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Production of AIN films: ion nitriding versus

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Article in Thin Solid Films · December 2004

DOI: 10.1016/j.tsf.2004.08.129

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 Thin Solid Films 469–470 (2004) 295 – 303
www.elsevier.com/locate/tsf

Production of AlN films: ion nitriding versus PVD coating

U. Figueroa, O. Salas*, J. Oseguera
Instituto Tecnológico y de Estudios Superiores de Monterrey-Campus Estado de México,
Carretera a Lago de Guadalupe km. 3.5, Atizapán, México 52926 México

Available online 30 October 2004

Abstract

The properties of AlN render this material very attractive for optical, electronic, and tribological applications; thus, a great interest exists
for the production of thin AlN films on a variety of substrates. Many methods have been developed for this purpose where two processes
stand out: plasma-assisted nitriding (PAN) and PVD coating. In the present paper, we compare the processing advantages and disadvantages
of both methods in terms of the characteristics of the layers formed. AlN production by ion nitriding is very sensitive to presputtering
cleaning and working pressure. Layers several micrometers thick can be produced in a few hours, which are formed by a fine mixture of
Al+AlN. The surface morphology of the layers is rather rough. On the other hand, formation of PVD AlN coatings by DC reactive magnetron
sputtering is more readily performed and better controlled than in ion nitriding. PVD results in macroscopically smoother AlN films and with
similar thickness than the ion nitrided layers but produced in shorter processing times. The morphology of the PVD AlN layers is columnar
with a fairly flat surface. Mechanisms for the formation of both types of AlN layers are proposed. One of the main differences between the
two processes that explain the different AlN layer morphologies is the energy of the particles that arrive at the substrate. Considering only the
processing advantages and the morphology of the AlN layers formed, PVD performs better than PAN processing.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Aluminum nitride; Aluminum ion nitriding; Aluminum reactive magnetron Sputtering

1. Introduction still be carried out. However, as a consequence, most of

This paper presents partial results of an ongoing
research project at ITESM-CEM to produce AlN films
on Al substrates to improve their tribological properties for
mechanical applications. Two approaches to produce AlN
are currently evaluated: plasma-assisted ion nitriding
(PAN) and reactive magnetron sputtering (PVD). The
results from the production of AlN by ion nitriding have
been already reported [1]. This information together with
the most relevant published literature on the subject [2–6]
indicates that a presputtering cleaning stage to eliminate
the impervious Al2O3 layer is always necessary prior to
nitriding. Only in one instance this step has been
eliminated [2]. During nitriding, despite the efforts to
maintain a very low pO2 to minimize alumina reformation,
there is always some residual oxygen, but nitriding can
* Corresponding author. Tel./fax: +52 55 5864 5665.
E-mail address: osalas@itesm.mx (O. Salas).
0040-6090/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2004.08.129
the papers report the presence of oxidized phases in the
AlN layer. Regarding the effect of substrate composition,
some investigations indicate that alloying elements, such as
Mg, favor the formation of AlN [2], but all studies were
successful in nitriding pure Al in addition to Al alloys.
Normally, hexagonal polycrystalline AlN is reported with
very small grain size in the tens of nm range. In one case,
a duplex columnar-equiaxic AlN structure has been
observed [3]. Also, in a couple of instances [4,5], the
presence of metallic Al within the layer was observed.
The literature review for AlN deposition by PVD
processes [7–20] reveals that the majority of the studies
are focused on electronic or optical properties and only a
few papers are devoted to tribological applications. Table
1 summarizes the information on PVD processing
conditions reported in the literature. The following
paragraphs describe the relevant structural characteristics
of the films obtained. Reactive magnetron sputtering of
Al on single KCl crystals, aluminum and glass substrates
296 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303

Table 1
Summary of experimental conditions for AlN PVD coating from literature
Reference PVD method Target Substrate Pretreatment conditions
Base Cleaning Power Time
p (Pa) p (Pa) (W) (min)
[6] d.c. RMSa Al (99.95%) disks, Al, KCl monocrystals, 710 4
110 1 420 15
10 cm diam. low C steel, glass pure Ar
4
[7] d.c. RMS Al (99.95%) disks, Si, KCl monocrystals, 710 110 1 430 15
10 cm diam. low C steel pure Ar
4
[16] d.c. RMS Al (99.95%) disks, KCl monocrystals, 710 to 110 1 430 15
4
10 cm diam. low C steel, glass 810 pure Ar
4
[11] d.c. RMS Al (99.999%) disks, NR 510 NR NR NR
5 cm diam.,
5 mm thick
4
[16] r.f. RMS Al (99.999%) disks, Si monocrystal 410 NR NR NR
10 cm diam. disks (100)
5
[12] d.c. triode Al (99.999%) disks, Glass 1.3310 NR NR NR
5 cm diam.
3
[17] MS Al (99.999%) disks, Glass 110 NR NR 30
d.c. RMS 10 cm diam., 3 mm thick
[15] d.c. RMS Al (99.999%) disks, 7059 Corning glass NR NR NR NR
15 cm diam.
[18] d.c. tetrode MS Al (99.999%) disks, Si, SiO2, steel NR NR NR NR
6 cm diam.
4
[14] d.c. and r.f. RMS Al and Ti Rotating Si disks 210 NR NR NR
a
RMS: reactive magnetron sputtering.
b
NR: not reported.

produced thin AlN polycrystalline films that were Al rich
under various total pressures indicating the presence of N
vacancies in the AlN lattice. Higher total pressures result
in more stoichiometric AlN films with enhanced electro-
chemical behavior [7]. Oxygen as a thin Al2O3 layer and
carbon detected in the films were associated to sputtering
gas mixture and residual chamber oxygen and pump
contamination, respectively. In similar studies by the
same group [8,9], AlN films with a smooth and uniform
structure free of cracks were produced. The films were
polycrystalline with very small grain size (15–30 nm),
hexagonal AlN structure, and thickness between 326 and
366 nm. XPS results reveal the presence of surface
oxynitrides and oxides. Their electron diffraction analysis
shows AlN (110), (102), (002), and (100) rings where the
(100) seemed to be the most intense. Nakamura et al.
[10] synthesized AlN films by Al evaporation and
simultaneous irradiation with nitrogen ions. They found
that higher substrate temperature leads to the formation of
films with higher crystallinity and smaller grain size. The
intensity of the (002) and (101) AlN orientations
increased with decreasing N ion (deposition) energy.
The energy input per incorporated atom of d.c. and r.f.
sputter deposition of AlN in pure N2 atmospheres was
investigated by Drqsdeau and Koppenhagen [11]. For d.c.
discharges, there is an increase of the input energy
proportional to the logarithm of pressure. They attribute
this effect to an increase in the cathode dark space with
pressure that in turn leads to a higher amount of
secondary electrons to escape from the magnetron;
however, they do not elaborate further in how this
affects the energy input at the substrate. Furthermore,
their observation of an increase in deposition energy with
increasing pressure is in disagreement with several
authors [7,15,19], which report the opposite trend and
normally associate it to an increase in the probability of
collisions before the sputtered atoms reach the substrate
surface when the pressure is increased. Búc et al. [12]
produced AlN films by d.c. sputtering with balanced and
unbalanced magnetrons on Si substrates with an extra
coil used to confine the plasma above the target. XRD
analysis indicated that the AlN films produced with an
unbalanced magnetron had the hexagonal wurtzite struc-
ture with a (002) preferred orientation, while those
produced in the balanced mode show the normal (100)
orientation. AlN films of various compositions were
produced by reactive sputtering in the work of Vacandio
et al. [13]. Increasing the nitrogen partial pressure from 0
to 0.013 Pa led from pure Al to stoichiometric AlN with
a transition state in which both Al and AlN coexist.
Glocker [14] compared the incident energy at the
substrate during reactive d.c. and low frequency a.c.
sputtering of AlN. The a.c. process results in approx-
imately 64% greater energy flux per deposited atom, 15%
lower deposition rate, a plasma about four times denser,
and electron energies somewhat greater than the d.c.
plasmas. As a result, more ion and electron bombardment
of the substrate is experienced in the a.c. case. Este and
Westwood [15] used r.f. and d.c. discharges to produce
AlN and TiN. In N2 atmospheres, the residual stress in
 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303 297

Table 1 (continued)
Deposition conditions Remarks
Working pN2 T (8C) Time Voltage d (cm) Power (W) i C (A)
p (Pa)
2 3
710 (N2+Ar) 910 NRb 15 min NR 13 NR AlN: 174 nm thick;
AlN grain size: 15–30 nm
310 2, 110 1, 710 3, 510 2, b130 2h 240–280 13 1.2 AlN: 366 nm thick
110 1 (N2+Ar) 110 2 substrate
310 2, 110 1 1.510 2, 910 2 NR 2 h, 1.5 h 240 13 1.2 AlN: 102 and 182 nm thick

0.5–1 (N2+Ar) NR NR NR 180 to 250 7 Balance/unbalanced magnetron.

Bias voltage to substrate.
AlN 800 nm
0.09–1.6 (N2+Ar) 25%N2+75%Ar V300 1h NR 6 100 to 500 NR Bias voltage to substrate

2 2
810 0 to 1.710 NR NR NR NR NR 0.15

6.610 2 to 1 50%N2+50%Ar 200 NR NR 5 NR 300 Facing target and planar

210 1 to 1 100% N2 6.5 Unbalanced magnetron
110 5 NR NR NR NR NR NR NR

0.5–1 (N2+Ar) pN2/pAr=0.3 70, 130, NR NR 10 to 30 750 and 830 NR

and 400
NR pN2/pAr=0.2 to 0.5 b80 NR NR 9.5 1.5103 NR

the AlN films went from 19 GPa compressive to 2.5 GPa compressive stresses was associated to bombardment of
tensile as the pressure increased from 0.2 to 5 Pa with the film by neutral atoms reflected with high energy from
zero stress observed at ~1 Pa. The presence of the the target. The conditions to control the stoichiometry of

Fig. 1. Schematic drawing of the d.c. reactive magnetron sputtering unit for PVD runs. (1) Piranni gauge, (2) cold cathode gauge, (3) pressure gauge
controller, (4) leak valve, (5). 908 on/off valve, (6) target, (7) magnetron, (8) auxiliary heater, (9) timer, (10) turbomolecular pump, (11) rotary vane pump,
(12) gate valve, (13) sample (substrate), (14) thermocouple, (15) shutter, (16) temperature control, (17) gas supply system, (18) d.c. power supply, and (19)
vacuum chamber.
298 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303

Table 2A
Summary of experimental PVD conditions
Sample no. Target sputtering stage Deposition stage
Temperature Time Pressure Gas mixture Temperature Time Pressure Gas mixture
(8C) (min) (Pa) (sccm) (8C) (min) (Pa) (sccm)
PVD 15 (d=2.5 cm) room temperature 10 0.4 6Ar 120 120 0.2 6Ar+2N2
PVD 14 (d=3 cm) room temperature 10 0.4 6Ar 92 120 0.2 6Ar+2N2

AlN films during planar reactive magnetron sputtering
were investigated by McMahon et al. [16]. They
observed that control of film stoichiometry can be more
easily achieved in a mode of controlled cathode voltages
at constant flow rates.
In summary, it is evident that most of the PVD
processes reviewed rely on d.c. reactive magnetron
sputtering to produce AlN layers. The nature of these
layers is of course closely related to processing conditions,
particularly work pressure, substrate to target distance and
voltage, which in turn will affect the energy of the
impinging particles and the structure of the layer and the
residual stresses developed.
When comparing the literature review on both PAN
and PVD processes, a few observations stand out. Even
though lower base and work pressures are required for
PVD processes, minimization of residual oxygen in the
reactor is not critical in this case. Also, in PVD, lower
temperatures were reported to achieve successful forma-
tion of AlN as compared to PAN, and no heating of the
substrate was required. On the other hand, normally
thicker layers are reported for PAN processes than for

Fig. 2. (a) Typical PVD run sequence. (b) Typical PAN run sequence.
 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303
PVD. In any event, according to the literature, both
processes can readily produce AlN layers. The purpose
of this paper is to determine the best route, PVD or
PAN, to produce AlN layers based in a comparative
analysis of the structural characteristics of the layers as
well as on the easiness and control of the AlN formation
conditions.
2. Experimental procedure
2.1. PVD process
Substrate disks of 50.8 mm in diameter and 7 mm in
thickness were cut from a soda lime glass plate. The AlN
films were deposited by d.c. reactive unbalanced magnet-
ron sputtering of an aluminum target in a gas mixture of
argon and nitrogen. A schematic drawing of the reactor is
presented in Fig. 1. The diameter of the aluminum target
was 50.8 mm and thickness was 3.175 mm with a purity
of 99.96% Al. Two deposition runs were carried out at
constant gas mixture of 6Ar+2N2 sccm and work pressure
of 0.2 Pa and two substrate to target distances (d), 2.5 cm
(sample PVD 15) and 3 cm (sample PVD 14), as indicated
in Table 2A. The typical deposition sequence is displayed
in Fig. 2a. Initially, the vacuum chamber was evacuated to
a base pressure of 110 3 Pa, and high purity argon (6
sccm) was introduced at a pressure of 0.4 Pa. Next, the
target was sputtered-cleaned at 310 V for 10 min and then
nitrogen (99.96% pure) was introduced and the working
gas mixture (6Ar+2N2 sccm) was adjusted to a total
pressure of 0.2 Pa. Deposition was carried out for 2 h at
this pressure applying a voltage between 250 and 270 V
and avoiding electrical arcs. The substrates were not heated
externally. The substrate temperature indicated in Table 2A
is assumed to result from plasma heating due to ion
bombardment.
2.2. PAN process
A schematic drawing depicting a typical PAN run is
shown in Fig. 2b. Although details on the procedure to
obtain these samples has been described elsewhere [1], the
relevant process parameters are indicated in Table 2B.
PAN samples were characterized by glancing angle X-ray
diffraction (GAXRD) while PVD samples by conventional
XRD (CXRD). Both were analyzed by optical (OM) and
Table 2B
Summary of experimental PAN conditions
Sample no. Cleaning presputtering stage
Temperature Time Pressure
(8C) (min) (Pa)
PAN 2 350 30 50
PAN 6 400 15 50
299
scanning electron microscopy (SEM)+energy dispersive
microanalysis (EDS). Additionally, PAN samples were also
analyzed by XPS and the results were presented in a
previous paper [1].
3. Results and discussion
3.1. X-ray diffraction
Fig. 3a–d show the diffraction patterns for PAN
(GAXRD) and PVD (CXRD) samples, respectively. Both
processes produce h.c.p. Wurtzite type AlN, and no
evidence of any cubic AlN was found in either case. In
the case of the PAN samples, not only the signal is more
intense, but also all the AlN peaks appear on the
diffractogram, while in the PVD spectra, the peaks are
rather low and only the expected most intense (100) peak
plus the (110) reflection are observed. The relatively wide
peaks in all, the PAN and PVD, XRD patterns indicate that
small grain size was obtained in both techniques.
Currently, more PVD experiments are being carried out
to investigate the relationship between process parameters
and preferred orientations and residual stresses in the AlN
layers.
The higher intensity of the AlN peaks in the PAN XRD
patterns is likely to arise from the enhanced surface signal
GAXRD versus the CXRD used to analyze the PVD
samples. Another interesting difference is the absence of
Al peaks in the PVD diffractograms. One would expect
that the Al peaks present in the PAN patterns arise from
the Al substrate, while in the case of PVD, do not appear
because a glass substrate was used. However, considering
that the PAN layer was analyzed by a surface technique
(GAXRD), the Al signal observed must come from
elemental Al inside the AlN layer at or near the surface.
As mentioned in the Introduction, other authors have also
observed the presence of metallic Al in AlN PAN layers
[4,5]. In the case of PVD patterns, no Al peaks appear, but
the presence of Al either elemental or as an excess Al in
the AlN lattice can still not be ruled out; further analysis is
necessary though. In any event, a distribution of elemental
Al within the layer will be of great importance especially
in terms of the tribological and mechanical properties of
the layer. The absence of amorphous glass peaks in the
PVD diffractograms indicates that the AlN layer formed in
that case was rather thick.
Nitriding stage
Gas mixture Temperature Time Pressure Gas mixture
(sccm) (8C) (min) (Pa) (sccm)
12Ar+3H2 350 120 80 12Ar+3H2+42N2
12Ar+3H2 390 120 80 12Ar+3H2+42N2
300 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303

Fig. 5. (a and b) SEM views of PVD samples 15 and 14, respectively.

Fig. 3. (a and b) GAXRD spectra for PAN samples 2 and 6, respectively. (c
and d) CXRD spectra for PVD samples 15 and 14, respectively.
3.2. Surface morphology
Figs. 4a,c and 5 show the typical surface morphologies of
the PAN and PVD samples, respectively. Even the flattest
surface obtained by PAN in Fig. 4a shows a much rougher
appearance that any of the PVD surfaces. In previous work
[1], it was found that the extent of surface roughness in the
PAN samples was closely associated to the duration of the
presputtering cleaning treatment. According to Ref. [6], in
PAN processes, a minimum presputtering time is required to
produce an Al surface free of Al2O3. This is achieved when
a certain value of Al+/O+ is reached, which is associated to
an equilibrium between sputtering and redeposition of
Al2O3. It follows then that presputtering times shorter than
this minimum will result in Al surfaces with residual Al2O3,
which will prevent the formation of a completely smooth
AlN surface. Even if presputtering times longer than the
minimum are used and an Al2O3-free surface is obtained,
some degree of roughness is still expected due to bombard-
ment with the highly energetic particles present in this
process, especially at the grain boundaries. In fact, the

Fig. 4. (a and b) SEM top view and OM cross-sectional view of PAN sample 2. (c and d) SEM top view and OM cross-sectional view of PAN sample 6.
 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303
energy required to sputter Al is ~13 eV with Ar+ [20], and
the average energy of the Ar ions should be between a few
eV up to 400 eV (this last value corresponds to the applied
voltage) [6]. Additionally, the occurrence of local surface
micromelting within the AlN layer and macromelting along
the surface grains of the substrate during nitriding is
possible and should contribute to the larger surface rough-
ness. Ion bombarding and its effects are considered central
in the PAN layer formation mechanism discussed later. In
the PVD process, production of a smoother layer is expected
considering that less sputtering of the AlN will occur given
the lower energy of the particles arriving at the substrate.
Furthermore, even if some protuberances form, high surface
mobility of these particles can even them out. Finally, the
difference in roughness may also be attributed to some
degree to the roughness of the substrates used in each case.
The glass substrates for the PVD layers were smoother than
the Al substrates used for the PAN samples. The rougher
surfaces in the PAN samples will probably lead to a lower
tribological performance with respect to the smoother
surfaces of the PVD samples.
3.3. Cross-sectional morphology
Figs. 4b,d and 5 show the cross-sectional views from the
PAN and PVD samples, respectively. In the PAN samples,
the rough nature of the AlN layer stands out again as
compared with the almost flat surface of the PVD samples,
especially when Fig. 5d is considered, where roughness is in
the order of tens of micrometers due to the coarse grain
topography that develops during this process. In the flatter
PAN sample, some discontinuities are observed along the
layer. These cracks have been associated to thermal stresses
produced during cooling of the sample by Chen et al. [4]. In
contrast, Fig. 5 shows the dense flat structure developed in
the PVD samples. In the case of the sample PVD 15 (d=2.5
cm) where the layer is thicker, it is clear that a columnar
morphology developed. In the thinner layer of sample
PVD14 (d=3 cm), it is difficult to discern the morphology.
Clearly, the target to substrate distance is central in terms of
growth kinetics. Considering the polycrystalline nature of
the layers, as indicated by the X-ray diffraction results, it
can be concluded that the deposition conditions resulted in
the development of a Z2 type structure in which surface
diffusion allows enough atom mobility to produce a
crystalline columnar dense layer. An interesting feature in
the PVD samples is the rather large thickness of the AlN
layers produced. It varies between 1 Am for PVD 15 (d=3
cm) and 5 Am for PVD 14 (d=2.5 cm), which are much
larger than any of the AlN PVD coatings reported in the
literature reviewed. Comparing the base and work pressure
values, the applied voltage and the target to magnetron
distance selected for the present experiments with those
summarized in Table 1, the thicker AlN layers obtained in
this work are probably due to the much shorter target to
substrate distances (d) used in the present experiments.
301
Considering that not only the deposition conditions were
much more easily obtained and controlled in the PVD
experiments, but also that the treatment time was much
shorter to produce similar AlN thickness (~7 h for PAN vs.
~2.5 h for PVD including the pretreatment periods)
indicates that PVD may be the most adequate technique to
produce these layers. Additionally, it should be emphasized
that in the case of PVD, no heating of the substrate is
required. Nevertheless, results from tribological and adhe-
sion tests should also be considered in the selection of a
technique to produce AlN on Al substrates.
To further establish and discuss the differences between
the two processes, in the following paragraphs, AlN
formation mechanisms are proposed for each case based
on the processing experimental conditions and on the
microstructural analysis of the AlN layers.
3.4. PAN layer formation mechanism
According to the microstructural and phase identification
results, we propose the mechanism for AlN layer formation
in the PAN process illustrated in Fig. 6. It starts with the
Al2O3-free surface after the cleaning presputtering stage
(Fig. 6a) where some roughness is already observed due to
severe preferential sputtering of the soft Al surface and grain
boundaries by the highly energetic ions produced in this
process. At this point, it is important to mention that one of
the consequences of ion bombardment is heating of the
substrate, which in addition to the external heating may lead
to grain and precipitate growth and even surface melting in
any stage of the process.
The sequence of events proposed during nitriding are
largely based on a study of atmosphere characterization
during AlN production by ion nitriding performed by Quast
et al. [6]. This study indicates that during nitriding, in
addition to the Ar+ and Al+ species already present from the
presputtering treatment, N++N+2 ions now appear. According
to these authors, N+2 species are more abundant but less
energetic than the N+ ions, which although fewer, their
energy distribution shows a peak at the highest possible
values given by the voltage applied. In principle, both ions
may react with the clean Al surface to form AlN particles;
however, it is expected that N+ species react more readily,
since reaction with N2+ would have to involve an extra step
of dissociation to form N+ ions before it can form AlN
molecules. Furthermore, the higher energetic N+ particles
may also penetrate the Al surface to react with the Al atoms
in the substrate interior. Once the AlN nuclei form, the
continuing N++N+2 and Ar+ ion bombardment leads to
preferential sputtering of the softer Al surrounding the
harder AlN nuclei (and everywhere else, Al is exposed on
the surface) forming surface protuberances (Fig. 6c). Further
growth of the AlN can now occur below the initial nuclei up
to a thickness that allows penetration of ions to reach the
AlN/Al interface and react there with the Al underneath.
Diffusion of N through AlN to reach the Al substrate and
302 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303
Fig. 6. Proposed PAN layer formation mechanism.
react to form AlN is not expected if stoichiometric AlN is
formed, since the solubility range of N in AlN is nil. Thus,
from the start, a mixture of Al+AlN is formed as
protuberances with an outer AlN layer and unreacted Al
inside. Simultaneously, on the rest of the exposed Al surface
next to the protuberances, more nuclei may form and the
process repeats until eventually all the surface is covered by
a rough structure that is a fine mixture of AlN+Al nodules.
Since now the Al surface is covered by AlN (Fig. 6e) and N
diffusion through it is not feasible, additional growth of the
layer may occur by local melting of the Al cores and
eruption of the molten Al through thin AlN zones (some
AlN resputtering) (Fig. 6f). Once the molten Al erupts
(likely by capillarity) through the layer on to the surface and
solidifies there, the nucleation process repeats (Fig. 6g).
Even formation of AlN in the molten Al cannot be ruled out.
As a result, a layer composed by a fine mixture of AlN+Al
is continuously formed (Fig. 6h). This mechanism could
account for the presence of Al in the surface as evidenced by
GAXRD and contribute to the surface roughness observed.
The presence of a fine network of Al in the layer formed
may also explain why such thick layers were formed in the
present work as compared to some reported in the literature
whose thickness was limited by the dielectric nature of a
layer entirely formed by AlN. Furthermore, it is also
expected that the presence of Al in the AlN layer may have
a beneficial effect on its wear behavior due to an increased
toughness. Chen et al. [4] and Quast et al. [5] also report
metallic Al intermixed in their AlN layers obtained by PAN
processes.
It is clear that high energy ion bombardment of the
substrate is central in the formation of AlN in PAN
processes, but also leads to undesirable layer and substrate
morphologies.
3.5. PVD layer formation mechanism
In the case of the PVD process, the sequence proposed of
AlN formation involves generation of highly energetic Ar+
ions by the unbalanced magnetron. These ions, upon
collision with the target, will sputter Al atoms and Al ions
that will leave the target with some of the kinetic energy
from the collision. Additional Al ions may form when the
Al-sputtered atoms enter the plasma region. Reaction of the
Al species with the N particles to form AlN in this process
may occur both in the plasma volume and on the substrate
surface. According to Smith [21], for the pressure range
used in the present experiments, both diffusion of particles
as well as collisions in the plasma atmosphere are expected.
It is still unclear which reaction dominates, but since
formation of AlN on the surface would require deposition,
adsorption, and migration of the Al and N ions until they
can meet and bind, it would be expected that AlN formation
by reaction in the sputtering gas mixture occurs more
 U. Figueroa et al. / Thin Solid Films 469–470 (2004) 295–303
readily. Once the formation of the AlN molecules occur,
they are deposited on the substrate surface in a fairly
uniform manner. The uniform thickness of the layers
obtained indicates a uniform population of AlN particles
in the sputtering gas mixture, no preferential deposition sites
in the substrate leading, and enough particle mobility at the
surface to even out any crevices or protuberances that form.
One of the main differences between PAN and PVD
processes is the energy of the particles that arrive at the
substrate. Even though in the PVD experiments, since the
base pressure was low and the target-substrate distance
small, it is expected that the ions will arrive on the substrate
surface with still a significant fraction of the collision
energy; in PAN, the particles are much more energetic. For
example, Glocker [14] reports an incident energy per d.c.
sputtered Al atom of 14.1 eV, while Quast et al. [6] observe
ions energies up to the corresponding voltage level used for
PAN processes (up to 400 eV for the present experiments).
This higher energy leads to high surface roughness due to
resputtering of the AlN layer and Al surface melting, and
also to grain and precipitate growth in the substrate that
affects adversely its mechanical properties. Some resputter-
ing of AlN may also be expected in PVD due to Ar+
bombardment, but it will not be as severe as in PAN.
Moreover, ion bombardment in PVD can be controlled to
enhance layer characteristics such as residual stresses and
density.
4. Conclusions
The comparison of the experimental conditions to
produce AlN layers by a PAN and a PVD processes as
well as the structural characteristics of the layers obtained
indicates that PVD has more advantages over PAN, since it
produces smoother, more uniform layers with similar
thickness in shorter processing times. Furthermore, PVD
conditions for AlN formation are more readily obtained and
better controlled than in PAN, and no heating of the
substrate is required. The AlN-proposed mechanisms based
on the experimental conditions and microstructural analysis
for each process suggest that the energy of the species
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involved in each case is central in determining the structure
of the layer. Higher ion energies in the PAN process are
necessary to form the AlN layer, but also lead to severe
sputtering (roughening) of the AlN layer and degradation of
the substrate microstructure. These effects are not expected
in PVD and thus smoother more uniform AlN layers form in
this case.
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