown to be planar, by analogy to the methyl
radical, and therefore contains a pure p Jr orbital whose energy
level lies at the p-orbital energy, which is at midgap. However,
Robertson suggests that the dangling bond defect possesses a
significant s content, due to s - p mixing. Therefore, the dan-
gling bond energy level is lowered, as s states lie deeper than
p states. This results in the p-type conductivity of the undoped
forms of amorphous carbon [299].
The early experimental data for describing the electronic
structure of a-C is summarized by Robertson [300]. Using cur-
rent/temperature measurements, Robertson has reviewed work
which has shown that for sputtered and glassy GAC, conduction
follows variable-range hopping with an c~-1 value of 1.2 nm
and N ( E F ) of 1018 eV -1 cm -3. Robertson also showed that
the temperature dependence of conductivity was curved and did
not fit any law particularly satisfactorily. Above 400 K it was
ascribed to band-tail conduction. Chan et al. [35] showed that
from a range of 300 to 500 K, it was not easy to ascribe any
single conduction mechanism as the fits were similar with both
band-tail and variable-range hopping. But with a fit to band-tail
hopping made, an activation energy of 0.34 eV was derived,
which was much smaller than half the bandgap, suggesting that
the Fermi level was not at midgap.
103/r (K") irrl/4(K-I/4 )
Fig. 88. Variation of current versus temperature for hydrogenated and un-
hydrogenated GAC films. Reproduced with permission from [285] 9 1984,
Wiley. (a) / versus 1000/T, (b) I versus 1/ T 1/4.
ties of GAC:H, as compared to sputtered GAC. Both types of
film were grown using RF sputtering. First, the conductivities
of GAC and GAC:H were similar, implying that the optical gap
and conductivity were ruled by the size and number of s p 2
islands rather than the hydrogen content. Second, in the case
for films where the s p 2 : s p 3 proportion was below its percola-
tion threshold, the conduction at high temperatures appeared
to follow some type of activated (band-tail) hopping process
and some type of T 1/4 relationship at room temperature, im-
plying variable-range hopping. This was in accordance the the
behavior cited by Orzeszko et al. However, the calculations of ot
and N (EF) yielded unrealistic values (c~- l < 10 - 7 c m - 1 and
N ( E F ) > 1045 cm -3 e V - l in one case). By fitting an Arrhe-
niuslike relationship for the conduction at room temperature,
and assuming a process of hopping between neighbouring s p 2
islands using a model from Mott [282], a good fit was obtained
to the equation

6.7. Electronic Properties: GAC Films cr -- ( 2 e 2 R 2 / k T ) l ) p h N T r T e x p ( - w / k T - 2c~R) (6.13)

The current versus temperature plots for GAC films were
reported and investigated by Orzeszko et al. [285]. They evap-
orated GAC with or without a hydrogen atmosphere was
compared to the resulting current versus temperature curves.
Unhydrogenated films showed a reasonably close T 1/4 de-
pendence, but the hydrogenated films showed a better T -1
relationship. This suggested that variable-range hopping played
a greater role in the case of the nonhydrogenated film, as shown
in Figure 88. Therefore, assuming a localization length ot-1 as
documented by Hill [290] of 7.5 • 106 cm -1, the density of
states N (EF) was carried out using the equations for variable-
range hopping. It was found that N ( E F ) was two orders of
magnitude lower in the case of nonhydrogenated films than hy-
drogenated films.
Similar measurements were carried out in more detail by
Dasgupta et al. [286], who looked into the electronic proper-
The term R is the distance between adjacent s p 2 clusters and is
crucial in calculating the conductivity variation of the material.
For conduction at higher temperatures, variable-range hopping
in the band tails was observed to fit the closest. For films with
an s p Z : s p 3 proportion above its percolation threshold, hopping
in the band tails appeared to be the only effective model. This
has been contradicted by Helmbold et al. [301], a reason being
that the values of thermopower generally found in the case of
GAC (and DAC) are very small, in the order of 10-30/zV/K.
Conduction in band tails should result in thermopowers sev-
eral orders of magnitude higher due to an appreciable activation
energy. Therefore, an alternative mechanism based on a multi-
phonon tunnelling model with weak electron-lattice coupling
was proposed. A hopping process between s p 2 clusters was
also assumed and the electron-phonon coupling was related to
the mean lattice spacing and the localization length. Activation
 AMORPHOUS CARBON THIN FILMS 473

!.
|
~ I 4.5 - ' I I ' I i

2.6 i
9 Rusli etaL
4.0
o T a m o r e t al.
i
x 2.4
(9 ~. 3.5 l
l x R i s t e i n e t al.
"10 > ', 9
r 9 9
3.0 X', 9

~
> 2.2 Q.
r
i

r 2.5 •
r
'-
ID 2.0 ._o 2.0 0 X ~
0 X"..
0 ~
o 1.5
1.8 W
".. 0

I I 1.0 "" .... 9.

................ -O"
100 -
...... 0.5
E 10 .2 0 200 400 600 800 1000 1200 1400
o
DC self-bias voltage (V)
~,.~10-4

9~ 106 Fig. 90. Variationin refractive index and room temperature conductivity as
o a function of optical band gap. Reproduced with permission [302], 9 1993,
c l O-a
"o Wiley.
0
~10-10
, I , I ~ ! m

0.0 0.5 1.0 1.5 2.0
Optical band gap (eV)
Fig. 89. Variationin optical band gap of DAC films as a function of DC bias
voltage (see [201,255,220]).
energies in the order of 0.015 eV were derived, which would
explain the small thermopowers.
6.8. Electronic Properties: DAC Films
Robertson cites [300] that the optical absorption data suggests
that most forms of a-C possess broad tails and hence a nar-
row bandgap (0.4-0.7 eV). However, DAC possesses a wider
bandgap, due to the reduction of the band tail density of states
as a result of the increase in sp 3 bonding. As already mentioned,
the highly localized midgap states can dictate the conduction
properties. These are formed as a result of the breaking of Jr
bonds, as the Jr bonding is weaker than the cr bonding. If the zr
defect is on a conjugated system (e.g., an aromatic ring), it can
delocalize with the ring. Any system with a half-filled Jr bonded
site, including odd-membered rings, such as azulenes, as well
as odd-numbered clusters, introduce states around E F and are
referred to as Jr defects. Dangling bonds are also classified as
zr defects, as the unpaired electron will preferentially occupy a
zr orbital.
6.8.1. D e p o s i t i o n P a r a m e t e r s
As already discussed, the DC self-bias voltage during depo-
sition plays a critical role in determining the optoelectronic
properties of the material. The variation of optical bandgap with
DC bias voltage, according to Rusli et al. [201 ], Ristein et al.
[255], and Tamor et al. [220], is shown in Figure 89. At bias
voltages close to zero, the films possess a bandgap of approxi-
mately 4 eV and are polymeric in nature (PAC). As the DC bias
voltage is increased, the bandgap shows a corresponding de-
crease as the film passes through a diamondlike (DAC) phase.
Eventually, above DC bias voltages of 600 V, the film becomes
graphitic in nature (GAC) and the optical bandgap falls to below
1 eV.
However, relatively few studies have been carried out which
refer to the effects on the electronic properties of DAC. Stenzel
et al. [302] cites the effect of DC conductivity on the optical
bandgap, as referred from earlier work. This variation is shown
in Figure 90. This can be therefore be correlated to the effect of
DC self-bias on optical bandgap, as documented by Silva et al.
[281] and Ristein et al. [303]. It is commonly observed that
an increase in the DC self-bias results in a decrease in optical
bandgap. At low bias voltages, i.e., on the earthed substrate ta-
ble of a PECVD process, the films are polymeric in nature and
possess a Tauc optical bandgap of 2.5-3 eV [304]. At higher
DC voltages the films become increasingly diamondlike and
then graphitic in nature with the optical bandgap falling to even-
tual closure at the highest voltages. Stenzel et al. found that the
room temperature conductivity showed an approximately expo-
nential fall with the increase in optical bandgap, corresponding
to values of 10 -2 ~2-1 cm -1 with an optical bandgap of 0.3 eV
(a GAC:H film grown with a DC bias of higher than 500 V),
to 10 -1~ f2 -1 cm -1 with an optical bandgap of 1.8 eV (a DAC
film grown with a DC bias of less than 100 V). Thus, the resis-
tivity can be varied greatly by changing the optical bandgap of
the material.
The effect of deposition temperature on the optoelectronic
properties was documented by Jones and Stewart [305] who
also grew films using an RF plasma. First, they found that both
the optical bandgap and the activation energy of DAC decreased
with increasing deposition temperature, from a value of 1.2 eV
at a deposition temperature of 175~ to 0.7 eV at 350~ This
could be explained by the increase in s p 2 content resulting in
a narrowing of the bandgap and hence activation energy. How-
ever, they found that the difference between optical bandgap
and activation energy remained constant as the deposition tem-
perature was changed, even though both were dependent on the
deposition temperature. This indicated that the position of the
Fermi level remained fixed relative to the valence band. How-
474 SILVA ET AL.

1.8

1.6
_ • ' I '
! ,o~k~k ...... -4 9

1.4
>(D 1.2 --'IBI--- - 9149149 ""'-. X ', / / t
o. 1.0 I
"Ill <1:-12 I

t
x
~0.8
l I
'~ 0.6 x -'J 107 V r |
O 0.4 10.8 ~ -18
9 Koidl et al. (Tauc) I
i,
0.2 o Burden et al.(Eo4 ) 10.9 ~ -20
" + Bounouh et al. (Eo4)
0.0 10"10 -22 . . . . . . . . . .
, I a I , I I ~ I ~ I -1x106-5x10 s 0 5x10 slx106 0 200 400 600 800 1000
0 100 200 300 400 500 600 E ( V cm 1) E v 2 ( V cm-1)1/2
Anneal temperature (~
Fig. 92. Poole-Frenkel conduction in DAC:H, after Khan et al. (a) J versus E
Fig. 91. Variationin optical band gap of DAC films as a function of annealing plot; (b) In J versus E 1/2 plot.
temperature (see [24, 307, 346]).

ever, at room temperature the conduction appeared to move eV between bandgaps of 1.3 and 1.5 eV. At lower temperature
toward EF, indicating hopping conduction. the temperature dependence was nonlinear, as observed by oth-
The effect of thermal annealing on the optical bandgap of ers.
DAC is shown in Figure 91, which describes the variation ac- There is much useful information here which has not yet
cording to Burden et al. [306] (in this case for DAC films grown been analyzed to date. First, conduction in these films at high
using magnetically confined PECVD), Bounouh et al. [307] (di- electric fields is bulk-limited and as the optical bandgap is in-
rect vapor deposition), and Koidl et al. [24] (PECVD). What is creased, it is likely that the density of donor/acceptor trap states
generally found is an increase in sp 2 content above a graphi- causing PF conduction decreases, causing a decrease in J0.
tization threshold, commonly around 350~ which has been The PF (i.e., high field) activation energy follows the optical
correlated with the decrease in optical bandgap around this tem- bandgap trend but always possesses a value just less than half
perature, as well as a decrease in resistivity of around five orders of the bandgap, suggesting that these traps are in a defect band
of magnitude also around this threshold [304]. However, Bur- close to but not at midgap. It has been stated that p-type con-
den et al. found that the optical bandgap increased at anneal ductivity is likely in the case of DAC and this suggests that this
temperatures of 125~ It was suggested that the passivation PF activation energy is to the valence band via hole conduc-
of dangling bonds due to the movement of hydrogen during tion. At high temperatures the carriers dictating PF conduction
the anneal had sharpened the band tail and hence increased the are likely to be excited to the valence band edge, resulting in a
bandgap. straight temperature dependence, but at room temperature and
below they are retrapped around the defect band resulting in the
curved temperature dependence akin to VRH or some alterna-
6.8.2. I/V Characteristics tive hopping process [286, 301 ] at lower electric fields.
The current versus voltage ( I / V ) characteristic is essential in A study to investigate the effect of contact material on the
order to ascertain the dominant high field conduction mecha- I / V characteristics was carried out by Konofaos et al. [311 ].
nism which is taking place in these films. In the most simple The films were grown on silicon substrates using a mixture
case, DAC films grown on metal substrates show a symmetrical of CH4 and H2 in a standard RF PECVD system, and sub-
J versus E characteristic [308-310], suggesting that conduc- stantial differences were observed in the I / V characteristics
tion is bulk-limited and not ruled by the differences in barrier between using gold and aluminum top contacts. This was ex-
heights at either contact. Egret et al. [308] showed that for plained by the presence of a Schottky barrier, which possessed
DAC, the conduction was dominated by the Poole-Frenkel (PF) a different height for the two materials. Also, it was found that
effect, which has been shown by others and is displayed in Fig- by growing films of different thicknesses, the J~ E characteris-
ure 92. As a test of PF conduction, films were grown with a tics were not the same, suggesting contact limited conduction.
range of refractive indices of 1.8-2.3 by varying the self-bias However, Allon-Alaluf et al. [312] grew DAC films on alu-
voltage, which corresponded to an optical bandgap range of minum substrates using a similar process and found that the
1.2 to 2.2 eV. The dependence of the PF fl factor with the I / V characteristics were symmetrical using gold or copper top
refractive index was observed, and/3 was found to vary ap- contacts, indicating an ohmic contact. There appeared to be a
proximately with 1/n which suggested that the PF equation low field asymmetry using aluminium top contacts, which was
was applicable. Furthermore, it was found that as the optical investigated using capacitance-voltage (C/V) measurements.
bandgap increased over this range, the current density at zero This indicated an interfacial barrier between the film and the top
voltage J0 decreased from 10 -7 to 10 -12 A cm -2, and the PF contact. This was further justified using Auger emission spec-
activation energy at high temperatures increased from 0.4 to 0.6 troscopy which showed a substantial concentration (20%) of
 AMORPHOUS CARBON THIN FILMS 475

3.0 ' I ' I ' I ' I ' I

10 .4 - ~
.m. 9 Chhowalla ot aL
10-5 - ~ -
> 2.5 ./= i. o Waidmann ot al."
10 -8 -
~, 10 7 -
v
i" ~ ~
Q-2.0
10 - ~ -
9~ 10 .9 - I
"~ 1.5
O.) 1 0 -~~ - ou
o 0 ..... 9 ................ "l

10 ~ -
o 1.0 J !
10 -,2 _
o "0
10-13 _ ",,,j 0
tU 0.5 !
10 "14 -
10-1s i I , , I , I i I i
-~ -2 0 2 4 6 8 0.0
Voltage (V) l I i I : I i I i I
9 Chhowalla et al!
Fig. 93. Band gap-modulated DAC superlattice/Si heterojunction showing 8 "7
o Fallon et al.
orders of magnitude of rectification. Reproduced with permission from [35], 9 EIO -e J
.,f
o J
1992, Elsevier Science. I versus V plot. '7, 9 ~'*" 0

C~ .-6"
> , 1 0 .7 9 9 , " "
~, j"

oxygen at the interface. It is possible that this result may ex- :=

0 .. .6
plain those of Konofaos et al.
However, others, such as Silva et al. [296], have discussed
"ol

~
~176 o
('-
0

k
o, dw

.
..

oO
9

-"
nb
,.-, "
"'"
0 "-

these diamondlike films in terms of space-charge-limited cur- 1

O "9 I , I , I , I

rent. From such measurements, using the analysis outlined 0 1 O0 200 300 400 500

previously and described in Lampert and Mark [298], an idea
of the density of states at the Fermi level has been derived, the
value being of the order of 1018 eV -1 cm -3 . This can be com-
pared to a spin density as derived from EPR of the order of
1 x 1020 cm -3 [303]. Using this reference, an extracted cor-
relation energy from photoelectron yield experiments is of the
order of 1 eV, thus giving a density of states of 1 • 1020 eV -1
cm -3 (cf. Section 5). However, diamondlike films with a higher
bandgap were also measured by Silva [313] and were found to
obey Poole or Poole-Frenkel conduction. Therefore, it can be
ascertained that most forms of DAC follow this type of conduc-
tion, and hence the density of defects dictates the conduction
properties of the material.
6.8.3. DAC Heterojunctions
These has been much work which has provided evidence for a
DAC:H/Si heterojunction. This was first shown by Amaratunga
et al. [314] which showed that the I / V characteristic of the
metal-carbon-silicon structure displayed rectifying behaviour.
This suggested an a-C/silicon junction and has been shown by
others [35,315,316]. Chan et al. [35] found that the forward to
reverse rectification ratio was six orders of magnitude, by grow-
ing a bandgap-modulated DAC superlattice film, as is shown in
Figure 93.
Capacitance-versus-voltage measurements are valuable when
investigating the nature of the a-C/Si interface. The early
evidence was obtained by Chan et al. [35, 317], following in-
vestigations carried out on sputtered a-C by Khan et al. [318,
319]. Chan showed that the observed frequency dependence of
the C~ V characteristic came about due to interface traps. This
was modelled and the interface trap density was found to be of
the order of 1010 cm -2 eV -1 and was comparable to that re-
ported by Khan et al. [318]. This value was also far lower than
the areal spin density as derived from EPR or deep level ca-
Ion energy (eV)
Fig. 94. Variation in optical bandgap and DC conductivity as a function of ion
energy for TAC films.
pacitance profiling in TAC, which suggested that the dangling
bonds in a-C films were not acting as trap centers. In compari-
son, Mandel et al. [320] carried out similar measurements and
found that the gap state density of states was in the order of 1016
cm -3 eV -1 . However, Munindradasa et al. [315] correlated the
C / V as a function of frequency with the field emission proper-
ties of the material. In this case, the amount of hysteresis was
low and the fiat band voltage was zero, suggesting an absence
of fixed charges.
6.9. Electronic Properties" TAC Films
Even though TAC possesses a high sp 3 content of around 80%,
there will always be a significant proportion of sp 2 bonds that
will introduce rr states into the bandgap. These will hence dic-
tate the electronic properties of the material by being closer to
the Fermi level.
6.9.1. Effect o f sp2/sp 3 Bonding
The change in the sp 2 content of TAC and its subsequent effect
on the electronic properties of the material are of paramount
importance in discussing the conduction within the material.
Surprisingly, relatively few studies that concentrate on the elec-
trical properties have been carried out. Fallon et al. [68] grew
TAC films using FCVA and varied the bias voltage of deposi-
tion in order to see if there was an optimum ion energy for the
promotion of sp 3 bonding. This was found at a bias voltage of
100 V, i.e., an ion energy of approximately 140 eV, and corre-
sponded to the maximum in resistivity, along with other factors
476 SILVA ET AL.

I " I ' I ' I ' I ' I ' I ' ' I ' I ' I ' I '
...................................... i...i
2.5 o Sattel et al. ~-3.0
> "..
o
> 9 9 Chhowalla etal. ,~

"--42.0 B ~2.5 +..__ ++--+-~ ..

Q.
9 9
~--§
E~
0 9 ".
_r "~ 2.0
tO
0 9
o 1.5 ~
~ . i .0 0
0 o
ILl
o 0 0 0 1.0 9 Sullivan etal.(TAC)
uJO.5 + Conway etal. (TAC:H) 9

I I
0.0 ~ _ 9 Fe!rarietal)TAC) I : : 1, -
'I : ' I = ' I ' ' ' II : : : : : : 9 o Sullivan etal 9 (TAC) 9 "
104 "7 10 .2
0 E 9 + Conway etal. (TAC:H) ...- "

,_ 10 2 0 "7o 10.4 .../

'~ 00 ~.m
10 6
o .......... o"
...~ .... .o--

9~ 10 .8
i__10-~ 9
"~10 -10
r 9 u
-ol 0-4
t-
0 10-12 "+.+_§
~o
0o 1 0 ~ 10-14 , I , I , I , I ,
o= 9 Chhowalla et aL 0 200 400 600 800 1000
10 .8
9 9 o Kleinsorge etaL Annealing temperature (~
10 "10 I i I i I , I , I , I , I ,

-100 0 100 200 300 400 500 600 Fig. 96. Variation in optical bandgap and DC conductivity as a function of
Deposition temperature (~ annealing temperature for TAC and TAC:H films. Reproduced with permission
from [125], 9 1999, American Institute of Physics. Reproduced with permis-
Fig. 95. Variation in optical bandgap and DC conductivity as a function of sion from [126], (~) 1997, World Scientific. Reproduced with permission from
deposition temperature for TAC films. [316], (~) 1998, American Institute of Physics9

The effect of varying the deposition temperature on the con-

ductivity and optical band gap has also been measured and is
such as compressive stress and plasmon energy. It was sug-
illustrated in Figure 95 as derived by Chhowalla et al. [69], Sat-
gested that the bandgap is at its widest at this energy. Another
tel et al. [323], and Kleinsorge et al. [324]. It is observed that
explanation proposed is the decrease in conduction (variable-
the optical bandgap shows a decrease from 2-2.5 eV to 0-1 eV
range or band-tail hopping) between s p 2 clusters, should the
as the deposition temperature is increased, and the conductivity
density of these clusters within an s p 3 matrix be reduced.
shows an accompanying rise of 7 - 1 0 orders of magnitude over
Similar trends on optical and mechanical properties have been
the temperature range. In the study by Chhowalla et al. [69],
shown by Xu et al. [66], Chhowalla et al. [69], and Waidmann
the sharp decrease in resistivity at higher deposition tempera-
et al. [321]. Figure 94 shows the variation in optical bandgap tures was explained by the increase in disorder of the film due
and conductivity with ion energy, according to various authors to energetic ion bombardment leading to gap states. It could
[68, 69, 321]. It can be seen that Fallon et al. and Chhowalla be explained similarly to the above result, though, i.e., an in-
et al. concur with the conductivity measurement, but the ion crease in the hopping probability between s p 2 clusters, as the
energy at which the optical bandgap is at its widest is 220 eV sp 2 content is increased. Chhowalla et al. also measured the
in the case of Waidmann et al. as opposed to 100 eV or less conductivity as a function of inverse temperature and found a
for the other authors. This illustrates the observation that dif- linear dependence. This suggested band-tail conduction and as
ferent groups have measured different energies at which the the activation energy was 0.45 eV, the Fermi level was not at
peak in sp 3 content occurs. This could be due to differences midgap.
in the degree of ionization or varying monochromacities of the
ion beam. Another point to note is that most groups measure
resistivity in TAC by the evaporation of planar (gap-cell) con- 6.9.2. A n n e a l i n g o f T A C
tacts which allow the measurement of surface resistance. This The only significant studies into the effects of annealing on the
method is problematic as it has been shown [322] that TAC electronic properties of TAC were carried out by Sullivan et al.
possesses a significant spZ-rich surface layer, so reliable mea- [126] and Ferrari et al. [125]. This is shown in Figure 96. In
surements of the bulk resistivity may not be obtained. In sone addition, the annealing data in the case of TAC:H as derived
cases this layer is etched but one canot ascertain whether the by Conway et al. are shown and will be discussed later. In the
surface layer is modified or terminated during this type of pro- case of TAC, a stress relaxation occurred around 600~ Sul-
cedure. Therefore, the most reliable method for measuring bulk livan et al. modelled this stress relaxation as a small change
resistivity would be through the film using m e t a l - c a r b o n - m e t a l in s p 2 content, of up to 6.5 at.%. Therefore, the variation in
structures. conductivity was compared with this change in sp 2 content. In
 AMORPHOUS CARBON THIN FILMS
particular, the conductivity appeared to be exponentially depen-
dent on the s p 2 concentration of the film. It was postulated by
the data that the enhancement of conductivity was governed by
variable-range hopping with a term for the variable separation
between s p 2 sites, assuming they occur in chains rather than
rings. A typical chain length was estimated to consist of 13 car-
bon atoms. Therefore, the conduction was thought to be ruled
by the length of s p 2 chains, which were lengthened through
annealing (though only from 13 to ~ 14), coupled with chain-
to-chain tunnelling.
Ferrari et al. also showed that the E04 optical gap stayed con-
stant (at 2.7 to 3.0 eV) until 600~ and therefore the change
in s p 2 content was likely to be low. They also concluded that
the decrease of resistivity of almost three orders of magnitude
(initially ~ 107 f2 cm) over this temperature range could be ac-
counted for by the slight increase in hopping centers. Above
600~ though, the resistivity decrease was much greater and
coincided with a fall in the optical bandgap, though the s p 3
percentage remained unchanged until 1200~ where it fell from
85% to 20%. This coincided with complete stress relief within
the films. It was possible that this final transition was triggered
by the formation of r-SiC. The Raman spectra associated with
these films were discussed in Section 4.
6.9.3. TAC Heterojunctions
Tetrahedral amorphous carbon has been shown to form a het-
erojunction with silicon [120, 325], in spite of the fact that
it was been shown that TAC forms a highly sp2-rich sur-
face layer as a consequence of the likely subplantation process
which results in a densification below the film surface [81].
These heterojunctions possess strongly rectifying I / V charac-
teristics and breakdown strengths above 100 V. From TAC/Si
heterojunctions, it was shown that the current flow was space-
charge-limited [297]. The turn-on voltages were 1.6 V for the
TAC/n-Si heterojunction and 0.4 V for the TAC/p-Si hetero-
junction, suggesting that the material was p-type. Using the
differential method, the density of states derived from the va-
lence band was of the order of 1021 cm -3 eV -1. Furthermore,
Palinginis et al. [261 ] carried out junction capacitance measure-
ments on TAC in order to derive the defect density. Using the
drive level capacitance profiling technique, a defect density of
6 x 1017 cm-3 was determined. The value as derived from EPR
was at least two orders of magnitude higher (cf. Section 5); this
was explained by the fact that this technique used only would
detect the D + or positively charged defect center.
6.9.4. P h o t o c o n d u c t i v i t y o f TAC
Photoconductivity in the case of TAC was first reported by
Amaratunga et al. [326]. It was found that the resistivity de-
creased from 107 to 105 f2 cm when the films were illuminated
under AM 1 light. The spectral response was then observed and
it was found to show a peak at around 750-800 nm, correspond-
ing to a photon energy of around 1.7 eV, which was close to
the optical bandgap. The quantum efficiency of the film was
477
between 10 and 12.5% over the 450-800 nm range and then
decreased. Also, it was found that the variation of photocon-
ductivity was independent of temperature, indicating that the
conductivity under light was dominated by carrier generation.
McKenzie et al. [327] found that photoconductivity de-
creases with increasing nitrogen content. Following this, Cheah
et al. [328] fabricated nitrogenated TAC/p-Si heterojunctions
and also observed that the optical absorption increases as a
function of nitrogen content. Also TAC(:N) films were grown
on p-Si substrates and the resulting reverse characteristic of the
TAC:N/Si heterojunction was found to increase by three orders
of magnitude. These factors also indicated promise for TAC:N
as a material for solar cell applications
The latest and most detailed studies on the photoconduc-
tivity of TAC and TAC:H have been carried out by Ilie et al.
[329, 330]. They first investigated the photoconductivity of the
undoped forms and found first that above 200 K the photocon-
ductivity decreased with temperature according to an activation
energy, and below 200 K it was independent of temperature.
Therefore, it was surmised that TAC was a low-mobility solid
w i t h / z r products in the order of 10-11-10 -12 cm 2 V -1 due to
the high defect density. The main recombination centers were
deep defects but tail states also caused recombination, and at
200 K there was a peak in conductivity corresponding to com-
petitive recombination between two classes of centers. A later
study showed that in the case of TAC'H, the photoconductiv-
ity is increased by nitrogen doping, as the material is doped
n-type. The photosensitivity obtained was approximately 200
under 35 mW/cm -2. The addition of nitrogen did not create
extra charged defect recombination centers.
6.9.5. Hydrogenated TAC
A study was carried out by Davis et al. [112] which measured
the properties of TAC deposited in the presence of varying flow
rates of hydrogen, and it was found that there existed a certain
threshold at approximately 0.05 sccm H2. Below this thresh-
old, the s p 3 fraction increased from 82 to 86% and the plasmon
energy increased from 29.8 to 30.5 eV, suggesting in increase
in carbon atom concentration with some hydrogen incorpora-
tion. Also, the optical bandgap increased from 1.9 to 2.1 eV and
the trap density decreased, when using a SCLC analysis as in
the case of Veerasamy et al. [297], the current injection was at
its sharpest at 0.05 sccm. These measurements suggested that
at these low hydrogen contents, there was a reduction in the
band-tail density due to the increased s p 3 content, effectively
as hydrogen would force an increase in the s p 3 content as it
cannot bond to carbon in an s p 2 configuration. This would re-
sult in a reduction in defect states below the Fermi level and
hence a movement of the Fermi level toward midband, causing
increase in activation energy and resistivity. This was observed
in the activation energy which increased from 0.22 eV in the
undoped case to 0.36 eV at a flow rate of 5 sccm H2 with a con-
current increase in resistivity from ~ 1 • 107 to ~ 3 x 107 ~ cm.
However, above 0.05 sccm H2, the trap density increased, and
the s p 3 content decreased down from 83 % to 77% at 5 sccm H2.
478 SILVA ET AL.
It was postulated that this was due to an increase in the number
of isolated sp 2 sites as the carbon-carbon coordination number
decreased.
In the case of TAC:H grown using a plasma beam source,
a variation in resistivity with ion energy similar to the case of
TAC was found [331 ]. At an ion energy of 200 keV, the resis-
tivity reached its maximum value of 2.5 x 107 f2 cm, indicating
that this was also the energy at which the peak in the sp 3 con-
tent occurred. There has also been evidence of a reduction in
the defect density by annealing [316]. This has been correlated
to a decrease in conductivity and increase in both activation en-
ergy and bandgap, around an optimum annealing temperature of
573 K, as shown previously in Figure 96. This is similar to the
trend described by Burden et al. [306] as shown in Figure 91,
which had previously demonstrated that annealing at 250~ in-
creased the optical bandgap of DAC. However, the study into
TAC:H was carried out in more detail and showed that these
films conducted via hopping at the band tails rather than at the
Fermi level, as the In J versus 1000/T plot showed a straight
line from 250 to 500 K. Therefore, the decrease in conductivity
and increase in activation energy as bought about by annealing
were attributed to the sharpening of the zr tails. This was later
corroberated [332] by evaluating the reciprocal Urbach slope,
which is proportional to the slope of the band tails in the energy
range just below the E04 gap. This value was found to increase
from 3.7 to 4.4 eV -1 from the unannealed sample to the sam-
ple annealed at 300~ implying a reduction in the density of
band-tail hopping sites. The postulated explanation for this was
a redistribution of H atoms to passivate dangling bonds by mov-
ing along the atomic network. In this way a six-atom cluster
would be converted, for example, into a four-atom cluster with
a wider bandgap.
6.10. Electronic Modification of Amorphous Carbon
A significant proportion of the work in a-C is related to attempt-
ing to electronically modify or "dope" the material. The most
commonly used method is to add gaseous nitrogen as an in situ
dopant during deposition. This is performed for two reasons.
First, nitrogen has been shown to be an n-type donor in the case
of diamond, albeit a deep one, so one of the major objectives
is to dope the material n-type. This is of interest because, as
has already been mentioned, a-C is thought to be intrinsically
p-type.
6.10.1. In Situ Doping o f Hydrogenated a-C: DAC, GAC,
and TAC:H
Several authors have reported the electronic doping of DAC by
the addition of gaseous precursors into the deposition cham-
ber during growth. The first reports of n- and p-type doping
were shown by Meyerson and Smith [333]. Films were grown
at using a DC glow discharge of acetylene at 150 and 250~
and gaseous addition of PH3 and B2H6 was investigated. It
was found that in the case of boron addition for films grown
at 250~ the activation energy showed a small rise from 0.6
to 0.65 eV at a diborane flow of 0.1%, followed by a fall to
0.3 eV at diborane flow rates of up to 10%. The conductivity
measurements showed the contrary, with a decrease from 10-11
to 10 -12 f2 cm at 0.1% diborane, followed by an increase of
u p t o 10 -7 ~ cm. This indicated that the DAC films were in-
trinsically n-type and could be doped p-type by the addition of
boron. Conversely, the films grown with increasing amounts of
PH3 showed only increases in conductivity (10-11 to 10 -7 f2
cm) and decreases in activation energy (0.6 to 0.3 eV), further
substantiating this claim. A later report [334] showed that the
thermopower for B-doped films was positive and for P-doped
films was negative, further indicating that doping was taking
place. However, the magnitude of thermopower was small, and
conductivity versus temperature measurements fitted a T 1/4
relationship, indicating a variable-range hopping mechanism.
The most important point to note, though, was that there was
no mention of bandgap in the study. It was later found that
the incorporation of a range of dopants would have the effect
of increasing the sp 2 content of the films, thus narrowing the
bandgap, decreasing the activation energy, and increasing the
conductivity though not necessarily as a result of electronic
doping, but rather a reduction of E g.
Jones and Stewart [305] then reported on the effects of
nitrogen, phosphine, and diborane doping into DAC:H. Both
diborane and phosphine were found to increase film conduc-
tivity. The effect of increasing the nitrogen content was to
decrease the optical bandgap from the initial value of 1.2 to
1.0 eV at a nitrogen flow ratio of 0.1, increase the conductiv-
ity at 227 K from 10 -7 to 10 -4 ~'2 - 1 cm -1, and decrease the
activation energy from 0.6 to 0.3 eV. However, the difference
between optical bandgap and activation energy remained con-
stant as the doping level was changed. This indicated that the
position of the Fermi level remained fixed relative to the va-
lence band irrespective of the doping level. Similar studies on
the effects of nitrogen modification were carried out by Amir
et al. [272], Stenzel et al. [302], and Khan et al. [304]. They re-
ported similar trends in terms of conductivity, activation energy,
and optical bandgap. Amir et al. performed thermopower mea-
surements which showed a positive sign for films containing
less than 1 at.% N, indicating conduction in the valence band
tail. Increasing the nitrogen content of the films changed this to
conduction around the Fermi level, as shown by the sharp re-
duction in the magnitude of the thermopower from 600 (0.2%
N) to - 4 # V K -1 (3% N). The change of the sign indicated
n-type conduction; however, the doping effect was very weak
and at still higher flow rates, the thermopower sign was once
more positive. Stenzel et al. suggested that the enhancement of
conductivity was due to a greater interconnectivity between ex-
isting clusters, resulting in enhanced hopping conduction.
In light of these contradictory findings, Helmbold et al. [301 ]
investigated the addition of phosphine into the deposition cham-
ber during DAC growth. They found that their current versus
temperature measurements showed a T 1/4 dependence which
was observed at and above room temperature. Therefore, a
model based on variable-range hopping was postulated; how-
ever, conduction appeared to be dictated by a "characteristic
 A M O R P H O U S C A R B O N THIN FILMS 479

10 0
temperature" at which all samples possessed the same conduc- o ' S c h w a n e } a L ((~AC)' ' ' ' ' ' '
_ 9 Amir etal(DAC) 9 .-&'"
tivity. All other parameters could be explained by factors such 1 0 -1 .

X Conway et aI.(TAC:H) .-"''"

as cluster diameter and lattice spacing. With this type of model, 1 0 .2
_ ..,-"

a shift in the Fermi level was excluded as changes in medium E

o
d:: b- ..... o- ..... e) . . . . o--
1 0 "3 - 9 _
range order could account for the variations in conductivity. 9 / t
/ .-
Silva et al. [335, 336] grew films on the driven electrode ~
~ 10-4 -- ,,/ o .-'" --
.m /" X .,'~
of a magnetically confined RF PECVD source, with a low DC ~ 10 5 _ o/p
," o
.,
.X"
_
t/ o.*~
self-bias of around 60 V and varying flow rates of nitrogen. It - /
~k /
9 -'"
0
was found that the optical bandgap increased from 1.65 to 2.1 0 10"6 ,, X . ,X.x 9

eV, and the Tauc B parameter increased from 300 to 580 cm-1 1 0 -7 .

eV -1 as the flow rate of nitrogen was increased from 0 to 7 I , I , "~ , I , I 1

0 2 4 6 8 10
at.%, which could be an effect of defect passivation. At higher N concentration (%)
levels of nitrogen (up to 13 at.%), the optical bandgap fell to less
than 2.0 eV, due to s p 2 reordering. Activation energy measure- Fig. 97. Variationof room temperature conductivity of nitrogen-doped DAC
films (see [272, 280, 331]).
ments showed that there were two regimes of conduction, one
at higher temperatures likely to be extended state conduction,
I ' I ' I '

and one at lower temperatures likely to be band-tail hopping. 1.0 9 Silva etal. -
o Schwan etal. "
It was found that the activation energy of the high temperature 0.9
/
l
mechanism appeared to increase from 0.5 to 0.92 eV and then > 0.8 /

decrease to 0.45 eV as the flow rate of nitrogen was increased, o')

>" 0.7 x
i., i x
x
the peak coinciding at 7 at.% N once more. It was assumed that (9
. /

x
c: 0.6
DAC is intrinsically p-type which agreed with the initial activa- LU
t- 0.5
tion energy value and bandgap. This value appeared to increase O
m 0.4
to half of the optical bandgap, suggesting that the Fermi level .m
tO
had moved to the center of the bandgap, due to the compensa- <~ 0.3
..... 6 " o ...........
0 0 "0 ..... ~. ..... 0--
tion of defects which led to p-type properties. Following this, 0.2
I , I , I , i , I "(~''"i"" , I , I , l ,

the activation energy decrease suggested n-type doping of the 0 2 4 6 8 10 12 14 16 18

material. A later study [337] showed from EELS measurements N content (%)
that the point at which the Fermi level was suggested to be in Fig. 98. Variationof activation energyof nitrogen-doped DAC films (see [280,
the center of the bandgap coincided with the point at which the 335]).
s p 3 fraction was at its highest. This point occurred at 7% atomic
nitrogen, which appeared to be a turning point. 3.0
' ' ' ' ' ' ',q' ' d, E~iIva'et lal.(19AC 1 '
This work could be compared to other studies, for example ,, , o Schwan etal.(GAC)

by Schwan et al. [77] who deposited GAC films using a plasma 2.5
o j"
" , 9 Amir etaL(DAC)
~" ..-" o 9 X Conway etaI.(TAC:H)
beam source (PBS). The films formed possessed a low hydro- o--O" -o- ....
~. 2.0 --6"" ............ X .... . 9
gen content of around 10%, which increased on the addition of
nitrogen, possibly due to the introduction of N - H bonds. Also "O !! "'X
c: 1.5
observed was an increase followed by a decrease in the optical j~ ':
_ :<.
bandgap, agreeing with the findings by Silva et al. However, it o 1.0 ..
was found that the electrical conductivity simply increased and ~. -=.~.. x
0 ":= .... i; ........
the activation energy decreased slightly as the nitrogen flow rate 0.5 .............9 _...~ i:
was increased. This meant that the Fermi level was only moving I , I , I , I , I'A:", ''" I , I , I ,

0 2 4 6 8 10 12 14 16
very slightly and other effects rather than doping were occur-
N content (%)
ring. For example, carriers may have been thermally activated
to a 7r* state, and the addition of nitrogen could have created Fig. 99. Variationof optical bandgap of nitrogen-doped DAC films (see [272,
N 7r* states which were situated below the C Jr* states, which 280, 331,335]).
the carriers were moving to. Therefore, the n-type dopant site
could have manifested itself as a mixed C - N zr* state. In com-
parison to this, Conway et al. [331] also grew films using a were grown using acetylene as the source gas, which contained
PBS and measured the optical bandgap and conductivity as a a nitrogen contamination corresponding to 4 at.% within the
function of nitrogen content. Here, it was found that the con- film. When methane was used, the polarity of the TAC:H/Si
ductivity showed increases with nitrogen content from ~ 10 -8 heterojunction was changed as the nitrogen concentration was
to "-~10 -5 f2 -] cm -1, and the optical bandgap showed a corre- increased, suggesting doping of the material through a compen-
sponding decrease from 2.0 to 1.0 eV (E04). No turning point sative state.
in the conductivity data as predicted by compensative dop- Figures 97-99 show the variations in optical bandgap, room
ing was observed. The explanation for this was that the films temperature conductivity, and activation energy as reported by
480 SILVA ET AL.
' ' ' ' ' " 1 ' ' .... "1 . . . . ''"1 ' ' ' ' ' ' " 1 ' ' :
various groups [77,272, 331,335]. Only those who have related 9 Davis el al. &/'

these parameters to the atomic nitrogen content within the films 1~176o Veerasamy et al. o/ ," i'"
have been included. As can be seen, the greatest problem is as- ,- 10-2 + Liuetal. o~ "~" i
;---- 9 Kleinsorge et al. /
certaining the variations in the undoped material, which depend
on such factors as self-bias voltage and deposition temperature. ~ 0,
9 .... "Z....
+
Also, there are large differences in the magnitude of optical [_> 10 .6 9 ~'....... "j~,,'" ::
bandgap as reported by different groups. This could be related "6 " ...... i~-= .... =~, 9 = , ~ /
to different methods employed in measuring such factors. As -o
Or" 1
0.8 "= 9
"'-. p___m
9 i ~_'" ~
. -'7"-~~
9
"'.. .....'+
./

has also been mentioned, activation energy measurements are r

, . . ,~.

10 -lo
problematic as some groups observe a T 1/4 relationship, some
. . , .,1,.I , , , ,,,,,I , , | =|,11| , | | .i ,,,l l. l

observe an Arrhenius relationship, and some observe two rela- 10 .2 10 1 10 ~ 101

tionships depending on the measurement temperature.
However, the following may be surmised. First, nitrogen has
the effect of increasing the conductivity. This could be either
due to doping or an increase in the sp 2 content. Second, dif-
ferent groups have seen different trends in terms of optical
bandgap and activation energy measurements. Some have ob-
served a decrease in optical bandgap [272, 331 ] which equates
to graphitization, and some have seen an increase in optical
bandgap with nitrogen content [77, 337]. This could equate to
a sharpening of the band tail (passivation) and hence a reduc-
tion in the defect density of the material. Meaurements made by
Khan et al. [310] have shown that the Tauc bandgap increased
from 0.7 to 1.0 eV as the N2 flow rate was increased, and this
was correlated to a reduction in Poole-Frenkel prefactor and de-
crease in paramagnetic defect density from 1020 to 1019 cm -3.
Although the latter can be explained by the pairing up of para-
magnetic spins due to doping, this is still strong evidence for
the passivation of midgap defects with the addition of nitrogen.
Therefore, it suffices to say that there is evidence for electronic
doping of DAC:H according to some groups, and also evidence
for either defect passivation or graphitization according to oth-
ers.
6.10.2. In Situ Doping o f TAC
The first reported case of successful electronic doping of TAC
was shown by Veerasamy et al. [338]. Phosphorus was incorpo-
rated into the films by use of a graphite/red phosphorus mixed
cathode. It was found that with an increase in cathodic phos-
phorus percentage, the conductivity was found to rise and the
activation energy fall. However, the evidence for n-type dop-
ing was weak as no initial increase in activation energy was
reported. However, electrical measurements of undoped and P-
doped TAC/n-Si heterojunctions showed a reversal in polarity,
suggesting that an n-type heterojunction had been formed with
the doped sample.
A later study [339, 340] documented successful n-type dop-
ing of TAC, this time by injecting nitrogen gas into the bend
region of the filtered cathodic vacuum arc system. The evidence
for n-type of doping of TAC was first a change in sign of ther-
mopower from positive to negative. Second, the resistivity and
activation energy of the films showed an increase followed by a
decrease, which assuming intrinsically doped TAC was p-type,
placed the undoped Fermi level at 0.3 V above the valence
band edge. The compensative case at which the Fermi level
N concentration (%)
Fig. 100. Variation of room temperature conductivity of nitrogen-doped TAC
films (see [ 112, 324, 339, 342]).
was found to be midgap corresponded to approximately 0.45
at.% nitrogen. Following this, the Fermi level was thought to
move to within 0.2 eV of the conduction band edge on the addi-
tion of nitrogen. The optical bandgap was also observed to fall,
indicating alloying of the material and sp 2 reordering. EELS
analysis suggested that at low nitrogen levels there was little
sp 2 reordering of the material, which was evident at higher ni-
trogen levels.
A similar study was reported soon afterward by Davis et al.
[ 111,327]. Similar trends in terms of variations of resistivity
and activation energy were reported. However, in this case, a
rectifying p - n junction consisting of nitrogen-doped TAC on
undoped TAC was also found. These trends have been repro-
duced elsewhere [341,342]. However, other studies [324, 343,
344] have seen only an increase in conductivity and a decrease
in optical bandgap as the nitrogen content is increased, which
is evidence only for sp 2 reordering.
In the case of Ronning et al. [343, 344], this could be as
the films were grown using mass-selected ion beam deposi-
tion and nitrogen was added by alternating the ionic species
layer-by-layer during deposition. This may have had an effect
on the doping efficiency or controllability of activated dopant.
However, it was found that conduction followed ohmic conduc-
tion at low fields, suggesting hopping conduction, and followed
Poole-Frenkel conduction due to two trap states, one around
E F and one at the conduction band edge, at high fields. The
addition of nitrogen or boron had the effect of modifying the
I / V characteristics such that the density of one trap state in-
creased far more than the density of the other state. This led to
a kink in the I / V characteristic and suggested that the addi-
tion of the dopant had the effect of vastly increasing the density
of states at the Fermi level. However, no change in activation
energy values was observed, suggesting no shift in the Fermi
level. Also, p - i - n diodes were fabricated and were not found
to rectify, suggesting no doping effect, or a pinned Fermi level.
With the MIS structures, heterojunction rectification was ob-
served, but the polarity did not appear to change with respect to
the doping of the film.
Figures 100-102 show the variations in conductivity, acti-
vation energy, and optical bandgap as a function of nitrogen
 AMORPHOUS CARBON THIN FILMS 481
' ' ' '''"1 ' ' ' ' ''"1 ' ' ' '''"1 ' ' ' '''"1 ' '

1.2 -= Davis et al.

o V e e r a s a m y et al. ,, .. M.. ,, .,
.4..:+..
~c~~-. c./ (g)\c /
~,
v
(2)
1.0
'-I-
-&
Liu et al.
Kleinsorge et/~l.
"

,
,
"

9
"
,
"
"'4"
':
..
(a)
~N I1 I II II
>, 0.8 ' "..
, .+
G)
t-

0.6 ,' 9
% ...........i..........................................
ie; ..........
in

............................. i i. ..............
O '
._ i I~
0.4 NI" ~ ' C / / " ~ " ' - C~ \C /
.g .....=+__,........., ........
<
O
0.2 ~' ~
t II
0.0 ........ i ........ I , , ,, .... I , , .,,,,,, . , ........................................................................................................................................................................... ..

10 a 1 0 .2 10 1 10 ~ 10'
N concentration (%) (c) (f)//c ~ c \\ (i) cI
Fig. 10l. Variation of activation energy of nitrogen-doped TAC films (see + -c- c\../c III
[112, 324, 339, 342]). N N
oo

I
' ' ' ' ' " 1 ' ' ' ' ' ' " 1 ' ' ' ' ' ' " 1 ' ":-'.'''"1 ' '
"~'.q..
2.5 Fig. 103. Possible configurations of nitrogen in a-C:H:N. The lines represent
9 ""1-
bonds" dots are unpaired electrons. The items within the dotted box are the
~- 2.o § doping configurations (after Silva et al. [337]).
O 9

~ 1.5
"o Robertson [345] attempted to ascertain the role of N in the
~ 1.0
..Q
doping process. In the case of diamond, the donor level was
o 9 D a v i s et al, 9 \9
\
~1 0 . 5 o Veerasamy etal. \ about 1.7 eV from the conduction band edge. In the case of
I-- -I- Liu et al. \ TAC, the substitutional N site was now shallow when compared
9 Kleinsorge etal.
0.0 to the zr* edge. However, the doping efficiency was likely to be
9 , , ,,,,I , , , , ,,,,I i , , , ,,,,I , , , , |,111 i

1 0 .2 10 1 10 ~ 101 low as most N would adopt its trivalent bonding configurations

N concentration (%) (see (a) in Figure 103), so the substitutional N + site (b) was
Fig. 102. Variationof optical bandgap of nitrogen-dopedTAC films (see [ 112, less likely. Alternatively, the N4 site could compensate existing
324, 339, 3421). midgap defects leading to the N+C3 state (c), which would re-
sult in in a full C defect state and an empty N donor level, and
hence a weak doping effect. However, in the case of a predomi-
content, as reported by various groups [324, 327, 339, 342]. nately aromatically bonded s p 2 material as in the case of higher
The atomic percentage of nitrogen content as a function of ni- nitrogen doping levels, N4 could still substitute a C atom in
trogen flow rate is taken from other studies where necessary an aromatic ring, contribute an electron into an Nzr* state, and
[66, 112]. What can first be noted is that at moderately high weakly dope it (e). However, it would be far more likely in this
nitrogen contents (1%), the optical bandgap closes, presumably case that nondoping pyridine- or pyrrolelike structures would
due to an increase in the s p 2 content. Second, the resulting vari- be formed (f). For an olefinic s p 2 bonded region, once again a
ations differ significantly in terms of conductivity. This could weak bonding effect can be brought about (h) in spite of other
be related to the relative fraction of s p 2 bonding which is also more likely configurations (g) or even s p 1 sites (i). Figure 103
controlled by such factors as the incident ion energy, as men- shows these structures diagramatically, as shown by Silva et al.
tioned earlier, or the monochromacity of the ion beam. Also, as [337].
has been mentioned earlier, these conductivity and activation
energy measurements may be compromised as only the sur-
6.11. Summary
face layer of the TAC film is probed, which may be sp2-rich.
Third, in terms of the evidence for doping, the compensated The electronic properties of a-C have been discussed with
state varies considerably according to the different groups. This trends in terms of growth bias voltage/ion energy, deposition
could be related to the method of nitrogen inclusion into the temperature, postdeposition annealing, and dopant addition.
plasma, as Xu et al. injected nitrogen gas directly into the ca- Variations in the electrical properties have been coupled with
thodic plume, resulting in a large degree of ionization. Liu et al. changes in factors such as paramagnetic defect density, s p 2
used an ion beam source, and the others added nitrogen sim- content, and optical bandgap. There is further evidence here for
ply into the deposition chamber or the torus. Finally, not all the point that conduction in a-C is governed by the density and
groups see a turning point in the values of conductivity and ac- distribution of the s p 2 hybridized states, whether these exist in
tivation energy corresponding to the compensated state. This chains or clusters.
also suggests that the reactor configuration has a large role in It has been seen that there is evidence of nitrogen possessing
determining whether doping is occurring or not. the ability to dope a-C films n-type; however, it also appears
482 SILVA ET AL.

that the doping process is complicated and a more careful anal-

ysis is required. In particular, electrical measurements have
been shown to concentrate on conductivity, activation energy,
and bandgap measurements, and useful information which may
be derived from the high-field conduction properties has been
largely ignored.

7. C O N C E P T S O F L O C A L I Z A T I O N AND
D E L O C A L I Z A T I O N IN a-C

Here we attempt to discuss in greater detail the phenomenon of

electron localization in a-C. It has already been mentioned that
this property limits the electronic properties of a-C a great deal
and results in hopping conduction, as explained by a variety of
mechanisms, over a wide temperature range. Fig. 104. Calculated partial density of states for an a-C network showing
The disorder in an amorphous material first causes scattering the high inverse participation ratio of the Jr states despite possessing 80% s p 2
and a reduction in the mobility of the carriers. If the disor- bonds. Reproduced with permission from [299], 9 1997, Elsevier Science.
der is increased, localization of the wavefunction may occur
where no movement of carriers is possible at zero Kelvin. At
finite temperatures tunnelling between localized states may oc-
cur. A localization length, R0, of PAC has been measured to be
1.0-1.5 nm by Silva et al. [347], which is significantly larger
than for a-Si (10-12 nm). Later calculations of the localization
radius using photoconductivity measurements showed it to be
as low as 0.2-0.3 nm for TAC and 0.9 nm for TAC:H [330].
Using the notation used by Anderson [348], it was shown that
if

3V/B > 1 (7.1)

where B(-- 2z V) is the bandwidth of the conduction band due

to the interaction between the atoms and z is the coordination
number for cr states, we get

~V/B = ~V/2zV > 1 (7.2)

and

d V / g > 2z (7.3)

In a-Si which only permits cr bonds, localization only oc-

curs at the tail states of both conduction and valence bands. In
the case of a-C where both Jr and cr bonds are present, as well
as defect states, the localization present can extend through the
gap [149]. Chen et al. [349] performed atomistic calculations
and showed that the entire rr band is localized. As shown in
Figure 104, the inverse participation ratio of the Jr states that
control the conduction properties is very high. The simulation
used a sp 2 bonding concentration of 80%, which is well over
the percolation limit, and despite this the conduction within the
material was poor. Interestingly in this case the disorder po-
tential ~ V is expected to be quite small and so there must be
another reason for the localization of the wavefunction. This
effect was found to be the interaction between zr states which
is controlled by the projected dihedral angle 4~ of two bonds,
as shown in Figure 105. In most cases the planes involving Jr
bonds ended up being close to orthogonal and so there was little
or no interaction as V, the potential well of each atom, tended
Fig. 105. Schematic of the low interaction between adjacent p-orbitals due to
their random orientation.
to zero. This meant that 6 V ( = V0 - V) was of a similar mag-
nitude to V so 6 V~ V tended to be greater than 1, resulting in
localization over the whole wavefunction.
This result is completely different from a-Si as in that case
all the bonds are tetrahedral cr bonds. Therefore, the tail states
in a-C will differ greatly from those of a-Si. It also means that in
the case of PL, it is likely that the generated electron-hole pair
will remain within a delocalized cluster, which is isolated from
the remainder of the network and give rise to a germinate pair.
This also means that the PL emission will be highly polarized
as seen by experiments [201 ]. Another artifact of the localized
tail states in a-C would be the intense room temperature PL as
 AMORPHOUS CARBON THIN FILMS 483

the carriers cannot diffuse apart easily and thereby get trapped t 9 Praweretal.
_//.~ .... -, ........... .~ ,, o Khan et al.
into a nonradiative recombination path as seen by experiments ,'i ..... ",i ..... "i ..... ',,i ..... ,',i ..... "i
o -I- McCulloch et al.
[347]. 1014 r o ~-2.5 0
0

1012 i o 0 _?_
+
7.1. Ion Implantation of a-C r ~2.0i
~01~ + o
Implantation of diamond has been carried out as a route to elec- +
tronic doping of the material. Boron has successfully doped N 6 o
diamond p-type [350], and there has been evidence for the I1

n-type doping of diamond using phosphorus [351 ]. The damage ~- 10 4

effects of ion implantation in diamond have also been widely
10 2 0.5 (~b i o +
reported. These include the onset of hopping conduction [352], Ca)
o __/~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(b!
and also the onset of s p 2 reordering [353]. There appears to be 0.0 ....................... 0 ....
100.0 1013 1015 1017 0.0 1013 1015 1017
a threshold ion dose in both cases above which the film reorders
Dose ( i o n s c m -2) D o s e (ions c m 2)
into an spZ-rich state and the electrical conductivity shows dra-
matic rises. This is related to the eventual overlap of damage Fig. 106. Variation of room temperature conductivity and optical bandgap of
PAC [356], DAC [354], and TAC [107] films as a function of carbon implant
cascades. However, at lower doses, it was found that diamond
ion dose.
transforms into an amorphous s p 3 bonded phase, in a way sim-
ilar to silicon. 100 ' I ' I ' I '

One of the earliest reports of the effect of ion implantation

~
10 "1 -

into DAC films was conducted by Prawer et al. [354]. This 10 .2 -

study used a novel experimental technique where the resistivity 10 .3 -
of the film was measured in situ during ion irradiation. It was ~,wE 104 -
found that there was a threshold dose below which no changes lO-S _ cont ~
10 .6 - 9 1E12
were evident, and after which the resistivity collapsed by as
10 -r -
much as six orders of magnitude. The bandgap showed a con-
10-8 -
comitant collapse, as did the hydrogen content. This suggested 10 .9 -
that the removal of hydrogen resulted in a depassivation of dan- 10 -10 I I = I , ,

gling bonds and a rise in the number of intergap states. This
caused the increase in conductivity at approx. 1015 ions cm -2
(which was thought to be of the type of variable-range hopping
in this case) and reduction in bandgap due to the smearing out of
band tails. Graphitization was thought not to occur until higher
doses, when the damage cascades were thought to overlap, as
in the case of diamond, and the films underwent macroscopic
graphitization.
This was similar to results found by Ingram et al. [355],
Khan et al. [356], and Doll et al. [357], who also reported on
n-type conductivity after DAC:H was implanted with nitrogen
ions. Whether this was a doping effect, or a consequence of
defect addition, was not ascertained. However, Khan et al. did
not see a resistivity threshold that occurred at the same dose
as for the optical bandgap collapse. This could be because the
as-grown material was polymeric and hence intrinsically much
more resistive. Therefore, the effect of small changes in resis-
tivity could be measured. However, it was suggested that some
degree of electron delocalization of the highly localized n states
was occurring that accounted for the large changes in resistiv-
ity as a function of ion dose, before the onset of macroscopic
reordering. Wang et al. [358] found an initial increase in re-
sistivity with an implantation dose of 1 • 1015 ions cm -2. IR
measurements suggested that at this dose the C - H s p 3 concen-
tration had increased, which would result in a decrease in the
density of hopping centers and hence higher resistivity.
McCulloch et al. [ 107] implanted carbon and xenon ions into
TAC and also performed in situ resistance measurements. In
-8x105 -6x10 s -4x10 s -2x10 s 2x10 s 4x10 5 6x10 5 8x10 5
E (V c m "1)
Fig. 107. Variation in J versus E characteristic of boron implanted PAC films
as a function of boron ion dose.
this case, it was found that there was no threshold behavior in
the resistivity trend, which was mirrored in the optical bandgap
trend. This suggested that there was a regime at intermediate
doses, in which a highly disordered sp3-rich but nongraphitic
material was being created. This was similar to the case in di-
amond and was corroborated using EELS measurements. For
very high doses, it was thought that conduction was due to
hopping between graphitic islands. It was also found, as by
Doll et al. [357], that using Seebeck measurements undoped
TAC was p-type and after carbon implantation the films became
n-type. Therefore, it was suggested that s p 2 bonded material
was being created, which contributed to the conductivity by
acting as n-type dopants and also narrowed the bandgap. A later
study [359] showed that the effect of irradiation at elevated tem-
peratures was to increase the s p 2 fraction at higher doses and
also the degree of reordering. Therefore, a graphitic material
was favored at elevated temperatures, also as in the case of dia-
mond. Figure 106 shows the variation in resistivity and optical
gap with implantation dose for DAC, TAC, and PAC films, ac-
cording to various researchers [ 107,354, 356].
Researchers have attempted to improve the conduction prop-
erties in a-C with the addition of impurities such as hydrogen
484
10 .2 i , I '
10 "3
E 0-4 - ~ \ / t
< \ / /
,',///
/ /
+
I I '
] r/
~ 10 7 -
~10 8
10 9 1
~ 104 nm
10 "1o
-lxl
t 08, I OS,
-5xl
,
5xl
lOS
E l e c t r i c field (V c m -~)
Fig. 108. Variation in J versus E characteristic of boron implanted a-C:H
films at a dose of 2 x 1015 cm - 2 , showing rectification in the case of the thicker
film.
and nitrogen into the band structure. Some encouraging results
have arisen in the case of FCVA [338], magnetron sputtering
[77], and PECVD with very high nitrogen content (alloying)
[337]. It is interesting to note that in the case of enhanced
conduction with FCVA and magnetron sputtering, significant
quantities of impurities have been needed to see any effects
(when compared to traditional doping of crystalline semicon-
ductors), but these effects were true and reproducible. Such
results have not been seen for any other a-C films using other
deposition techniques. One aspect that is common to both those
techniques is the use of intense ion bombardment creating
highly stressed and metastable structures. Extending this theme
further we have used ion implantation in an attempt to delocal-
ize electronic states within the a-C films that we have deposited
with very low defect densities [310]. The variations of the elec-
tronic properties as a function of ion dose for B implantation
are shown in Figure 107. It should be noted that the quantity
of implant used is much smaller than those used in the previ-
ous studies, but the changes in conduction are greater. It can
be seen that there is a current gain which we observe at a dose
of 2 x 1015 cm -e which is dependent on the applied voltage.
A closer analysis reveals that this corresponds to a degree of
hysteresis in the characteristic (see Fig. 108), which can be re-
moved by implanting a thicker film (104 nm as opposed to 80
nm) resulting in the implant only going through part of the film.
This suggests the formation of a Schottky junction, as true rec-
tification has been demonstrated in spite of only metal contacts
on either side of the film, for the first time in a-C. This suggests
delocalization of the film into a material onto which Schottky
contacts may be formed.
8. E L E C T R O N FIELD E M I S S I O N
8.1. I n t r o d u c t i o n
Carbon based cathodes have been proposed as the emitter mate-
rial for the next generation of fiat panel displays based on field
SILVA ET AL.
emission, due to their enviable property of emitting electrons
,,~,," from nominally fiat surfaces at relatively low electric fields
[360, 361 ]. This has attracted much publicity and research inter-
est with some of the major multinationals producing prototype
displays using this cathode material. With a global market for
flat panel displays estimated at US$20 billion by the year 2002,
_
this has given the amorphous carbon community much hope
_
as a possible outlet for active devices. Initial interest in carbon
films as cold cathodes was driven by the hope that these films
-
possessed negative electron affinity [362]. This meant that as
80 nm a cathode all that was needed was to ensure that there was a
supply of electrons injected into the conduction band of the
,
lxl
I 0 6
material, and that would allow for a suitable emission current
at the front surface. Early experiments and calculations pointed
toward negative or low electron affinity values whether the ma-
terial was crystalline or amorphous, which allowed electrons
to be extracted from the surface of the films at relatively low
electric fields [362, 363]. Yet, more recently, it has been shown
by models based on empirical results that the back contact to
the carbon films can be as important to the emission of elec-
trons at low electric fields [45, 364, 365] as the front surface
[126, 366, 367]. This has meant that a thorough review of the
emission process has been required in order for an acceptable
model to be proposed. It is also still open to debate if there is
an universally acceptable model, due to the plethora of differ-
ent films available in the literature and the misunderstanding of
trying to compare one set of films with another. A classic ex-
ample is in the films deposited by Gr~Sning et al. [368] which
have been compared by a number of authors to films deposited
by RF PECVD (for example, see [45]). A closer look at just
the material properties shows that Groning's films are graphite-
like (GAC) with no optical bandgap while the DAC films by
Amaratunga and Silva have an optical bandgap close to 2 eV.
Therefore, no parallels can be made in terms of field emission
models and transfer of experimental results for films that have
material properties that are dissimilar.
The primary reason for researching the field emission prop-
erties of amorphous carbon thin films has been the electron
emission at low electric fields, which has allowed for its
possible usage in flat field emission displays at voltages com-
patible with current complimentary metal oxide semiconductor
(CMOS) technology driver circuitry. Flat cathodes have consid-
erable advantages over their "Spindt" tip counterparts that are
more expensive and more complicated to fabricate on a large
area display. Yet, the initial designs for using a simple ma-
trix addressed two-terminal fiat carbon cathode [360] has not
been forthcoming due to material property considerations as
discussed later.
8.2. T h e o r y o f F i e l d E m i s s i o n
The electron emission that takes place from a metal surface is
principally determined by the strength of the applied field in
combination with the magnitude of the work function as shown
in Figure 109. In general, as the electric field is increased first
 AMORPHOUS CARBON THIN FILMS 485

can be expressed as
e2
V(z) -- h - eEz - (8.2)
16JrE0z
The latter potential results in a rounding of the potential bar-
rier and a lowering of the barrier height Ah when compared
with the triangular barrier. This results in a change in barrier
height
eE ]1/2
= 3.975 x 10-SE 1/2 (8.3)
Ah=e 4:rrEo

where the macroscopic electric field E is measured in V/m. For

a field of 20 V//zm the barrier lowering due to image charge
effects is approximately 0.17 eV. In addition to the assumption
with regard to the shape of the potential barrier, the FN theory
as applied to metals also assumes that [370]

Fig. 109. Schematic diagram of the different forms of electron emission that
(i) the metal has a free electron band structure,
can take place from a metal surface. (ii) the electrons are in thermodynamic equilibrium and
obey Fermi-Dirac statistics,
(iii) the metal is at zero temperature,
(iv) the surface is smooth,
(v) the work function is uniform across the emitting
surface and is independent of the applied field which is
turn is assumed to be uniform above the surface,
(vi) the Jeffreys-Wantzel-Krames-Brillouin (JWKB)
approximation may be invoked to evaluate the
penetration coefficients.

Within these assumptions the emission current J can be ex-

pressed as

2
a Eloca I exp i_b~3/2) (8.4)
J -- q~ Elocal
Fig. 110. The shape of the potential barrier when FN emission is taking place.
where a and b are constants with approximate values of 1.54 x
10 -6 eV V -2 and 6.83 x 109 e -3/2 V m - l , respectively. The
emission current density is determined from the emission cur-
thermionic emission over the top of surface barrier (work func- rent divided by the area of electron emission A, which will
tion) will occur, followed by emission over the field reduced generally not be equal to the area of an anode as measured by
barrier (Schottky emission). Emission will then occur partly experiment. The local electric field Elocal is usually related to
over the barrier if the temperature is high enough and partly the macroscopically applied electric field Eapplied by the equa-
through the barrier. As the temperature is lowered emission will tion
come from electrons tunnelling through the barrier (Fowler-
Elocal - / 3 Eapplied (8.5)
Nordheim tunnelling) from electron states near the Fermi level
and finally at very high fields, emission from states below the where/3 is the field enhancement factor. Values of/3 for ellip-
Fermi level (ballistic electron emission) [369]. In the Fowler- soidal tips or protrusions of radius r and height h can be given
Nordheim (FN) theory [370] of electron emission the shape of as [371]
the potential barrier at the front surface is important. Figure 110 h
shows two possible potentials; the first potential is taken as a /3 ~ 2 -I- - (8.6)
F
rectangular barrier of the form
provided h / r > 5.
V(z) =h-eEz (8.1) Fowler-Nordheim type emission of electrons would show
that the peak of the electron energy distribution was centered
where h is the surface barrier height, often regarded as the work at the Fermi level of the emitter with a sharp cutoff measured
function (4~) of the material. The second potential incorporates on the high energy side reflecting the thermal occupation of
the image charge effects which in Systeme International units electron states. The low energy side is characterized by an
486
Electron energy
n*- Si a-C(:H) layer vacuum distribution (a.u)
Fig. 11 I. The predicted FEED as a function of the emission process due to
(a) Fowler-Nordheim emission from the Fermi level at the back metal contact,
(b) hot electron emission from the conduction band of a semiconductor, and (c)
emission from the valence band of a semiconductor.
exponential decrease as the probability of electron emission di-
minishes and the barrier to tunnelling increases. In the case of
a semiconductor, electron emission may also occur from the
conduction band, valence band, defect states, and also surface
states. Measurement of the energy distribution of the emitted
electrons should be able to distinguish between the different
mechanisms. If electron emission originates from the conduc-
tion band then the distribution of electron energy should be
shifted to lower energies and possess a lower energy cutoff. This
shift of the field electron energy distribution (FEED) is due to
the potential drop between the surface and the back contact as
shown in Figure 111 a. In Figure 111 b and c the predicted elec-
tron energy distribution for emission via hot relaxing carriers
from the conduction band and from the valence band emis-
sion, respectively, are shown. Emission from the valence band
maximum has been reported in p-type diamond and from the
conduction band minimum from undoped diamond films. Fur-
thermore, in low conductivity materials internal electric fields
may be present, as observed by Geis et al. [364] in N doped
diamond films.
SILVA ET AL.
Gr6ning et al. [368] have performed both FE measurements
and also electron energy distribution measurements of N con-
taining films. The films contained up to 17 at.% N and were
found to be highly conducting. Using a 4 mm diameter stainless
steel anode they observed threshold fields for 1 nA emission to
be in the range of 20-25 V//xm. Plotting the I - V characteristic
on a FN plot gave an apparent work function of 0.16 eV as-
suming fl = 1. Energy resolved FE measurements were made
by placing a grounded Cu TEM grid 50/zm above the samples,
which was biased negatively at about - 1 0 0 0 V. The samples
were illuminated with either ultraviolet radiation or X-rays, al-
lowing ultraviolet photoelectron spectroscopy (UPS) and X-ray
photoelectron spectroscopy analysis to be performed to allow
measurement of the sample work function. They measured the
onset of field emission at the Fermi level with a low energy tail
and cutoff of UPS emission at 4.9 eV. Using this energy as the
value of film work function they determined from the FN plot a
field enhancement factor of 171 from which a local electric field
of 6500 V / # m was calculated. Since emission was observed
from the Fermi level with a high energy cutoff, characteristic
of FN tunnelling, they concluded that no field penetration oc-
curred. However, this is to be expected since the conductivity
of the film is so high the emission would be predicted to be a
"front" surface dominated process.
It is worth pointing out at an early stage an important exper-
imental fact when comparing threshold fields between different
research groups and with different types of samples. The two
most common geometries used to measure FE characteristics
are the sphere-to-plane geometry and the plane-to-plane geom-
etry. In the former case an anode (either point or large area) is
mounted between 10 and 100 # m away from the cathode mate-
rial, a high voltage is applied to it, and the current is measured.
In the case of the latter arrangement large area conductors such
as indium tin oxide (ITO) coated glass are used. This latter
configuration will tend to measure the turn on behavior of the
lowest emitting areas (sites) first and will tend to give lower
threshold fields when compared with the single point (probe)
measurement tests.
8.3. Planar Emitter Structures Based on C a r b o n
It is worth categorising several types of amorphous carbon films
for the analysis of their electron field emission process. Pro-
gressing with ascending energies required for the growth of the
films, we will consider emission from PAC, DAC, TAC, GAC,
and NAC films. It is also worth discussing that in the case of a-C
films that do not possess large numbers of defect states within
the films or graphitic or conducting regions in its microstruc-
ture, in general a conditioning process has to be encountered
before the emission of electrons takes place. Subsequent to the
initiation voltage required in the conditioning, emission takes
place at successively lower threshold fields which reaches a
minimum value after about four cycles. The hysteresis observed
in this process of conditioning is shown clearly in Figure 112,
and is nonreversible; i.e., once a cathode has been conditioned
it will remain conditioned despite the surface being examined
 A M O R P H O U S C A R B O N THIN FILMS
Fig. 112. Variationof the electron emission current as a function of electric
field, for successive voltage cycles of a typical PAC film. Note the reduction in
hysteresis for each successive cycle.
Fig. 113. A simulation study of conducting channels within the a-C matrix
that give rise to local field enhancement.
days later even after exposure to atmospheric conditions. This
points to the fact that surface termination or the front surface
dipole effects may play less of a role than originally thought.
We will show that by examining the various models avail-
able in the literature, there are some hypotheses that are more
suitable than others. According to our view, in most cases the
crucial forming step of the field emitting process is the condi-
tioning or first ramp up run in the experiment for a majority of
the films. We show results based on simulation that incorporate
inclusion of current channels or conducting regions.
The "worm-hole"-like current channels, if created during
conditioning, are highly localized spatially and are well sep-
arated from each other. This means that around each of the
conducting channels it is possible that high fields may be
sustained by space charge that are necessary in order for a con-
tinuous electron emission process to be sustained. It should also
be noted that in a dielectric such as a-C, which has a dielectric
487
Fig. 114. Variationof threshold electric field as a function of film thickness
for PAC/Si films.
constant ~Sr of ~4, a conducting channel would represent a di-
electric medium of 1 and thereby naturally give rise to field
crowding effects that may be seen from the front surface as "in-
ternal" field enhancement. This local/3 factor would be further
enhanced by inhomogenities within the amorphous films due
to the localized nature of the films electronic structure as de-
scribed in Section 7. Yet, it should be noted that for emission
to take place the matrix surrounding this conducting channel
must have its band structure suitably bent by the ionized car-
riers for electrons to be transported to the front surface of the
films for emission. See Figure 113. Such a model could also
be used to explain the very low thresholds reported in hydro-
carbon polymers [372]. The highly localized channels could
also act as conduits to remove any excess charge at the surface
due to its relatively low resistivity compared to the bulk of the
film. Recent simulation studies conducted show the channels to
be positively charged in comparison to the surrounding matrix
during electron emission, which would tend to indicate that the
channels can effectively act as electron sinks as well as electron
sources.
8.3.1. Polymerlike Amorphous Carbon Films
There are a number of reports on the electron field emis-
sion properties of these types of films [365, 373, 374]. These
films have low defect densities and so generally require a
high initiation electric field for emission to take place. Sig-
nificant hysteresis is observed in the first cycle after initiation.
Subsequent to the initiation process, the threshold field for elec-
tron emission has been shown to be controlled between 10 to
70 V//zm by varying the thickness of the undoped films by For-
rest et al. [365] (Fig. 114). Despite some of these films being
subject to very high electric fields of the order of 70 V//zm, no
morphological change was observed with a scanning electron
microscope after emission. The data show a very strong depen-
488 SILVA ET AL.

24 _ I ' ( a ) -L (a)
20
100 -
'7,
E 80
::L
12 w 60 -
o?, I I I I I I I "10
40--
I:: 6x1017 (b)_ LL
O
20--
o
"~
r 4xl 017 m
0 I I I I
"lO 1.5 1.7 1.9 2.1 2.3
C
9~. 2x1017
cO Refractive index
} I
2.6 (c)- (b)
2.4 .-. 100
I-- 80 9 J
2.2 I I I I I 1 I ~, 60 9 9 9. j
J
0 1 2 3 4 5 6 7
-~ 40 %0
i;" 20 ~ ~ "~/
N content (at. %)
0 I o I I I I
Fig. 115. Variation of (a) threshold field, (b) spin density, and (c) Tauc gap as
a function of N content for PAC films. 0 0.5 1 1.5 2 2.5
Tauc gap (eV)

dence of the conditioned threshold field on film thickness, with (c)

the required field showing a minimum turning point in the data 100 - -
at a film thickness close to 60 nm. The threshold field needed
80 -- ""i" .................
for emission increases on either side of this optimum thickness, E...j 9 . . . . . . ..

with the surface of the films not exhibiting any morphologi- 60 - - o '• 9
~ .~... 9 ..-" 9
cal changes when examined by an atomic force microscope _ 40-- o ~ - ~ o ". .-'o
(AFM) as a function of film thickness. Therefore, it is diffi- u_ 20-- ~. ......
O
cult to attribute the emission readily to an external local field o- I I I ! I
enhancement factor without further proof of its existence. Al- 0 500 1000 1500 2000 2500
though s p 2 clustering has been proposed as being a factor in the
Anneal t i m e (s)
controlling of the electron emission [366, 375], in these films
the growth conditions have been kept constant throughout the Fig. 116. Variationof the field emission as a function of annealing for PAC
deposition process and so no changes in the microstructure of films: (a) versus refractive index, (b) versus Tauc optical gap, and (c) versus
anneal time at 400~C.
the films are expected. The observed variations with film thick-
ness in these films were explained using the interlayer model
based on space charge induced band bending in thin films, as
discussed later in this chapter. the number of s p 2 clusters remains the same but that the cluster
In order to examine the other factors that control the emis- size is increasing. Therefore, the lowering of the threshold field
sion properties of these films, the variation of the threshold field with addition of N was attributed to an increase in the cluster
with nitrogen content for a series of films of thickness 60 nm size in the polymeric films. Yet, as discussed in the modelling
were also examined. In addition to monitoring the threshold of the emission process later in this chapter, for PAC films that
field, the EPR and Tauc optical gap were also examined, as have a large optical bandgap, low defect density, and a well
shown in Figure 115. Addition of N has been shown to reduce defined heterojunction for the back contact, in most cases the
the threshold field in DAC films [45] and also in TAC films limiting factor is controlled not by the front surface but by the
[376]. However, both these types of films have had large initial back surface.
paramagnetic defect concentrations and the nitrogen increase The variation of the emission properties as a function of
has generally ended up decreasing the spin density either by annealing has also been reported [373]. It was first shown by
defect passivation or doping. In the case of PAC films the addi- Forrest et al. [374] that large changes in the refractive index
tion of nitrogen also decreases the threshold field, but there is and Tauc optical gap could be obtained by modest variations
little or no decrease in the defect density. Therefore, we are able in the postannealing of these films. In this study an attempt was
to decouple the effects of defect passivation from field emission made to correlate the electron emission studies to the annealing.
in this case. In the polymeric films the continued decrease in the It was correctly concluded that no definite relationships could
Tauc gap without an increase in the spin density indicates that be obtained [374] due to the fact that there were also varia-
 AMORPHOUS CARBON THIN FILMS 489

30 I 1021 -- I i I =
E::L (a) _
_
- 9 (a)
_

25 B
_ _

E 1020 _
'10 0
v
_
_

20 m _
_
_

"O r _

O
t - 15 1019 = _
_
OO _
r _ 9 9 9
~ _
_
e-

l -
10 _

i0 TM
1021 I J I i I t I i I i _

(b) i I i ! I i I
,,?,
E -
(b)
1 020
_
o
9"o 20-
(D
c: 1 0 1 9
t ~

(9 nO
"10

o
z::: 10
,-
"~. 1 018 U'J

or)
.e-
1017 I = I i I J I J 1 l b-
0 I i I i I i 1 i I
5O 100 150 200 250 0 4 8 12 16

Negative self bias (V) N content (at. %)

Fig. 117. Variation of (a) threshold electric field and (b) spin density as a Fig. 118. Variation of (a) threshold electric field and (b) spin density as a
function of negative self-bias during deposition for DAC films. function of nitrogen content at a fixed bias during deposition for DAC films.

tions in the film thickness as the films were subject to annealing.
Therefore, Burden et al. [373] followed up the experiment mak-
ing certain that the sample film thickness was kept constant by
careful control of the deposition parameters in the study that
followed. A summary of the variations observed by them is
shown in Figure 116. The films discussed here were subject to
400~ anneals for times that varied from 0 to 2400 s. The dased
lines in Figure 116a and b can be predicted using the space
charge model described by Burden et al. In their analysis of
electron field emission, as the film thickness was kept constant,
they were able to use the refractive index as a microstructural
parameter and empirically show that for Poisson's equation to
be satisfied in a space charge induced band bending model the
following equation could be derived:
Bn 2
Eth ~ A -
(C-
n is the refractive index and A, B, C, and D are fitting parame-
ters that were given values of 90, 10, 5, and 0.5 for the best fit
for their films.
In the case of the threshold field variation with optical gap,
they argued that if the valence band remained static with respect
to the vacuum level when the bandgap varies [363], in the space
charge induced band bending model the barrier that electrons
need to overcome at the back n-Si/PAC heterojunction would
be proportional to the bandgap (assuming fully depleted bands).
Also discussed were the optimum anneal conditions for electron
emission with annealing as shown in Figure 116c.
8.3.2. Diamondlike Amorphous Carbon Films
Good examples of DAC films are those deposited on the
driven electrode of an RF PECVD system where during the
growth process there is also ion beam "subplantation" of growth
species involved. In other deposition systems such as sputtering
a similar result could be achieved by either having a second ion
source that is used purely to ion bombard the growth surface or
by the application of a negative self bias to the growth substrate.
In the case of the samples used in this study for illustrative
purposes, undoped a-C:H films were deposited using a stan-
dard capacitively coupled RF PECVD system with feed gases
of CH4 and He. The negative DC self-bias developed across the
plasma sheath was varied in the range - 5 0 to - 2 6 5 V at a fixed
pressure of 200 mT in the first set of samples shown in Fig-
ure 117. In this set care was once more taken in order to keep the
film thickness constant around 60 nm. The variation of the EPR
spin density is also shown in the figure in order to draw compar-
isons and to try and elucidate the mechanism that is responsible
(8.7) for the emission process. Similar studies have been performed
Dn 2)
where the threshold field has been plotted as a function of DC
self-bias and a function of chamber pressure (100-1000 mT) by
Silva et al. [377], but as the film thickness was not kept constant
it is not possible to discuss definite trends.
The variation of the field emission properties as a func-
tion of nitrogen content for a fixed bias condition is shown in
Figure 118. The variation in the EPR density as a function of ni-
trogen content is also shown for comparison. These doped films
were deposited using a magnetically enhanced plasma deposi-
tion system described in detail elsewhere [88] using the feed
gases CH4, He, and N2, with varying N2 flow rates at a fixed DC
self-bias and pressure. Changes due to N incorporation were
attributed to electronic doping rather than graphitization. The
doping effect observed in the films due to the nitrogen incorpo-
ration is weak, but clearly changes in the electronic properties
such as DC conductivity and activation energy are observed
[29]. All the films were deposited on water-cooled substrate
490 SILVA ET AL.
holders, with the temperature at the surface of the films not
exceeding 50~ during the deposition process. The DAC(:N)
films were deposited on n++-Si substrates, which were de-
greased and then Ar (He) plasma cleaned prior to the deposition
of the DAC(:N) thin films.
The variation of the threshold field with DC self-bias is
shown in Figure 117. As the self-bias is increased from - 5 0 to
- 9 0 V, the threshold field increases from a value of 18 V//zm
to a value close to 26 V//zm. For bias values above - 9 0 V, the
threshold field decreases to around 12 V//zm, where it remains
approximately constant. Higher fields have been reported for
undoped films by Lee et al. [378]. The measured spin density,
Ns, ofthese films rises rapidly from 3 x 1017 to 1.1 x 1020 cm -3
at - 1 2 5 V. At higher biases Ns increases only very gradually,
finally reaching 1.6 x 1020 cm -3. The Tauc gap falls rapidly
from 2.6 eV ( - 5 0 V bias) to 1.3 eV ( - 1 2 5 V) and then falls
gradually to about 1.1 eV at the highest bias voltages. In the
case of A Bpp there is an initial increase in the linewidth, reach-
ing a maximum of 1.4 mT at - 1 2 5 V bias followed by a rapid
decrease to 0.7 mT, which continues to decrease to 0.56 mT at
- 2 6 5 V bias.
These results show the existence of two regimes, above
and below - 1 2 5 V bias, and it is therefore convenient to
discuss the results from the two regimes separately. For the
sample deposited at - 1 2 5 V bias the measured spin density
is 1.1 • 1020 cm -3 and the observed linewidth is 1.4 mT. The
Lorenzian lineshape can be explained using dipolar broadening.
Above - 125 V it is thought that the narrowing of the linewidth
is due to rapid exchange of spins as the s p 2 clusters increase
in size, as discussed in Section 5. This is consistent with the
narrowing of the bandgap, and the reason for the converging
of the threshold field to a limiting value close to 12 V / # m
for these films. These films have a high s p 2 content (>65%
[377]) as well as a high bandgap (>2 eV) and as a consequence
overlapping of the clusters will result in electron delocalization
and/or enhanced hopping between the clusters that will enhance
the connectivity between the clusters. Application of an exter-
nal electric field results in extraction of electrons from the film
surface. Replenishment of the emitted electrons to the surface
layer is easily accomplished due to the good connectivity be-
tween the clusters and low barrier at the back contact due to the
low bandgap of the material. Emission from these high sp2-rich
films would be characterized as a "front surface"-type emission
and since the s p 2 clusters are located at or about the Fermi level
EF they would be expected to yield a peak in the FEED at EF.
The high conductivity of these samples means the films would
not be able to sustain any form of space charge. As the films
would have a high percentage of defect states within the films
it would not be possible to form a barrier (Schottky or hetero-
junction) at the back contact to the film. Therefore, as the back
contact is likely to be ohmic in nature it would be able to read-
ily supply electrons to the film and will not be controlled by the
back contact process discussed by Amaratunga and Silva [45].
This was shown by Hart et al. [379] for ~25 nm thick TAC
films onto substrates of different metals (varying work func-
tions). Several of these substrates (Ti, Mo, Si, and Cr) can
form interfacial carbides which could lower the barrier at the
back contact and possibly lead to the formation of a "classi-
cal" ohmic contact. However, the authors noted that since there
was a significant spread in the measured values of threshold
field between the carbide and noncarbide forming substrates,
the back contact does not play a significant role in determining
the emission characteristics of TAC films. Indeed from Section
5 it was shown that the defect density of TAC is greater than
1020 cm-3; such a defect density would tend to produce an elec-
trically "leaky" junction whereby a space charge could not be
sustained and is therefore not the determining factor for elec-
tron emission.
Reducing the self-bias to - 9 0 V decreases the spin density
by about two orders of magnitude and gives rise to an increase
in the Tauc gap. The rise in the Tauc gap shows that major struc-
tural changes in the film are occurring at the low bias voltages
with the films likely to have a higher s p 2 content due to C-H
bonding. These films are often polymeric. At low self-biases a
low concentration of small isolated s p 2 clusters forms. Initially,
the number of C atoms in each cluster is small (as inferred from
the large Tauc gap) but the greater energy available at higher
biases allows the formation of a greater number of larger, but
still isolated, clusters. This results in a reduction of the Tauc
gap and an increasing spin density, though the electron delocal-
ization in the cluster and/or hopping between clusters is kept to
a minimum. This leads to poor connectivity between the clus-
ters and results in films which need a higher applied electric
field for the onset of emission and explains why the threshold
field is higher at the lower bias voltages when compared with
the films deposited the higher biases. The subsequent drop in
ET for the film at the lowest bias voltages indicates that an-
other emission mechanism is also present in these low defect,
polymeric, wide energy gap films. This additional mechanism
is brought about by the presence of the high internal electric
field (up to 20 V/#m) at the a-C:H/Si interface which produces
"hot" electrons from the conduction band of the underlying Si
substrate [45,365]. The low concentration of the more conduc-
tive s p 2 clusters is unable to screen the field at the front surface.
In this way emission from these low bias deposited films would
be more correctly described as being determined by "the back
contact" rather than being a "front surface" dominated process.
The variation of the threshold field and spin density with N
content is shown in Figure 118. The threshold field in these ni-
trogenated DAC films drops monotonically from 20 to 3 V//zm
as the atomic nitrogen content in the films is increased from
zero to 15 at.%. The EPR spin density decreases by two orders
of magnitude from 4 • 1020 to 4 • 1018 cm -3 when 7 at.% of
nitrogen is introduced and remains close to 1018 cm -3 for sub-
sequent increases in nitrogen. The linewidth at zero nitrogen
decreases from 0.5 mT to close to 0.15 mT at the maximum
nitrogen content. The intervening points between the mini-
mum and maximum nitrogen content have a linewidth close
to 0.21 4- 0.01 mT. These results indicate that the nitrogen in
the films has a definite beneficial effect on the threshold field
and the emission current density. The EPR results appear to in-
dicate that other than in the first and last points of the data,
 A M O R P H O U S C A R B O N THIN FILMS 491

25 20 I 11111 I I I I I III I I I I I IIII I

E E
=:L 20- = 15
"o "0

15 = 10
"10
ot-" oe'-
L-
r" 10 x: 5
I-- I--

5 I I I I i I 0 t,~ll J , i il~ll I I I I I III1

0 50 100 150 200 250 300 350 0.001 0.01 0.1

Deposition Ion Energy (eV) N content (at. %)

Fig. 119. Variationof the threshold field of TAC films as a function of depo- Fig. 121. Variation of the threshold field of TAC films as a function of ni-
sition ion energy. Reproduced with permission from [382], 9 1998, Elsevier trogen content. Reproduced with permission from [382], 9 1998, Elsevier
Science. Science.

25 I I I I I I
Vacuum
Graphite level
E=
oEv Ec
20 Diamond (1 11 )
Diamond (111):H

= 15 ta-C
"0
or'-

'-
(- 10 a-C:H
i-.
"--e
polyethylene o
5 I I I I I I.
l I ! 1 !
0.4 0.5 0.6 0.7 0.8 0.9
-io -8 -6 -4 -2 0 2
Energy (eV)
sp3 fraction
Fig. 122. Band edge energies of the C-H system. Reproduced with permis-
Fig. 120. Variation of the threshold field of TAC films as a function of sp 3 sion from [388], 9 1997, Elsevier Science.
fraction. Reproduced with permission from [382], 9 1998, Elsevier Science.

analysis of the same data by Ilie suggests that it is the cluster-

there is little change in the spin density and linewidth, both of
which remain relatively low for these films. The films that were
deposited using magnetic confinement had a bandgap close to
2 eV, with the controlling mechanism for field emission being
attributed to band bending from space charge considerations.
The invariance of the EPR properties appears to indicate that
it is unlikely that the cluster sizes within the films are varying
significantly during the increase in nitrogen content from 7 to
14 at.%.
8.3.3. T e t r a h e d r a l A m o r p h o u s Carbon Films
The variation of the threshold field for TAC films with ion en-
ergy is shown in Figure 119. It is well established that the s p 2
content in TAC films is primarily controlled by the deposition
ion energy [92], which also controls many of the microstruc-
turai [68] and electronic [380] properties. It is very interesting
to note that the threshold field for electron emission in TAC
films can be so well correlated to the s p 2 content (Fig. 120).
In the case of laser ablated TAC films an opposite trend to
that shown in Figure 120 was observed with the films with the
lowest threshold having the highest s p 2 content [381]. Recent
ing of s p 2 states that are more important in the field emission
properties than the s p 2 content [366]. It should be noted at the
outset that the TAC films discussed here have a large defect
concentration that far exceeds the DAC or PAC films. A form-
ing process or initiation field was needed before stable emission
could be observed on some of the films [382], but not all [366].
Once more no surface damage was observed after forming.
Field emission as a function of nitrogen content is shown in
Figure 121.
The variation observed in the threshold field as a function of
energy mirrors the variation of the s p 2 content, which shows a
peak in the value close to 80% s p 2 at an ion energy of - 1 0 0 V
[68]. The results of Satyanarayana [382] were attributed to a
change in the electron affinity which was controlled by the s p 2
content as shown in Figure 122. In the case of nitrogen doping
there were clearly two regimes, with films deposited with high
nitrogen content ( > 0 . 4 % ) showing a increase of the threshold
field which was attributed to increased graphitization of these
films and thus reduced s p 2 content. On the other hand reasons
for the lowering of the threshold fields at low nitrogen lev-
els was not discussed in any detail. Cheah et al. [383], who
obtained similar FE results, attributed the observed variations
492 SILVA ET AL.

~ . 10 -4 ' ' ' ; I ; ' ' ' I i ; , ~ 1 T ; , , , ; ~_1/i I I B m _~-~ ;U~ Multiwalled C a r b o n

'I
,, 9 9 C :D.ID O E r U 0"
Nanotubes/Fragments
9 n+_ta.C/p*'.Si, ==- u ~c " o ~A"
E _ i l l oo _-3 .3,~0 9 ^ 0$ I
E 10s o n+-ta-C/n*+-Si, =" = o 8 o ~ I<~ zx~c'ee'"8 ,~e 9
++
9 i-ta-C/p -Si oBPI _ c, A
~-, 10-6 .. 9 no o ,'9o.-
>, c i-la-Cln-Si
9* 9 |ramoE~
9
~^
1
O* /,Lg.- a-C:N 0.1 - 0 . 2 ~tm
o3 9 p-ta-C/p -Si o 9 I
c" 1 0 -7
..

," p - t a - C l n - S i
o
.,_, 10-8 .., ~ ~ ~ .
c oo
9 Si S u b s t r a t e
i,,_.
t._ 10-9
S3
o
(- 10-10
O
o) Carbon Nanoparticles Embedded in a Nitrogen-
.0~ 10-11
L/~,~jllA
+ 9 ' ~T:
Doped Amorphous Carbon Matrix
E
LU )|, Fig. 124. Schematic diagram of multiwalled carbon nanotube fragments em-
10-12 , , , ,, , ~ i , ~ , , , , I i i , ; , : ; , ; ; ,

0 10 20 30 40 50 60 bedded in an a-C matrix. Reproduced with permission from [387], 9 1999,

Electric Field (V/gm) MYU.

Fig. 123. Dependence of field emission on the substrate type and doping level
for TAC films. Reproduced with permission from [383], 9 1998, ???.
8.3.5. Nanocomposite Amorphous Carbon Films
A typical NAC film that has nanoparticles embedded in an a-C
in their properties to space charge induced band bending that matrix is shown schematically in Figure 124. The embedded
will be discussed in detail in the following section. It should be nanoparticles in this case are fragments of multiwalled nan-
noted that TAC films deposited on different systems could have otubes that have been embedded in an a-C matrix using the
vastly differing properties. cathodic vacuum arc technique for deposition. Simply by hav-
Field emission studies on TAC films have also been per- ing a high pressure region of He or N2 gas adjacent to the
formed by Cheah et al. [383], with similar threshold fields, cathode striker Amaratunga et al. [387] showed that is was pos-
though higher threshold fields were reported by Park et al. sible to rapidly condense the carbon arc into nanoparticles [ 1]
[384], Chuang et al. [385], and Missert et al. [381]. However, such that composite films could be produced. Coil et al. [70]
lower fields have also been observed by Talin et al. [367] and too showed similar microstructural results using the FCVA sys-
Xu et al. [386]. Results that show a dependence on the substrate tem to deposit cathodes. Typical results obtained from the NAC
on which the films have been deposited has also been reported films are shown in Figure 125. Clearly, the threshold fields ob-
by Xu et al. [383]. See Figure 123. In the figure it is clear that in tained are very low, with some scatter in the data as a result of
order to explain the results a space charge induced band bending various channels turning on and off. Each of these individual
model must be invoked due to the dependence of the threshold channels will have different emission characteristics, and the
field on substrate carrier type as well as the doping levels of the composite result is shown in Figure 125. The effect of nonuni-
substrates. form emission from the surface was shown by Amaratunga
et al. when they etched the front surface of their films and
showed that although there was an improvement in the emis-
8.3.4. Graphitelike Amorphous Carbon Films
sion threshold, this was at the expense of increased fluctuations
There are a number of papers that have been published that in the emission characteristics. The results were explained us-
show electron emission with very low threshold fields from ing a Fowler-Nordheim tunnelling and hot electron emission
polycrystalline graphite films. The example we will use in this composite model, in which the DAC matrix acts as an interlayer
study for a GAC film is a cluster assembled carbon thin film that moderates the emission and will be discussed later. When
[61]. The films were deposited using a supersonic beam of they compared the enhancement factors of their film assuming
carbon clusters in the laboratory of Milani [59], and the depo- a work function of 5 eV, the/~ factor increased from 1200 to
sition process is described in detail under cluster beam sources. 1950 after the surface etch treatment. This further illustrated
Raman spectroscopy was used to establish beyond reasonable the nanocomposite nature of their films.
doubt the graphitic nature of the deposited films with a promi-
nent D band and a G peak at 1573 cm -1 which indicated
8.4. Modelling of the Electron Emission Process
ordered regions of sp 2 phase. The cluster size was around 2 nm,
with a bandgap of close to 0.6 eV. Due to the graphitic nature The large variations available to the a-C microstructures make
of the film, the characteristics would be best described using a it difficult to postulate a single model that can explain all the
Fowler-Nordheim process, where the work function should be observed characteristics within the films. But it is possible to
fixed at 5 eV. When this is performed a local enhancement fac- formulate some basic rules that can be applied in the elucidation
tor of 350 is obtained. This is not an unreasonable number for of the emission mechanism in the a-C films. The first attempts
a nanoclustered film, which is likely to have highly localized to explain the emission process in a-C (and polycrystalline dia-
emission from the front surface. mond) based on negative electron affinity have been overtaken
 AMORPHOUS CARBON THIN FILMS 493

1.0xl0 ~ 1~) 47 i '' I ' I __' I 1 .... i, , I , ' ! '

10"7: ~, Q01

80x 0' 9 / l:

->" o.ox,
o._ .r. ; ,~,~ I:" a
9 (b) w v') 9
10"' -

a~ 4 . 0 x 1 0 "7 0 ~ i ~ ~ ; ; 0o oo
Electric Reid (V/pro) 0

E ~ ~~ "
N 2.0x10 7 ~ Before etching
O o After etching 9
o _V
o (a)
0.0 ' '~ ,

Electric Field V/gm

Fig. 125. Electron field emission characteristics of NAC films that show improvements to the thresh-
old field after a surface etch treatment, at the expense of increased fluctuations. Reproduced with
permission from [387], 9 1999, MY.

Electric Field (Vpm 1) ing a # factor of 1 for mirror smooth films), 0.01-0.06 eV,
1 0 .9 ,
20.0
,
10.0
,
6.7
,
.5.0
,
4.0
,
and the range of emission areas, ~, 10 -24 cm 2, are nonrealistic
when compared to experimental observations. Similar values
~ ~ 1 5 %
were obtained for undoped DAC films [377], doped and un-
1~176 o~~~%~176 4% v v v , ,irr ~
~, o l o doped TAC films [382], and nearly all the forms of a-C films
> <> vv
~'E examined by researchers when a # factor of 1 was used for
10"11 7 1% <>
9 -
the mirror smooth films. According to FN theory, there are two
~:> I0Iz o / . ' ~ zx o parameters that control the emission process. First there is the
0,,,.q~ zx ~ o o barrier height between the electron source and vacuum at the
1
0 "13 9 A A A ~ A _ surface, and second there is the # factor or local field enhance-
ment. The barrier height is usually the work function for metals
10 "14 I I t I I and the electron affinity for semiconductors both of which are
o.oo o.os o.1o O.lS o.zo o.2s 0.30 invariant with doping. Therefore, the variation of the threshold
I / Electric Field (pmV -I)
field for emission with change in nitrogen content cannot be
Fig. 126. Fowler-Nordheim curve for nitrogenated DAC films. Reproduced explained using classical FN theory. With the need to reconcile
with permission from [45], 9 1996, American Institute of Physics. this apparent contradiction in the emission current as well as
the barrier values and emission areas measured for a-C films in
general, a thin film model for field emission was proposed that
by events that firmly point to this as being of secondary impor- was based on a space charge induced band bending giving rise
tance. In a-C, as shown by Robertson [388] in Figure 122, the to hot electron processes [45]. In this model the a-C films acted
low electron affinity of some of its configurations does help in as an interlayer with the true cathode being the underlying Si
expelling electrons from the films once it has entered the con- or metal substrate, with the crucial factor being the heterojunc-
duction band, but getting the electrons to the conduction band tion or Schottky barrier that formed at the back contact being
is not straightforward. needed for the creation of hot electrons.
On an historic note, researchers first tried to explain the The need for space charge from the depleted bands of a-C
emission process at low electric fields using the FN equation. can be viewed simply using basic semiconductor equations. If
The FN curves for the nitrogen doped DAC films are shown in we were to take an ideal vacuum/semiconductor or insulator
Figure 126. The threshold field is shown in Figure 118 and gives interface, where there is no accumulation of charge, and apply
an increase in current density with increasing nitrogen content, the Laplace theorem, from the conservation of electric flux as
with a concomitant reduction in the threshold field for electron given by Gauss' law we find that the electric field within the
emission. The FN curve shows linear regions that are expected thin film must be lower than the applied electric field by a factor
for tunnelling currents. But the range of barrier values (assum- given by the ratio of the material dielectric constant to that of
494 SILVA ET AL.

v a c u u m (Ematerial/Evacuum). As the dielectric constant of vacuum

(a)
is 1, this means that in the case of a-C films, the maximum F-,ac F-,,,c
electric field that can exist within the material purely due to field
~Jrface A
penetration would be anything between 0.2 to 0.5 of the applied
electric field outside the material. As we have seen emission of
eV 13.7 eV
electrons below a macroscopic field of 10 V / # m regularly, it is F~ EF
difficult to see how a fraction of such an electric field will be
.~.
able to allow for the emission of electrons from these cathodes.
It should be noted that for there to be electron emission from
a flat metal cathode electric fields as high as a 1000 V//zm are n-Si a-C:H:N vacuum metal
required. (b)
On the other hand, if space charge based depletion is present
F-,ac
in the a-C based cathodes, the solution to Poisson's equation
gives rise to electric fields that are up to 5-10 times greater than
the applied macroscopic electric field as shown by Amaratunga eV
and Silva [45]. With fields of this magnitude, it is not difficult
to envisage a hot electron process based on space charge in- Ec e_

duced bands as shown in Figure 126. As discussed previously,

by the addition of inhomogenates in the thin films it is possible 3.4 eV
to increase the internal electric fields even further. The proposed
model is applicable to any material system as long an the thin n-Si
film can support space charge, and it has been used to explain
emission from a-Si [389], a-SiC [390], and polycrystalline di-
amond [391] too. In the case of polycrystalline diamond, the
space charge is supported across the grain boundaries of the di-
amond crystallites. a-C:H:N I3.7 eV
The proposed band diagram for emission from a-C films
vacuum
based on the space charge bending model is illustrated in Fig-
ure 127. Figure 127a shows the proposed band diagram at metal

equilibrium for the heterojunction based hot electron model for (c)
electron emission. It is based on assuming that the a-C thin film F-,ac
is n-doped and has an electron affinity close to 2.5 eV (see Fig-
ure 122), a Fermi level of 0.5 eV based on the activation energy
studies [29], and approximately 1016 cm -3 ionized nitrogen ev t
donors. It should be noted that the band bending at the n ++- Ec
Si/a-C interface is such that there is a collection of electrons at
the surface which experience a barrier that oppose their move-
ment into the conduction band of the a-C layer. When a bias I2.9 eV
is applied to the heterojunction and the anode voltage becomes
positive, and the applied field is large enough to fully deplete
n-Si
the carbon thin film, it can be shown that the field observed by
the electrons that tunnel through the heterojunction barrier into F-vac
the conduction band is much greater than the applied electric
field (> 18 V//zm) due to the space charge considerations. This
field decreases parabolically within the DAC:N thin film as it a-C:H:N l 13.7eV EF
traverses toward the surface of the semiconductor (Fig. 127b). vacuum ....
According to the band diagram shown in Figure 127b, the pool
of electrons gathered at the n++-Si/a-C interface has a built-in
metal
barrier that prevents the tunnelling/thermal excitation of elec- Fig. 127. The proposed field emission mechanism based on space-charge-
trons into the conduction band of the a-C layer before the
induced band bending in a-C thin films.
interlayer band bending is large enough for the electrons to
overcome the energy barrier for emission into the vacuum. The
electrons can now lose up to 3 eV in phonon ionizations and they will collect at the front surface of the a-C thin film and de-
still retain enough kinetic energy to enter the vacuum level in crease the band bending in the space charge layer as shown in
the a-C thin films and thus emit in to the vacuum. In the case of Figure 127c. Yet, until the total band bending is lost, there will
electrons that do not have enough energy to reach the vacuum, be some electrons emitted from the a-C thin films.
 AMORPHOUS CARBON THIN FILMS 495

EVAC 102 9 I " I " I " I " I " I' ' I ' '| ' I " I " I '
EVAC ..
\ J 0 2 etched . . . .

\ ; 10"' ,~~ots'P~ti i'Ii''-

E F = Ec
J H2 etched ~ ..,o~ ..,~
EF
10 r'
Ev
>, ,, o~ ~Ar etched
9~ 10~
= .." o : ~.
| ." o
a,., lO' 9 ~ <,~
n+ - Si a-C:N nanotube a-C:N
nanotube
vacuum
C" 9
o 9.
oO - unetched
:3 1 "=
0
oe o
10"~ r ;
, , k E v A c 100eV ta-C
\ / 10.10 , l . i , I . i . i , I 9 i . i , i ..,<1 , I ,

0 2 4 6 8 10 12 14 16 18 20 22 24

e
Electric Field (V.~lm"1)
_e.~
Fig. 129. Variation of the emission current density of as deposited TAC and
after 2 nm etch by Ar, H 2, and 02. Reproduced with permission from [379], 9

\ ~
..~
1" --i-~ A~
C
1999, American Institute of Physics.

n+ - Si a-C:N nanotube a-C:N ! vacuum

nanotube
Fig. 128. The heterojunction based model for electron emission in NAC films.
Reproduced with permission from [387], 9 1999, MY.
Recent modifications to this model have now shown that it
is possible for the collected negative charge at the surface to be
removed from the surface via conducting dielectric channels. It
has been shown using computer simulations that when a more
conductive filament or channel is introduced into the thin film,
there is a tendency for the electric field lines to emanate away
from these "dielectric channels" such that on an E-field plot,
as shown in Figure 113, electrons will be attracted toward them
during electron emission. But it should be noted that having
more than one channel within a space of 80 nm decreases the
advantageous properties of the additions. The possibility of the
existence of clustered sp 2 regions that could form such chan-
nels has been shown by Ilie et al. [366], using Raman analysis.
The analysis performed is based on the modified analysis of
Raman spectra introduced by Ferrari et al. [231] which show
that the sp 2 clustering in TAC films varies as a function of de-
position conditions. Such a mixed phase incorporated into an
a-C film would be invisible to most surface analysis equip-
ment available today. Also, it should be noted that the electric
fields surrounding regions of these channels must be bent sig-
nificantly due to space charge for the model to work.
A composite but serial "dielectric channel" space charge
model was proposed by Ilie et al. [366], where they discussed a
variant of the above discussion. In this case, the dielectric chan-
nel acted as a field enhancement conduit, whose/7 factor was
used primarily for electron emission from the thin film surface
at these localized regions. In the schematic diagram that was
introduced the band bending shown was attributed to the fill-
ing up of amphoteric gap states close to the Fermi level due
to negative space charge. In the discussion that followed, emis-
sion due to triple junction effects and/or the presence of space
charge was not discounted. This model supersedes the earlier
enhanced/7 factor due to the patch antenna surface termina-
tion model of Robertson [388, 392]. An emission process due
to mixed s p 2 / s p 2 phase materials was introduced by Xu et al.
[393], where it was proposed that a step based space charge
model could be used to explain the emission from thin TAC
films. Also, the effects of surface termination on field emis-
sion properties were convincingly dismissed by their findings
for different surface elements as will be discussed later.
Amaratunga et al. [387] also used the results based on the
interlayer model [45] to successfully explain the variations of
their NAC films. A band diagram explanation of the emission
process of the NAC films is shown in Figure 128 with (a) no
applied field and (b) applied field. In this case the internal junc-
tions of the particles and the a-C matrix allow for heating of
electrons within the thin film, with the emission process at the
outer end of the particle being purely due to FN-like tunnelling
(high/~ factors). Note that the band diagrams are symmetric
about the y-axis due to the nature of the multiwalled nanotubes
as well as the surrounding matrix. Variations in the threshold
field with and without etching of the front surface was success-
fully explained by the surface to vacuum being either the host
matrix or the nanotube.
Recently, Xu et al. [386] examined the electron field emis-
sion properties of a number of a-C thin films and came to the
conclusion that the emission process cannot be described by any
single mechanism. They proposed that for emission in carbon
films there are two major regimes, with the intermediate region
being a composite of the two. In their analysis all emission
below 10 V//zm was attributed to thermionic emission, with
emission for fields above 100 V//zm due to FN based field emis-
sion. This model was illustrated using numerical calculations
for a-C films with varying barrier heights and fitting the results
496 S ILVA ET AL.

to the unified electron emission model of Murphy and Good.

This analysis is totally consistent with the discussion above,
with thermionic or hot electron emission virtually controlling
all of the emission in most thin films. The only divergence is
when high internal fl factors or local enhancement comes into
play due to mechanisms such as clustering.
Modinos and Xanthakis [394] have proposed an alternative
mechanism for emission from the diamondlike carbon (DAC:N)
films deposited and measured by Amaratunga and Silva [45].
The results of their calculations show the presence of a high
density, > 1021 7r states cm -3 eV -1, in the mobility gap and
it is from these Jr states near the Fermi energy that the electron
emission originates. The addition of N results in an upward shift
of the Fermi energy toward the conduction band. However, in
order that the calculated emission current density matches the
experimental values given in [45], Modinos and Xanthakis were
forced to assume that the emission occurs at hemispherical pro-
trusions at the surface. While they do not give dimensions of
these protrusions, they have estimated that they at most produce
an enhancement of the electric field by a factor of around 150.
In this way the high density of zr states and properties of the
front surface determine the electron emission. No surface fea-
tures or structures were observed in the DAC films by atomic
force microscopy to support such an enhancement factor at the
surface.
If we were to consider the rate limiting step in the electron
emission process of a thin film semiconductor, it will either be
at the back contact to the film, transport within the thin film, the
emission from the front surface of the films, or a combination of Fig. 130. CITS measurement of (a) STM image and (b) STS I - V curves
two or more of the above. According to the hot electron model for untreated TAC:N films. Reproduced with permission from [395], (g) 1999,
developed for the wide gap materials, the transport within the American Vacuum Society.
semiconductor and the emission at the front surface of the film
is less of a limiting process than the back contact as long as the
different local concentrations of s p 2 clusters through the film
thin film can maintain the fully depleted space charge layer that
extending from the surface.
supports the band bending. If the transport within the material
Films deposited at high self-biases which have a high spin
is not hot electron based (highly defective or graphitic films),
density > 1020 cm -3 (a high s p 2 content) and good connectivity
then bulk material properties become more and more signifi-
between the clusters exhibit the lowest threshold fields. Such
cant, with this extending to the front surface due to clustering
films would be characterized as "front surface emitters." Films
of the s p 2 states. The number and size of s p 2 clusters lying at or
with a comparable spin density but with poorer connectivity
near the Fermi level then controls the emission and it is impor-
show higher threshold fields since the s p 2 cluster is not large
tant that the clusters are large enough for efficient connectivity
enough. The films deposited at the low biases having low s p 2
between clusters. In this way the a-C films deposited under dif-
content (low spin density) have lower threshold field by virtue
ferent conditions will consist of a matrix of s p 2 C with regions of the good field penetration and the presence of a high internal
of varying s p 2 cluster concentrations and sizes. Since these electric field at the back contact.
clusters will have different dielectric constants, the applica-
tion of the external field will result in local field enhancements
around the clusters and will aid in the emission of electrons. 8.5. Field E m i s s i o n as a F u n c t i o n of Surface Modifications
A similar conclusion concerning the importance of the size of Shi et al. [393] and Hart et al. [379] have studied the effects
the s p 2 cluster has also been reached by Ilie et al. based upon of postdeposition surface treatments using ion beam bombard-
a correlation between the measured values of threshold fields ment and ion plasmas, respectively. In the study performed by
for various types of amorphous carbon films. They determined Shi et al. undoped and n + doped TAC deposited at 100 eV
that the optimum size of the clusters for emission, in-plane cor- using the FCVA method was subjected to H, O, and Ar ion
relation length to b e 1.5-2 nm depending on the specific type bombardment. Growth at 100 eV in undoped TAC results in
of film investigated. This model can also explain the nonunifor- the maximum s p 2 content and n-type doping was achieved by
mity of emission across the surface of the samples in terms of the addition of N. They noted that the threshold field in the un-
 AMORPHOUS CARBON THIN FILMS 497

doped films decreased from 18 to 14 V//zm after treatment with

each of the ions. For n+-TAC ion beam treatment resulted in
a decrease from 12 to 8 V//zm. The saturated emission current
density of the post-treated films was noted to improve by about
an order of magnitude and appeared to be independent of the
ion used. Shi et al. also measured the effects on the threshold
field of undoped TAC of varying the H ion energy from 50 to
800 eV. In this ion energy range the threshold field increased
from 14 to 22 V//zm. Hart et al. studied the effects of reactive
ion etching using H2, 02, and Ar gases as shown in Figure 129.
Since TAC has an sp2-rich surface layer extending about 1 nm
from the surface, Hart et al. removed up to 2 nm of the sur-
face, thereby allowing examination of the effects of this surface
layer. As-deposited films had a threshold field of 8 V/#m. Etch-
ing in a H plasma reduced the threshold field to 3.0 V//zm if 0.5
nm was removed (incomplete s p 2 surface layer removal) and
3.9 V / # m if 2 nm (complete s p 2 surface layer removal). For
02 etching the threshold field decreased to 5 V / # m for both
a 0.5 and 2 nm etch. Ar plasma etching reduced the threshold
field to 6 V//zm. Finally, emission maps using an ITO anode
as a phosphor show that the emission site density measured at
20 V/lzm increased from about 50-100 cm -2 in as-deposited
films to 1000 cm -2 for 02 etched films, 2000 cm -2 for Ar
etched films, and 4000 cm -2 for H2 etched films. Treatment
with H2 plasmas would be predicted to increase the probabil-
ity of C - H surface termination. Therefore, within the confines
of the negative electron affinity model of Robertson et al. dis-
cussed previously [388], it would be expected to reduce the
emission barrier at the front TAC/vacuum interface. However, a
reduction in the threshold field was also observed for 02 plasma
treatment which should raise the front surface barrier since the Fig. 131. CITSmeasurement of (a) STM image and (b) STS I - V curves for
surface would be terminated with C - O bonds. The reasons for the post-treated TAC:Nfilm. Reproduced with permission from [395], 9 1999,
the reduction of the threshold field after O ion treatment are American Vacuum Society.
unclear. Since Hart et al. used a parallel plate geometry to mea-
sure FE characteristics the lowering of the threshold field is due
to a higher emission site density and thus a greater distribution
of sites with lower threshold fields. Atomic force microscopy emission is observed from diamond surfaces and Shi et al. at-
showed that the RMS roughness of films did not change after tributed the emission at this level to a near 100% spa-rich phase.
plasma treatment and therefore surface features do not play a In this way Cheah et al. believe that after treatment nanoclusters
significant role. of spa-rich material with spa-rich boundaries are formed. Since
AFM and also scanning tunnelling microscopy (STM) have the s p a clusters have lower electron affinities than the spe-rich
also been employed by Cheah et al. [395]. AFM images showed areas they provide an efficient way for electrons to be emitted
that for n+-TAC films the surface roughness did increase from into vacuum.
0.193 to 0.242 nm over a 500 • 500 nm 2 area after ion beam Further information about the role of surface treatment has
treatment. In addition nanoscale clusters were visible after been obtained from the implantation of C60 ions into PAC films
treatment. Both STM and also current imaging tunnelling spec- by Carey et al. [396]. In this study films were implanted with
troscopy (CITS) have been used to attempt to correlate surface 10 keV C60 ions to doses of 7.5 x 1013, 1.25 • 1014, and
effects with tunnelling effects. STM images shown in Fig- 2.65 • 1014 cm -2. The ion source was a C60 sample evapo-
ures 130 and 131 reveal that H treated films contained clusters rated in a heated crucible. C60 ions were also implanted at the
as well as untreated areas. CITS measurements of the clustered highest dose into Si substrates and the average threshold field
regions show that they require lower voltages for the onset of for virgin single crystal Si was 60 V//zm. The average threshold
emission. UPS was used to examine both the untreated and field for a conditioned nitrogenated and non-nitrogenated film
post-treated films. In as deposited films UPS measurements as a function of C60 ion dose is shown in Figure 132a. It can be
indicate electron emission at about 4 eV with some emis- seen that after the initial dose of 7.5 x 1013 cm -2 the threshold
sion attributed to defect levels at lower energies. After Ar ion field increased by nearly a factor of two for both films. How-
treatment emission of photoelectrons occurs at 0.6 eV. Similar ever, at a higher dose of 1.25 • 1014 cm -2 the threshold fields
498
7O I I
E 60
=~-|
_~
o
501
40
e--
~ 30
e-
I---
20
1.8
, I i !
X
/-
ID
"0
1.7
J ters the field experienced inside the semiconductor and, within
1.6
1.5 I , I t I t
o lx1014 2x1014
Ion dose (cm -2)
Fig. 132. Variationof (a) the threshold field and (b) the refractive index with
implant ion dose of C60. Reproduced with permission from [396], 9 2000,
American Institute of Physics.
reduced to values 36 and 40 V / # m for the non-nitrogenated
and nitrogenated films, respectively. The threshold field then re-
mains constant for the non-nitrogenated film at the highest dose
of 2.65 • 1014 cm -2. For the nitrogenated film at the highest
dose the threshold field again rises, approaching that measured
for C~-0 implants into Si substrates ( ~ 6 0 V/#m). The refractive
index of the films as a function of dose is shown in Figure 132b.
No significant change is observed in the refractive index for ei-
ther type of film after the lowest dose implantation. For higher
doses the refractive index increases rapidly, reaching a value
of 1.77 for the non-nitrogenated film, close to that of sp2-rich
graphite (1.8). In the case of the nitrogenated film, at the high-
est dose, no reliable refractive index or thickness data could
be obtained. Finally, preliminary AFM has indicated that at the
lowest implanted dose some nanostructural features 10-20 nm
tall and 50-100 nm in diameter are observed. Even though sur-
face features are present on the films after implanting to a dose
of 7.5 • 1013 cm -2 and an increase in the threshold electric
field compared with the unimplanted films is observed, we do
not believe that the surface protrusions play a significant role in
field emission. The field enhancement factor, r , can be related
to the diameter of the surface r feature via
fl - - d / [ k r ( R - r)]
where k is a constant ~ 5. For a vacuum separation d of 15/zm,
this gives an enhancement factor of between 5 and 8. Silva
et al. [397] showed that self-texturing of the surface of nitro-
genated DAC films can occur leading to an enhancement of a
factor of 8-10 due to changes in the surface morphology of
these films. However, the current densities measured in field
emission testing were over 100 times the current density from
SILVA ET AL.
a nontextured film from which they also concluded that the sur-
(a)
face protrusions do not play a significant role in controlling the
field emission properties. Molecular dynamic simulations indi-
T
cate that a 10 keV C60 ion will on average penetrate 3.5 nm
into a DAC film and will not have a significant effect on the
bulk of the material. It is envisaged that the C60 fullerene on
impact will break into sp2-rich clusters that will get embedded
into the surface of the DAC film. It was proposed that a surface
i I
(b)
sp2-rich conductive layer will thus be formed, making it easier
for charge collection at the surface to occur. This, in turn, al-
the confines of the space charge induced band bending model
described in Section 8.4, will make electron emission harder
by increasing the energy barrier at the DAC/vacuum interface.
Electrons that gain energy by traversing down the electric field
I
due to the fully depleted interlayer will collect at the front sur-
3x1014 face of the cathode and thereby increase the surface potential
(collection of negative charge) of the cathode. The subsequent
reduction in the threshold field for the non-nitrogenated film at
dose of 1.25 x 1014 cm -2 can be attributed to the reduction in
thickness of the film discussed earlier (Section 8.3). It should be
noted that in the case of the nitrogenated film, due to their lower
mechanical strength and lower crosslinking, enhanced sputter-
ing of the film will occur. Therefore, in the case of the highest
ion dose for the nitrogenated film, it is believed that little or
none of the original a-C:H:N film remains at the surface subse-
quent to the implant.
In summary, there are a plethora of different carbon films
from which electron emission has been obtained at relatively
low threshold fields. Amorphous carbon films appear to be
unique in that most forms of carbon films give field emission at
low fields. Each of these films has a unique structure with some
common features with the catergorized a-C films discussed in
this review. It is important that researchers first understand the
basic microstructure of their a-C films before venturing into
postulating a possible electron field emission mechanism in
their films. There are a few more established emission models
to which the electron emission from a number of these films can
be attributed and the variations with the physical properties ex-
plained. It is envisaged that this topic will continue to grow for
many years to come and it is imperative that a set nomenclature
is established.
9. A M O R P H O U S C A R B O N - B A S E D D E V I C E S
9.1. E l e c t r o n i c D e v i c e s
A number of devices have been fabricated based on amorphous
(8.8)
carbon. One of the more straightforward electronic devices
is probably the p - n junction. There has only been one re-
ported case of this device as documented by McKenzie et al.
[327]. A graded film of TAC/TAC:N was grown onto a plastic
substrate and the resulting film was found to rectify by approx-
imately one order of magnitude. However, it was reported that
the defective surface layer may play a part in hindering the de-
vice performance.
 A M O R P H O U S C A R B O N THIN FILMS 499

I ' I ' I ' I ' I ' I '

9 Vg= 0 V
was only in the order of 10 - 6 c m 2 V - 1 s - 1 , and the character-
5
o Vg= -50 V ~ ~ istic did not saturate, suggesting band-tail rather than extended
9 Vg= -75 V state conduction. The high field conduction showed a near V 2
.~4
<r 9 Vg=-lO0 V
dependence which was attributed to space-charge-limited cur-
"-'
r 3 ~ 9 rent.
=... 9
Chan et al. [399] has demonstrated a working a-C-based
to 2 mE heterojunction bipolar transistor (HBT). A 50 nm DAC film
c- ~ 9 oO
"~_ IlIE &A&&& 0 0
was used as the emitter, which was grown onto p-implanted
a 1 ii o o~176
I A&&& O0 0 O0 Si which was contacted as the base, and the underlying n-type
0 I I I I I o I I I I I I I I I I I II
Si substrate functioned as the collector. The collector current as
I , I ~ I , I , I , I ,
0 10 20 30 40 50 60 a function of the collecter-emitter bias is shown in Figure 134.
Drain voltage (V) A Gummel plot of the characteristics obtained showing the vari-
ation of Ic versus 18 is also shown. It can be seen that the
Fig. 133. TAC TFT drain characteristics as a function of gate bias. Repro-
duced with permission from [398], @ 1996, IEEE. collector current increases with IB and VCF~. This was shown
to be due to carrier injection from the DAC emitter and not
2.5 due the leakage current across the reverse-biased junction. No
current gain was observed, though, and it was surmised that
- - - Ib~.6mA ,'..1 current injection took place from trap states in the DAC film,
--- n,.0.v,,a "1 which suggested a pinned Fermi level in a deep acceptor band
---. - - - lll=~.8mA o ." o,~
,-. 1.5 ...... lh~.9mA ~ 9~ /r~ centered around 0.3-0.35 eV from the valence band edge.
...... 9 /
'!!
NACs have been investigated for use in supercapacitors.
,-mu ................... ' I " /~
1 These are electrochemical duoble-layer capacitors formed by
.. . . . . _ ..... - :,/] two electrodes, a separator and electrolyte. The ions of the elec-
0.5 trolyte are adsorbed onto the charged electrode, resulting in a
"Helmholz layer." As the surface area must be maximized in
I I I I 1 order to increase the capacitance of the device, and an inert
4 8 12 16 20 material is required, NAC has been used for the electrode. Fur-
v @gpc) thermore, NAC may be grown over large areas on a variety of
substrates which further enhances its potential in this role. A ca-
10 .3 pacitor with series resistance R = 1/13 f2, C = 0.099 F, and
f
maximum power density of 506 kW/kg was fabricated, which
10 -5 / suggested that NAC was very attractive for this particular appli-
I
I
cation.
10_7

10.9 9.2. Novel Devices: Nonvolatile Memories, Antifuses, and

i0-II
10-13
0 0.5
Fig. 134. (a) Output and (b) G u m m e l characteristic of the H B T structure. Re-
produced with permission from [317], 9 1993, Elsevier.
Various groups have attempted to fabricate thin film transis-
tors (TFTs). The only documented transistor based on a-C was
documented by Clough et al. [398]. Here, a TFT was fabricated,
and a coplanar design was chosen so that the TAC surface sp 2
layer could be etched using a nitrous oxide plasma. The channel
length was varied between 10 and 3 0 / z m and the gate insulator
was silicon nitride. The drain characteristic for this transistor
is shown in Figure 133. It was found that the TFT operated
in the p-channel enhancement mode, as would be predicted if
undoped TAC was p-type. The calculated field effect mobility
MIMs
-- -- -- Ib ( A )
-------- Ic (A) !
The other remaining applications of a-C films have been in a
niche capacity. Gerstner et al. [400] suggested that TAC:N may
1 1.5 2 2.5 have promise as a material for use in nonvolatile memories. It
v~ (v) was observed that these films showed switching, in that that
after a negative bias was applied across the film, a kink was ob-
served in the forward bias, and the small signal resistance of
the forward bias was found to fall from an "OFF" state to an
"ON" state. Hence, the film possessed a "memory" of whether
the last bias was negative or not. This is shown diagrammati-
cally in Figure 135. This was explained by suggesting that the
"OFF" state corresponded to conduction by hopping around the
Fermi level, and the "ON" state corresponded to Poole-Frenkel
conduction, according to I / V and I / V / T data. Therefore, it
was suggested that the negative switching bias resulted in elec-
trons being promoted from deep acceptor traps to shallow donor
traps, where they could conduct according to Pool-Frenkel con-
duction. The switch from "ON" to "OFF' was as a result of the
accumulation of electrons in the conduction band enhancing the
refilling of electrons in the acceptor traps. This memory effect
500 SILVA ET AL.

bottom contact. The same would occur with excessive contact

10 "3
E 300 pressure resulting in punch-through of the film. Also, the short
r
circuit may be only observed when a small voltage is applied.
o 200
10 -5 n,' No information as to the reproducibility of these devices was
100 documented and therefore there may be some conjecture as to
whether this was a true antifuse effect or not.
r
10 -7 1 2 3 4 5
.= l/l_(mA)
It has already been stated that DAC is a promising material
k..
if used as a switching element in metal-insulator-metal based
10 .9 __ ] LCDs, as documented by Egret et al. [308]. This is due to the
fact that in present TFT-based technology the function of the
10-11 ,
transistor is to allow charge to flow into or out of the pixel. Two
terminal devices will perform a similar role at reduced cost,
although the driver circuitry would be more complex. At high
10-,~ 1 1 fields DAC exhibits PF conduction which allows a sharp turn-on
0 1 2 3 4 5 6 7 8
voltage and hence suitability for this application. In particular,
Voltage (V)
the dielectric constant of DAC is of the order of 5-8 which re-
suits in a high value for the PF/3 factor, resulting in a sharper
Fig. 135. I / V characteristic of nonvolatile TAC:N memory device. Repro-
turn-on voltage than other materials (Ta205 for example).
duced with permission from [400], 9 1998, American Institute of Physics.

0.04 | # |
9.3. Solar Cells
t
ae

0.03 se
It has also been mentioned that TAC:N shows promise as a pho-
0.02 "kink" appears in --____ toconductive material [328]. This due to its benefits in terms of
forward direction..
0.01 photoconductivity and high optical absorbance. However, oth-
ers such as Lee et al. [402] have also attempted to fabricate
~ e.-
o
p-i-n solar cells using boron-doped DAC (DAC:H:B) as the p-
fO -0.01
layer. As the DAC:H:B layer was too resistive for it to make up
-0.02 4 the whole contact, it was proposed to grow an ultrathin layer of
it between the transparent conducting oxide (TCO) and p-SiC
-0.03
layer, in order for it to add to the SiC layer and enhance the
-0.134 I

-1 o 1
Voltage (V)
Fig. 136. I/V characteristic of antifuse based on DAC (C]) and DAC:N:F (e).
Reproduced with permission from [401], 9 1998, IEEE.
occurred with a write time down to 100 #s and the memory
retention time was in the order of months.
An antifuse is a device which forms a state of low resistance
when a threshold electric field is passed, a-C shows promise
for such a device, such as low OFF-state leakage current, ON-
state resistance, and dielectric constant. Most importantly, a-C
antifuses do not show O N - O F F switching. Liu et al. [401 ] fab-
ricated and reported upon DAC and DAC:N:F antifuses using a
sandwich structure and A1 top contacts, and the resulting I / V
characteristic is shown in Figure 136. It was found that the
breakdown voltage was about 1.4 • 106 V cm -1. The break-
down was attributed to the temperature effect of current heating
resulting in hydrogen loss and hence sp 2 reordering. This re-
suited in a graphitic phase being formed, which caused the
observed low-resistance state. However, it must be noted that
DAC sandwich structures are notoriously difficult to measure
as any particulate matter underneath a top contact would render
the device useless by causing a short circuit between the top and
2 built-in potential of the cell. It was found that the collection ef-
ficiency of the cell was enhanced with the DAC:H:B layer. This
was thought to be due to the reduction in band bending experi-
enced by the holes flowing toward the TCO front contact.
Another interesting potential application of a-C thin films
is as an antireflection coating. Indeed, PAC films possess a
wide Tauc bandgap (2.6 eV), low refractive index (1.5-1.7), and
low optical absorbance. Furthermore, by varying the deposi-
tion conditions these parameters can be tuned so that multilayer
antireflective (AR) coatings can be realized. A brief study of
PAC-based AR coatings was carried out by Khan et al. [403].
It was found that it was possible to optimize film thicknesses to
70-85 nm and refractive indices to 1.5-1.7, which followed the
required parameters for a double-layer AR coat onto a glass-
fronted standard a-Si:H solar cell.
There has also been work carried out into the growth of
boron-implanted C60 thin films, serving as the p-layer in het-
erojunction solar cells [404]. However, such films are beyond
the scope of this review.
9.4. Summary
Some possible applications for a-C based devices have been
demonstrated. It must be noted, though, that most of these roles
are in a niche capacity and that the electronic properties of a-C
 AMORPHOUS CARBON THIN FILMS 501

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