HISTORY OF THIN FILMS

GROWTH, TECHNIQUES, CHARACTERIZATION

Péter B. Barna
Research Institute for Technical Physics and Materials Science of HAS
Budapest, Hungary

Autumn School 2005 on Advanced Materials Science and Electron Microscopy

Humbold University of Berlin
Oct. 4th - Oct. 7th, 2005
OUTLINE
Thin films in 20th century
HISTORY OF THIN FILMS
Number of publications dealing with thin films is enormously large,
impossible to review the investigated problems and results,

but the analysis of the

OUTCOME can be tutorial

The main aim of this lecture is to introduce an attempt for synthesizing
a view on the structure evolution of elemental and multicomponent
polycrystalline thin films, which could be considered as the key issue
when thinking about the future of the research and development or even
about the diagnosis of technology.

FUTURE
_____________________________________________________________________
This view is mainly based on the fruitful discussions caried out on this topic
during the last years with Professors J.E. Greene, L. Hultman, I, Petrov and Gy.
Radnóczi, as well as with my PhD students Dr. M. Adamik and Dr. A. Kovács.
Thin films in 20th century:
* kind of material peculiar to condensed phase:
structure can be engineered at atomic level
new properties
* became a basis of advanced technologies, devices and industries
* studied in frame of multidisciplinary research
vacuum science
solide state physics and chemistry
surface science
crystal growth
statistical/computational physics
adavanced characterization methodes

"Just as rapid advances in vacuum technology were necessary to launch the

modern era of thin film technology, it was the phenomenal growth of surface
science and applications, together with the continued development and
increasing availability of high resolution transmission electron microscopy,
that allowed the emerging field of thin films to slowly evolve from a highly
advanced empirical art, driven by a very real set of economic and social
benefits, toward an identifiable field of science."
(J.E. Greene, J. Vac. Sci. Technol., A 21(2003)S71)
HISTORY
End of 19th century - unusual properties of deposits on the walls of glass discharge tubes
erosed interest of researchers: optical&electrical properties (P. Drude, Ann. der Physik, 36(1889)532)

1927: - electron diffraction on thin films (Davison - Germer)

1930th- - practical application: high reflectivity surface mirrors on non- conducting substrates
1940th - vacuum and thin film (PVD) techniques, devices;
- electron microscopy (Ruska);
1960th- - in situ electron microscopy (Bassett, Pashley, Poppa, Pócza, Honjo) ;
- surface decoration (Bassett, Bethge, Distler);
- ultrahigh vacuum technique;
- surface analytical methodes: Auger spectroscopy, LEED, SEM, ESCA;
- structure zone model: compilation of experimental results (Movchan-Demchishin)
1970th - - high resolution (also surface imaging) and analytical TEM ( Halle School);
- chemical vapour deposition (CVD);
- computer simulation: atom-by-atom structure building (Gilmer&Bennema,
Barna,Thomas et al; Dirks&Leamy)
- molecular beam epitaxy (MBE);
- CERMET (nanocomposite) resistor films (Neugebauer);
1980th - - atomic resolution surface imaging techniques: STM, AFM (Binning&Röhrer)
- atomic layer epitaxy;
- electron energy loss analysis - dedicated scanning TEM;
1990th - aberration corrected ultrahigh resolution analytical TEM (Urban);
2000th - advent of in situ techniques (UHV TEM, fast STM, synchrotron)
 The pioneering reviews - books

W. Espe and M. Knoll: Werkstoffkunde der Hochvakuumtechnik,(1936)

S. Dushman: Scientific Foundation of Vacuum Techique, (1949)
H. Mayer: Physik dünner Schichten, Teil I (1950) und II (1955)
O. S. Heavens: Optical Properties of Thin Films (1955)
L. Holland: Vacuum Deposition of Thin Films, (1956)
M. Auwärter: Ergebnisse der Hochvakuumtechnik und der Physik dünner Schichten, (1957)
K. L. Chopra: Thin Film Phenomena, (1969)
L. I. Maissel, R. Glang: Handbook of Thin Film Technology, (1970)
H. Mayer: Physics of thin films Parts, I and II, (Complete bibliography), (1972)
B. Lewis, J.C. Anderson: Nucleation and Growth of Thin Films (1978)

Remark: the book of B. Lewis, J.C. Anderson is a comprehensive rewiev of the results on the
elementary processes of structure formation revealed partly by in situ TEM experiments.
 OUTCOME
Development of
* a resource of scientific knowledge on
preparation, structure evolution and structure - property causality of thin films

* advanced and sophisticated thin film preparation devices

and methods based on advances in vacuum technology
* advanced characterization devices and methods

as a consequence of these
THIN FILMS HAVE TAKEN A PROMINENT PART in
* revolutionary development of new active and passive elements,
devices and industries;
* metamorphosis of society to "information society"
 TOPICS OF INVESTIGATIONS AND THE CAUSALITY
Important aspect of technology: evolution of the material structure

TECHNOLOGY
TECHNOLOGY
PREPARATION APPLICATION
APPLICATION
PREPARATIONMETHOD
METHOD
- -material(s)
material(s)
- -source
source
- -parameters
parameters
PHYSICAL
PHYSICALand
andCHEMICAL
CHEMICAL
PROPERTIES
PROPERTIES

TECHNOLOGY
TECHNOLOGY
STRUCTURE
STRUCTUREEVOLUTION
EVOLUTION STRUCTURE
STRUCTURE
self
selforganizing
organizingprocess
process
controlled ••phase
phasestate
controlledby bytechnology
technologyparameters
parameters state
••morphology
- - nucleation morphologyofofgrains
grainsand
and
nucleation surfaces
surfaces
- - crystal
crystalgrowth
growth ••structure
structureofof crystals
crystals
- - grain
graingrowth
growth - -restructuring
restructuring ••orientation
orientation ofcrystals,
of crystals,texture
texture
••chemical composition
- - surface
surfacechemical
chemical interactions
interactions
chemical composition
••homogeneity
homogeneity
- - phase
phaseformation,
formation,transformation
transformation ••substrate
substrate- -film
filminterface
interface

Relationships investigated generally Causality

Relationships to be understood Route of tailoring
for tailoring film
The main aspect of thin film technology is that the "self
organizing" structure evolution takes place
by an atom-by-atom adding process
at temperatures far from thermodynamic equilibrium
which allow the controlled synthesis of
metastable phases
artificial structures: multilayers, nanocomposites
Further possibility to control the structure evolution and structure is the co-
deposition of minute amount of active additives, an example: aluminium
deposition
Tailoring of nanocomposite structures by codepiting inhibitor additive

Physically separated microcrystals in

CoCrTa recording media (Sinclair, 1992)

Cross-section In-plane

FePt recording media doped with SiO2 (Sáfrán et.al. Thin Solid Films, in print)

cross section
 Operation of oxygen as
inhibitor additive at the
deposition of Al films
Grain morphology and
texture of Al films deposited
at TS = 0,3 Tm
as a function of

Koxygen = Joxygen/JAl
the incident Oxygen (Joxygen) to

Aluminium (JAl)) flux ratio

P.B. Barna, M. Adamik, Thin Solid Films,
317(1998)27
 STRUCTURE EVOLUTION
self organizing process

realized in can be described by the

fundamental phenomena pathway of structure evolution
course of the fundamental phenomena

related to thermally activated

atomic processes
temperature dependence

nucleation
adatom migration
derived
structure zone models
crystal growth
adatom self surface diffusion
basis for the evaluation
of experimental results
grain growth
bulk diffusion

P.B. Barna, M. Adamik, Thin Solid Films, 317(1998)27; I. Petrov, P.B. Barna, L. Hultman, J.E. Greene, J.
Vac. Sci. Technol.,21(2003)S117)
 Fundamentals of the self organising nature of thin film
growth

STRUCTURE EVOLUTION
self organizing process controlled by

determined by the
TECHNOLOGY
PARAMETERS
concrete - electronic structure of
structural constituent atoms
conditions types of crystal structure
at any instant
structural
preconditions - thermodynamics
- kinetics
phase state
material structure
Role of kinetics: diffusion-limited two-dimensional aggregation of atoms
a-Ge islands grown on cleaved NaCl (100) surface. Computer
Au deposition on Ag(111) simulation of growth on a square lattice considering limited edge
M. Klaua, Proc. 2nd Colloqium
on Thin Films, ed. E. Hahn, diffusion (D1) (A.Barna, P.Thomas, et al., Thin Solid Films, 48, (1978) 163)
Budapest, 1967, p. 152.

Variation of
the shape
with the edge
migration
distance (D1)
of adatoms:
a) D1 = 0
c) D1 = 4
f) D1 = 8
DISCUSSION IS FOCUSSED on
* fundamental phenomena and path-way of structure
evolution
which can make possible
- to understand
* the formation mechanisms of various structures
* operation of additives/contaminants
* interpretation of experimental results
- tailoring designed structures to achieve the specified properties
- selection and tailoring the adequate preparation method and
parameters
- diagnosis of thechnolgy
* aspects and problems of the preparation of thin film structures by
simulation and physical experiments
"Crystal growers have been moving inexorably closer to being able to deposite
layers and hence to control film properties on an atom-by-atom basis. We are
nearing an era in which it will be possible to deposite
"designer" materials with a specified set of properties."
(J.E. Greene, MRS Bulletin, 26(2001)777)
 Types of thin films and preparation modes

mono crystal polycrystal amorphous

elemental multicomponent
mono phase mono or poly phase

prepared by prepared by

MC/MD simulation (MC/MD simulation)

physical experiments physical experiments

contamination contamination
deviation from
stoichiometry
 Aspects and problems of the preparation of thin film
structures by simulation and physical experiments
Preparation by simulation experiments:
Kinetic Monte Carlo (MC) and molecular dynamic (MD)
- related to idealized systems: species, building the structure, are known
- present direct insight into the behaviour of adatoms and atomic interactions

- but: high amount of data of activation barriers are required

- crucial is the knowledge of the correct potentials
source

Preparation by physical experiments: material

conditions are far from idealized system:

contamination
- substrate contamination ( bulk, adsorbed gases)
enviroment
- deposition takes place in an environment:
co-depositing environmental impurity species (mostly
not controlled and known)
substrate
 Effect of contamination on the nucleation density and orientation of
Au crystals on NaCl cleaved surfaces
carbon contamination of the surface dependence of Au nucleation density on the
developed during heat treatement of level of contamination during deposition
NaCl: affected: nucleation density and
M.Kroh, H.Bethge, Thin Solid Films, 57(1979)227
orientation
M. Krohn, Á. Barna, Proc. 2nd Colloqium on Thin Films,
ed: E. Hahn, Akadémiai Kiadó, Budapest, 1967, p.45
clean contaminated

Krohn-Bethge
high purity
deposition

[111] [001] + random

 Effect of additives on the monolayer growth: epitaxial Pt film
(Poelsema et al.: Acta Phys. A, 53(1991)369)

Effect of oxygen on the surface growth morphology of Al films (TS = 3000 C)

(Barna et al.: phys. stat. sol. a., 55, (1979) 427 )

truncation by step bunching

Kox~10-3 Kox~10-2 Kox>10-1 Kox~ 10-3

 Effect of CO adsorption on the growth of Pt on Pt(111) surface at 400 K
(M. Kalff, G. Comsa, Th. Michely, PRL 81(1998)1255) (STM topograhs, scan size 1700 X 2500 Å.)

Parcial pressure of CO during deposition, mbar

< 5x10-12 1x10-10 4.7x10-10 9.5x10-10 1.9x10-9
"clean"

"In conclusion, we have demonstrated that all aspects of homoepitaxial growth

on Pt(111) are influenced by minute amounts of adsorbed CO."
 Conclusions on impurity effects
" Experiencing the development of unusual structural features one has to search for contamination
effects, at first." (P.B. Barna, Proc. 9th International Vacuum Congress, Madrid, 1983, p. 382)

"when reactive surfaces are under study, data from apparently well-characterized
samples may be governed by contaminant effects. The reason is that gas species
from the ambient tend to adsorb at defects, such as island edges, where their effects are
likely to be particularly large. When this is the case, it is unclear what inferences to
draw from agreement of simulations with experiment."
(P. J. Feibelman, PR B 60(1999)4972.

"The experiments presented indicate also that in order to obtain results representative
for a clean growth system, impurity atom to deposit atom impingement rates
(Kimp/dep = Nimp/Ndep) of 10-4 or below may be necessary. This is substantially less
than previously anticipated." (M. Kalff, G. Comsa, Th. Michely, PRL 81(1998)1255)

That means: for clean system at 1 monolayer/s deposition rate the

total pressure of active gases in the preparation system ( e.g. water
vapour, oxygen, CO, etc.) should be less than 10-10 Pa.
Advanced systems make
possible comprehensive
investigation of thin film
growth processes

Schematic diagram of a
computer-controlled
multichamber UHV gas-
source molecular-beam
epitaxy system
(J.E. Greene, MRS Bulletin, 26(2001)777,)
Fundamental phenomena and path-way of structure evolution
elemental system: growth of high purity indium film at Ts = 0,6 Tm,
(UHV in situ TEM experiment, J.F.Pócza, Proc. 2nd Coll. on Thin Films, Budapest, 1967)
 The elementary atomic processes and related fundamental phenomena of
structure formation operating in various stages of film growth (elemental film, TS> 0,3Tm)
GROWTH atomic processes
STAGES FUNDAMENTAL PHENOMENA

NUCLEATION migration of adatoms on substrate

CLUSTERING/NUCLEATION primary

ISLAND self surface diffusion

GROWTH CRYSTAL GROWTH on substrate
NUCLEATION primary

self surface diffusion

CRYSTAL GROWTH
COALESCENCE 1 bulk diffusion
COALESCENCE TYPE I complete
NUCLEATION secondary

self surfce diffusion

COALESCENCE 2
CRYSTAL GROWTH
CHANNEL GROWTH bulk diffusion
COALESCENCE complete/incomplete
GRAIN GROWTH abnormal
NUCLEATION secondary

THICKNESS self surface diffusion

GROWTH CRYSTAL GROWTH
bulk diffusion
(P.Barna, in Diagnostics and Application of thin films, GRAIN GROWTH abnormal/normal
Ed. L. Eckertova, I. Ruzicka, IOP, 1992, p.295)
 PATH-WAY of STRUCTURE EVOLUTION of ELEMENTAL FILMS in range TS ≥ 0,3 Tm
(P.Barna, in Diagnostics and Application of thin films, Ed. L. Eckertova, I. Ruzicka, IOP, 1992, p.295)
STAGES of STRUCTURE EVOLUTION STRUCTURAL PRECONDITIONS
PHENOMENA active in the next growth stage

SUBSTRATE
NUCLEATION
CLUSTERS – NUCLEI random, random
CRYSTAL GROWTH on substrate
INDIVIDUAL SINGLE CRYSTALS
COALESCENCE primary- random, secondary- random
complete
t y p e I liquid like INDIVIDUAL SINGLE CRYSTALS
secondary nucleation random texture
t y p e II random texture
incomplete
POLYCRYSTALLINE ISLANDS
CRYSTAL GROWTH and RESTRUCTURING texture
GRAIN GROWTH in polcrystalline matrix CHANNELS
secondary nucleation
CONTINOUS POLYCRYSTALLINE
FILLING THE CHANNELS
texture
CRYSTAL and GRAIN GROWTH
AS-GROWN STRUCTURE
columnar, polycrystalline
uniform grain size - texture in cross section
GB-s: perpendicular to the film plane
 DERIVATION of the STRUCTURE ZONE MODEL of elementary thin films
growing on amorphous substrate
thickness random competitive growth texture restructuring growth texture

grain growth (abnormal)

(crystal growth) crystal growth (competitive) crystal growth
nucleation nucleation nucleation
Zone I 0,1 Zone T 0,3 Zone II TS/Tm
adatom migration adatom migration adatom migration
on substrate on substrate on substrate
(very limited)
self.surf.diff. self.surf.diff. self. surf. diff
(very limited)
bulk diffusion
GB migration
 STRUCTURE EVOLUTION IN ZONE T: COMPETITIVE GROWTH OF
Aluminium CRYSTALS ON AMORPHOUS SUBSTRATES at TS= 100K
(Simulation experiment: F.H.Bauman, D.L.Chopp, T.Diaz de la Rubia, G.H.Gilmer, J.Greene,
H.Huang, S.Kodanbaka, P. O’Sullivan, I.Petrov, MRS Bulletin, 26 (2001) 182)

(111) crystals, (100) crystals

oo1 oriented crystals of low diffusivity (low potential energy) grow faster
than 111 oriented ones of high surface diffusivity (high potential energy)

Characteristic for Zone T: coalescence (grain growth) does not operate

On amorphous substrates nuclei are randomly oriented, growth competition
takes place among the crystals of various orientation during film growth
developing V-shaped columns and changing texture with film thickness
(competitive growth texture).
 ZONE T structur in TiAlNC coating grown on oxidized Si substrate
V-shaped columnar morphology and competitive 111 growth texture

flat - smooth surface

111 texture FFT

 random competitive growth texture restructuring growth texture

Conclusions on structure evolution in elemental thin films

* correlation exists between grain size, grain morphology, surface
topography and texture, these are developing together
* the in-plane size (column diameter) and the orientation of crystals
can be controlled by the temperature
* the as-deposited structure has low thermal stability
* the possible zones are: Zone I, Zone T and Zone II
* in Zones I and II the structure and orientation are uniform along
thickness, crystals penetrate through the film
* no grain boundaries parallel to the substrate, i.e. no equiaxed grain
morphology (Zone III ) can exist
that means: %
conventional structure zone models compiling experimental results
are realted to systems contaminated by inhibitor impurity:
Zone III is present
Movchan-Demchishin Thornton
1969 1974

Messier et. al Grovenor et. al

1984 1984
Fundamental phenomena and path-way of structure evolution
two component system: growth of carbon doped indium film, Ts = 0,6 Tm,
(in situ TEM experiment, Pócza et al., Jpn. J. Appl. Phys., Suppl. 2, Part 1.(1974)525)
Nucleation and competitive growth of constituent's phases composition: A1-xBx,
x<0,1 : limited mutual solubility, no reaction phase of A1-xsBxs

constituent A: majority
component
constituent B: additive B or A1-xsBxs phases are growing in 2D surface
composition: A1-xBx, x<0,1 covering layer : tissu phase, inhibitor additive,

primary nucleation delayed

of A, nucleation of
segregated secondary
B or A1-xsBxs phases are growing in 3D
inclusions
Bpecies adsorbed phase B on
adatoms on the growth surface of
growth surface of primary phase A
primary phase A
 Tailoring of TiN structure by codepositing Si

Modfel of TiSiN nanocomposite

structure,
S. Veprek, Thin Solid Films 297(1997)145

3 nm

Changes of TiN structure with increasing Si concentration

J. Patscheider, Th. Zehnder, M. Diserens, Surf. Coat. Technol., 146-147(2001)201
STRUCTURE ZONE MODEL of oxygen doped aluminium film
(P.B. Barna, M. Adamik, in Protective coatings and thin films, (Eds. Y. Paulea, P.B.Barna, Kluver 1997, p.279)
 The conventional and the derived structure zone models
conventional derived
effect of inhibitor additive
Movchan-Demchishin Thornton
1969 1974

Messier et. al Grovenor et. al

1984 1984 Barna-Adamik, 1988
3-D INCLUSIONS DEVELOPED IN CO-DEPOSITED FILMS

Al-Pt (2 at%) Al-Ni (5 AT%)

Al6Pt as secondary phase P.B.Barna, in L.Eckertova, T Ruzicka,

Diagnostics and Applications of Thin Films,
A.Kovács et al., Proc. ICEM15,
IOP 1992, p.295
Durban SA, 2002, p.687
Conclusions
(P.B. Barna, M. Adamik, Thin Solid Films, 317(1998)27; I. Petrov, P.B. Barna, L. Hultman, J.E. Greene,
J. Vac. Sci. Technol.,21(2003)S117)

• The structure evolution in polycrystalline films (both elemental and

multicomponent) can be described by a pathway (characteristic for every
materials system) on the basis of the same fundamental phenomena of
structure formation:
nucleation, crystal growth, grain growth
• The operation of every single fundamental phenomenon is related to a thermally
activated atomic process (temperature dependence of the pathway)
• The atomic processes are:
adatom diffusion (Ts > ~ 0,05Tm) (nucleation)
self surface diffusion (Ts > ~ 0,1Tm) (crystal growth, coalescence)
bulk diffusion (Ts > ~ 0,3Tm) (grain growth)
in multicomponent films additionally:
chemical interaction among species
including
process induced segregation of excessive pecies
resulting in
delayed nucleation of secondary phase(s)
 FUTURE

• Combination of dedicated physical and simulation experiments at carefully

designed conditions with special attention to possible contamination effects
• Dedicated experiments on model material systems for collecting data on the
elementary atomic processes (surface and bulk) controlling the cours of the
fundamental phenomena of structure formation
• Comprehensive causality analysis of preparation-structure-properties
• Comprehensive structure analysis (bulk and surface) at atomic resolution
• Extended application of in situ and combinatorial experimental methods