RESEARCH ARTICLE | DECEMBER 02 2011

Reaction mechanisms for atomic layer deposition of

aluminum oxide on semiconductor substrates 
Annelies Delabie; Sonja Sioncke; Jens Rip; Sven Van Elshocht; Geoffrey Pourtois; Matthias Mueller;
Burkhard Beckhoff; Kristine Pierloot

Journal of Vacuum Science & Technology A 30, 01A127 (2012)

https://doi.org/10.1116/1.3664090

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Reaction mechanisms for atomic layer deposition of aluminum oxide on
semiconductor substrates
Annelies Delabie,a) Sonja Sioncke, Jens Rip, and Sven Van Elshocht
Imec, Kapeldreef 75, B-3001 Leuven, , Belgium
Geoffrey Pourtois
Imec, Kapeldreef 75, B-3001 Leuven, Belgium, Chemistry Department, and PLASMANT, University of
Antwerp, Universiteitsplein 1, B-2610 Antwerp, Belgium
Matthias Mueller and Burkhard Beckhoff
Physikalisch-Technische Bundesanstalt (PTB), Abbestr. 2-12, 10587 Berlin, Germany
Kristine Pierloot
Chemistry Departement, University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
(Received 12 August 2011; accepted 31 October 2011; published 2 December 2011)
In this work, we have studied the TMA/H2O (TMA ¼ Al(CH3)3) atomic layer deposition (ALD) of
Al2O3 on hydroxyl (OH) and thiol (SH) terminated semiconductor substrates. Total reflection x-ray
fluorescence reveals a complex growth-per-cycle evolution during the early ALD reaction cycles. OH
and SH terminated surfaces demonstrate growth inhibition from the second reaction cycle on. Theo-
retical calculations, based on density functional theory, are performed on cluster models to investigate
the first TMA/H2O reaction cycle. Based on the theoretical results, we discuss possible mechanisms
for the growth inhibition from the second reaction cycle on. In addition, our calculations show that
AlCH3 groups are hydrolyzed by a H2O molecule adsorbed on a neighboring Al atom, independent of
the type of backbonds (Si-O, Ge-O, or Ge-S) of AlCH3. The coordination of Al remains four-fold after
the first TMA/H2O reaction cycle. V C 2012 American Vacuum Society. [DOI: 10.1116/1.3664090]

23 August 2023 08:35:04

I. INTRODUCTION
Atomic layer deposition (ALD) is an advanced technique
to deposit thin films on a substrate through a cyclic process
of self-limiting chemisorption reactions of gas phase precur-
sors.1 The use of self-limiting chemisorption reactions
makes it possible to control the deposition at the atomic level
and to conformally coat complex nanostructures. The TMA/
H2O ALD of Al2O3 (TMA ¼ Al(CH3)3) is one of the most
used ALD processes. In Si based solar cells, Al2O3 deposited
by ALD is emerging as an excellent surface passivation
layer.2–4 The reduced electron-hole recombination has been
explained by a low interface state density in combination
with negative fixed charges in Al2O3 that shield electrons
from the interface.4 Al2O3 is also widely investigated as a
high-k dielectric in combination with high mobility channel
materials such as Ge or III-V compounds.5 Obtaining both
low interface state and border trap densities, requirements to
achieve the high mobility in the transistor channel, is quite
challenging.5,6 Other applications for ALD Al2O3 include
dielectrics in memories, moisture barriers, GaN based power
devices, photonic devices and others.
The use of self-limiting chemisorption reactions in ALD
results in accurate thickness control: for bulk deposition, the
amount of deposited material per cycle is constant and
referred to as the steady growth-per-cycle. However, excep-
tions have been reported during the early stages of the depo-
sition on the initial substrate.1,7 Some starting surfaces are
a)
Author to whom correspondence should be addressed; electronic mail:
annelies.delabie@imec.be
not reactive with the ALD precursors. The ALD film can
then nucleate at particular defect sites on the initial substrate,
resulting in an island growth mode. The growth-per-cycle in
the first reaction cycles is then lower as compared to the
steady growth-per-cycle. This is referred to as growth inhibi-
tion. Good nucleation is especially important for ultrathin
films that should be continuous and pinhole-free, e.g., gate
dielectric oxides. In the latter case, growth inhibition or
island growth has been associated with a high leakage cur-
rent,8 poor scaling of the equivalent oxide thickness (EOT),9
and electrical passivation.10,11
Recently, a new complex growth-per-cycle evolution was
resolved for Al2O3 ALD on semiconductor substrates,
including hydroxyl (OH) terminated SiO2/Si and S passi-
vated Ge (100).11–13 In the first reaction cycle, the steady
growth-per-cycle value of 4E14 Al/cm2 was measured, but
the growth inhibition started from the second reaction cycle
on. The growth-per-cycle reduction in the second reaction
cycle implies that the sites at the starting surface itself are re-
active with the ALD precursors, but that the surface species
formed during the first reaction cycle are less reactive than
both the initial surface and bulk Al2O3. Theoretical calcula-
tions indicated that tetrahedral Al surface species are formed
during the TMA reaction with thiol (SH) terminated Ge.12
In this work, we present, together with the experimental
growth curves, a theoretical study of the TMA/H2O ALD of
Al2O3 on semiconductor substrates. We investigate growth
mechanisms for ALD on OH and SH terminated surfaces by
theoretical calculations based on density functional theory
(DFT). First-principles calculations are being increasingly
used to contribute to a better understanding of the surface

01A127-1 J. Vac. Sci. Technol. A 30(1), Jan/Feb 2012 0734-2101/2012/30(1)/01A127/10/$30.00 C 2012 American Vacuum Society
V 01A127-1
01A127-2 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide
chemistry of ALD on semiconductor substrates.12–29 These
theoretical studies allow us to compare the thermodynamic
and kinetic aspects of different reaction mechanisms. Based
on the results, we propose possible mechanisms accounting
for growth inhibition from the second reaction cycle on. Addi-
tionally, more insight is obtained in the surface chemistry of
TMA and H2O during Al2O3 ALD on the initial substrate.
II. EXPERIMENTAL DETAILS
OH terminated SiO2 was obtained by first cleaning 200 or
300 mm Si (100) substrates in a 0.5% HF/H2O solution, and
then re-oxidizing the H terminated Si surfaces in an O3/H2O
solution with an O3 concentration of 20 ppm. As such, fully
OH terminated SiO2 with a nominal thickness of 1 nm is
obtained.30 The OH content of this surface was previously
determined to be 4 – 6 OH/nm2.31
The S passivated Ge (100) substrates were prepared by
dissociative adsorption of H2S on Ge at 320  C as described
in Refs. 11 and 32. The Ge(100) substrates were first cleaned
in 0.5% HF for 40 s. and rinsed in water for one minute. The
HF cleaned Ge substrates were transferred to a CVD reactor,
a H2 bake was performed at 650  C at 40 Torr for 10 mins
(to desorb O or C that can be present after HF clean), fol-
lowed by H2S treatment at 320  C at 20 Torr for 1 min. After
the S passivation, the samples were transferred to the clus-
tered ALD reactor avoiding air exposure. The S content is
6 SH/nm2.11,32
The ALD reactor is a hot wall cross flow ASM PULSAR
2000 or PULSAR 3000 reactor. Al2O3 ALD was performed
at 300  C and at 1 Torr using TMA and H2O as precursors.
The Al content on the Si samples has been determined by
reference-free TXRF analysis.33 The measurements have been
carried out at the plan grating monochromator (PGM) beam-
line of PTB at the synchrotron radiation facility BESSY II.
Employing calibrated instrumentation for this kind of meas-
urements allows for the quantification of the Al deposition
without any reference materials or calibration standards. The
tunable x-ray energy of synchrotron radiation has been
adjusted below the silicon K-absorption edge in order to
reduce the background contribution associated with silicon
fluorescence. This results in improved detection limits and
reduced relative uncertainties for the aluminum quantification.
The relative uncertainties achieved for the determined alumi-
num depositions are about 15%, the main contribution origi-
nating from the fundamental parameters employed.34
Total reflection x-ray fluorescence measurements on the
Ge samples were performed to determine both the Al and S
content of the samples, using an ATOMIKA 8300 W TXRF
system. As x-ray source a W anode was used and operated at
a power of 2.75 kW (50 kV, 55 mA). A monochromatic
x-ray beam was obtained with an energy of 9.67 keV
(WLb). The radiation incident on the surface with a grazing
angle was set at 70% of the critical angle. The acquisition of
x-ray fluorescence was applied for 1000 s lifetime and the
obtained peak intensities were quantified using the sensiti-
vity factors obtained from a 1ng Ni standard on a Si
substrate.
J. Vac. Sci. Technol. A, Vol. 30, No. 1, Jan/Feb 2012
01A127-2
III. THEORETICAL DETAILS
We use theoretical calculations based on DFT to investi-
gate reaction pathways of TMA and H2O on the surface sites
at the initial semiconductor substrate. A set of model clusters
is used to represent the surface sites. The small cluster models
are Si(OH)(SiH3)3, Ge(OH)(GeH3)3, and Ge(SH)(GeH3)3 and
contain only one surface site [Fig. 1(a)]. Multiple surface sites
are represented by larger cluster models Si7H8(OH)4,
Ge7H8(OH)4, and Ge7H8(SH)4 [Fig. 1(b)]. These clusters are
based on the structure of fully OH or SH terminated Si or
Ge(100) surfaces with an OH (or SH) density of 6/nm2. For
Si7H8(OH)4, the O-O interatomic distances are 3.48–3.50 Å
(intra-dimer), 2.93–2.94 Å (inter-dimer) and 4.16–4.93 Å
(inter-dimer diagonal).
The structure of SH terminated Ge is well represented by
the Ge7H8(SH)4 cluster, as proposed in Ref. 32. The struc-
ture of the hydroxylated 1 nm SiO2/Si is uncertain and it is
therefore difficult to represent it by cluster models. There-
fore, we use OH terminated Si(100) as a model system in the
theoretical calculations. The average OH density of hydroxy-
lated 1 nm SiO2/Si is 4-6 OH/nm2, similar as for OH termi-
nated Si(100). It should however be noted that the specific
arrangements of the OH groups will be different (i.e., more
random in an amorphous SiO2 structure). Moreover, some
Si-O-Si bridges in between the OH sites might also be pres-
ent, which can also react with TMA through dissociative
23 August 2023 08:35:04
adsorption (see discussion).7 The Ge7H8(OH)4 cluster is con-
sidered for comparison.
Density functional theory calculations on these clusters
and their interaction with TMA and H2O were performed
using the B3LYP gradient corrected hybrid functional35–38
and the def2-TZVP basis sets.39 These basis sets provide
results that are close to the DFT basis set limit.39 Geometry
optimizations without boundary restrictions were performed
to locate the stationary points on the potential energy surface
(PES). Frequency analyses were performed to check the na-
ture of the structures (e.g., minimum or transition state) and
to calculate the zero-point energy (ZPE) corrections. The
transition state structures reported below all represent saddle
points, characterized by one negative eigenvalue in the Hes-
sian matrix. The eigenvector with the negative eigenvalue
was found to correspond to the reaction coordinate of the
considered reaction. All calculations were performed with
the PCGAMESS code.40,41
FIG. 1. (Color online) Cluster models Si(OH)(SiH3)3(a) and Si7H8(OH)4 (b).
01A127-3 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide
IV. RESULTS
A. Growth inhibition from the second reaction cycle
Total reflection x-ray fluorescence reveals a complex
growth-per-cycle evolution for TMA/H2O ALD in the first
50 ALD cycles, despite the high coverage of OH or SH sites
on the initial surfaces (Fig. 2). In the first reaction cycle,
4 Al/nm2 is deposited on both surfaces, which corresponds
well to the steady growth-per-cycle for Al2O3 ALD at
300  C.7 However, from the second reaction cycle on, the
growth is inhibited: the growth-per-cycle decreases to 1.5 Al/
nm2 on SH terminated Ge and to 2.5 Al/nm2 on OH terminated
SiO2. In the next 20 reaction cycles, the growth-per-cycle
gradually increases back to the steady value of 4 Al/nm2.
This growth-per-cycle evolution is markedly different
from the well documented growth inhibition for ALD
observed for H terminated Si substrates.7,42,43 On H termi-
nated Si, growth inhibition was observed from the very first
reaction cycle on. This has been understood in terms of a
low reactivity of the SiH bonds with the ALD precursors. On
H terminated Si, 0.1 Al/nm2 was measured after the first
reaction cycle for TMA/H2O ALD at 300  C in a commercial
ALD reactor.43 The TMA dose in this type of ALD reactor
FIG. 2. Amount of Al deposited (a) and growth-per-cycle (amount of Al de-
posited per ALD cycle) (b) as a function of the number of cycles for Al2O3
ALD on SH terminated Ge, hydroxylated SiO2, and H terminated Si as
measured by TXRF. The dotted line in (b) indicates the steady growth-per-
cycle of 4 Al=nm2.
JVST A - Vacuum, Surfaces, and Films
01A127-3
is  103 Langmuir. Note that only after TMA exposures
of 108 Langmuir (corresponding to 1 h exposure, which
is not practical in a commercial ALD reactor), the Al areal
density reached values observed for standard TMA expo-
sures (4 103 Langmuir) on OH terminated SiO2.
The growth-per-cycle reduction in the second reaction cycle
implies that the sites at the starting surface itself are reactive
with the ALD precursors, but the surface species formed dur-
ing the first reaction cycle are less reactive than both the initial
surface and Al2O3. Either the surface species created during
the first TMA reaction are not reactive with H2O in the first
reaction cycle, or the surface species created during the TMA/
H2O reaction cycle are not reactive with TMA in the second
reaction cycle. In the next sections, we investigate the kinetics
and thermodynamics of the first TMA/H2O reaction cycle by
means of theoretical calculations based on DFT.
B. TMA chemisorption versus ligand exchange
reaction
A possible mechanism for the growth-per-cycle reduction in
the second reaction cycle is the replacement of reactive SiOH
(or GeOH or GeSH) sites from the starting surface by less reac-
tive SiCH3 (or GeCH3) sites during the first TMA reaction. This
could occur through the following ligand exchange reaction
(We note that the term “ligand exchange” is used for a some-
what different mechanism than commonly in the literature on
23 August 2023 08:35:04
ALD; see, e.g., Ref. 7) in which a surface -OH (or -SH) site is
exchanged with a methyl group of TMA (for the case of SiOH):
AlðCH3 Þ3 þ SiOH ! SiCH3 þ AlðCH3 Þ2 OH:
As a result, the Si (or Ge) surface becomes methyl termi-
nated and Al(CH3)2OH (or Al(CH3)2SH) is formed. If SiCH3
(or GeCH3) groups are formed, they will be difficult to hy-
drolyze (see below). As such, SiCH3 (or GeCH3) groups can
block TMA chemisorption in the second reaction cycle.
We compare the ligand exchange reaction with the fol-
lowing TMA chemisorption reaction:
AlðCH3 Þ3 þ SiOH ! SiOAlðCH3 Þ2 þ CH4 :
In the chemisorption reaction, the Al-O (or Al-S) bond is
formed and the H from the cluster is transferred to one of the
methyl groups of TMA in order to release CH4. For the
comparison, we use the model clusters Si(OH)(SiH3)3,
Ge(OH)(GeH3)3, and Ge(SH)(GeH3)3. The PES of both reac-
tions are shown in Fig. 3.
Both chemisorption and ligand exchange reactions start
with the formation of a coordinative bond between the Al of
TMA and the O of –OH (or S of SH) sites of the cluster. The
coordination of Al in the complex is near-tetrahedral. The
coordinative complex between TMA and GeOH or SiOH is
stronger as compared to GeSH, as indicated by the more nega-
tive binding energies (–14.9 and –10.2 versus –4.4 kcal/mol,
respectively). This is in agreement with previous DFT calcu-
lations on cluster models for GaAs substrates.23
The chemisorption reactions are strongly favored kineti-
cally over the ligand exchange reactions. This is indicated by
01A127-4 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide 01A127-4

Ge7H8(OH)4,and Ge7H8(SH)4 [Fig. 1(b)] contain four OH (or

SH) groups and therefore better represent the OH or SH termi-
nated surfaces.
The calculations indicate that TMA can favorably react
with up to three reactive sites. We define the following con-
secutive chemisorption reactions (for OH):

AlðCH3 Þ3 þ 2 OH ! ðOÞðOHÞAlðCH3 Þ2 þ CH4

ðreaction IÞ
ðOÞðOHÞAlðCH3 Þ2 þ OH
! ðOÞ2 ðOHÞAlCH3 þ CH4 ðreaction IIÞ
ðOÞ2 ðOHÞAlCH3 ! ðOÞ3 Al þ CH4 ðreaction IIIÞ

In each chemisorption reaction, an Al-O bond is formed, and

a H atom from one of the OH groups in the cluster is trans-
ferred to one of the methyl groups of TMA in order to
release CH4 (see Fig. 4 for cluster Si7H8(OH)4). Reactions I
and II also incorporate the formation of an additional coordi-
native bond between Al and the second or third -OH site,
respectively, occurring immediately after the formation of
the dimethylaluminum (DMA) or monomethylaluminum
(MMA) group. The coordinative bond is a similar interaction
as in the initial coordinative complex formed between TMA
and a surface site (as described above), and increases the Al
coordination from threefold planar to near tetrahedral instead

23 August 2023 08:35:04

of trigonal in the absence of other sites. The binding ener-
gies, energy barriers and reaction energies as defined in
Fig. 4 are summarized in Table I.
FIG. 3. (Color online) PES calculated for (a) the chemisorption reaction and
(b) the ligand exchange reaction of TMA with -SiOH, -GeOH and -GeSH
sites in the cluster models Si(OH)(SiH3)3, Ge(OH)(GeH3)3, and Ge(SH) 1. TMA chemisorption reaction I
(GeH3)3. The structures of the stable minima and transition states are pre-
sented for reactions with Si(OH)(SiH3)3. The energy barriers are shown in Reaction I starts with the formation of a coordinative
between brackets. complex between TMA and the surface site, similar as
observed using the small cluster models. The binding ener-
the lower energy barriers to form the transition state structures.
gies obtained from the large and small clusters differ by less
The transition state of the chemisorption reaction contains a
than 2 kcal/mol, indicating that the backbonds of SiOH,
pentacoordinated Al atom due to an additional interaction with
GeOH and GeSH have little or no impact on the strength of
the H that is transferred from the OH to the CH3 group. The
the coordinative bond. This is in agreement with our previ-
ligand exchange reaction involves a pentacoordinated Si (or
ous study of the TMA chemisorption on S passivated Ge
Ge) atom in the transition state that allows the exchange of the
substrates.12
OH and CH3 ligands between Al and Si. This unfavorable
The use of large cluster models including four -OH groups
coordination for Si or Ge results in a higher energy barrier.
allows us to investigate H transfer reactions from different -
The calculations also indicate that the chemisorption reac-
OH (or -SH) sites in the cluster. The different transition state
tions are also thermodynamically favored over the ligand
structures for the Si7H8(OH)4 cluster are shown in Fig. 5. The
exchange reactions for all considered sites (SiOH, GeOH and
transition state structure with the lowest energy corresponds
GeSH): the calculated reaction energies obtained for the
to the one obtained using the small cluster models [Fig. 5(a)].
ligand exchange reactions are less negative as compared to
It involves a (1-2) H transfer from the -OH involved in the
the chemisorption reactions.
coordinative bond with TMA. The energy barrier with respect
To conclude, the calculations demonstrate that the chemi-
to the energy of the coordinative complex is 11.2 kcal/mol
sorption of TMA occurs faster than the ligand exchange
(Table I). A H transfer from an OH group that is not involved
reactions, and is also thermodynamically more favorable.
in the coordinative bond results in a higher energy barrier.
The energy barrier for the (1-5) intra-dimer H transfer reaction
C. TMA chemisorption reactions with multiple surface
(13.8 kcal/mol) is slightly higher as compared to the (1-2) H
sites
transfer. The energy barrier for the (1-6) inter-dimer H trans-
In this section, we further investigate TMA chemisorption fer is much higher (18.8 kcal/mol). Thus, the energy barrier
on more relevant cluster models that include multiple surface largely depends on the orientation of the OH group involved
sites in close proximity. The cluster models Si7H8(OH)4, in the H transfer reaction. Similar differences in energy

J. Vac. Sci. Technol. A, Vol. 30, No. 1, Jan/Feb 2012

01A127-5 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide 01A127-5

FIG. 4. (Color online) PES for the TMA chemisorption reactions I, II and III with Si7H8(OH)4. The values for the binding energies (BE), energy barriers (EB)
and reaction energies (RE) as defined here are shown in Table I.

barriers are observed for the TMA chemisorption on the
Ge7H8(SH)4 cluster (Table I). The energy barrier is higher for
the reaction with SH, indicating that the surface reaction with
SH sites is slower than with OH sites. We conclude that the
(1-2) H transfer will be the most important reaction channel
because of the fastest reaction kinetics, whereas the (1-5)
intra-dimer H transfer might contribute with a slightly lower
rate constant.
All reaction energies for reaction I are negative, indicat-
ing exothermic reactions (Table I). As already mentioned

23 August 2023 08:35:04

above, the DMA species form a coordinative bond immedi-
ately after its formation. This interaction can occur with the
TABLE I. Energies (kcal=mol) as defined according to Fig. 4 for the TMA
three different sites from the cluster, leading to different
chemisorption reactions I, II and III. BE ¼ binding energy for the formation
of the coordinative complex, EB ¼ energy barrier, RE ¼ reaction energy. reaction energies for reaction I. The most stable reaction
products have an intra-dimer or inter-dimer coordinative
Orientation BE EB RE bond (Figs. 6(a) and 6(b), respectively). A diagonal inter-
dimer coordinative bond [Fig. 6(c)] is less favorable as indi-
Si7H8(OH)4 I intra-dimer –11.3 11.0 (1-2) H transfer –53.0
cated by the less negative reaction energy. Moreover, due to
13.8 (1-5) H transfer
18.8 (1-6) H transfer
the large O-O (or S-S) interatomic distance, the interaction
inter-dimer –54.3 induces large distortions in the cluster model that are not re-
inter-dimer –50.4 alistic in a Si or Ge lattice. Reactions with OH are more exo-
diagonal thermic than the corresponding reactions with SH.
II intra-dimer 22.2 (1-2) H transfer –30.6
III intra-dimer 27.9 (1-2) H transfer 8.4
2. TMA chemisorption reactions I, II versus III
Ge7H8(OH)4 I intra-dimer –15.0 12.3 (1-2) H transfer –55.5
14.8 (1-5) H transfer The TMA chemisorption is not limited to the formation
19.6 (1-6) H transfer of DMA (reaction I). Further reaction to MMA (reaction II)
inter-dimer –55.8 is favorable, at least when reactive sites are available at suffi-
inter-dimer –51.3 cient proximity. This is in agreement with recent calcula-
diagonal tions for OH and SH terminated Si(100) substrates.12,19
II intra-dimer 25.2 (1-2) H transfer –29.6
When comparing the consecutive TMA chemisorption reac-
III intra-dimer 28.4 (1-2) H transfer 8.3
tions I, II, we observe higher energy barriers for reaction II,
Ge7H8(SH)4 I intra-dimer –4.7 15.1 (1-2) H transfer –38.4 indicating that the reaction kinetics becomes substantially
16.9 (1-5) H transfer slower. The reactions also become less exothermic.
26.2 (1-6) H transfer Reaction III, in which all CH3 groups are released from
inter-dimer –36.2 Al, can be excluded. For OH terminated substrates, the reac-
inter-dimer –26.9
tion becomes endothermic by 8 kcal/mol. For SH terminated
diagonal
substrates, the reaction is still slightly exothermic
II intra-dimer 21.4 (1-2) H transfer –26.0
inter dimer 23.5 (1-2) H transfer –26.4
(2.3 kcal/mol) but the energy barrier is huge (36 kcal/mol).
III intra-dimer 36.0 (1-2) H transfer 2.3 We did not find stable structures with interactions of TMA
with a fourth site.

JVST A - Vacuum, Surfaces, and Films

01A127-6 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide
FIG. 5. (Color online) Different transition state structures for the TMA
chemisorption reaction I with the Si7H8(OH)4 cluster: (a) 1-2 H transfer, (b)
1-5 intra-dimer H transfer, (c) 1-6 H inter-dimer H transfer.
We conclude that TMA can react according to reactions I
and II on fully OH or SH terminated surfaces, with the for-
mation of DMA and MMA surface species.
3. Chemisorption of two TMA molecules in close
vicinity
As two adjacent OH (or SH) sites are still available after
reaction II, we also investigated the chemisorption of a second
TMA molecule with the Si7H8(OH)4, Ge7H8(OH)4, and
Ge7H8(SH)4 clusters. Because of the large computational cost
of the calculations, only the reaction product is calculated.
The calculations indicate that two adjacent MMA groups can
reach a tetrahedral coordination on four O (or S) atoms, each
MMA group being bonded to three O (or S) sites and sharing
two of these O (or S) bonds (Fig. 7). The shared bonds are
multiple center bonds and therefore have an electron deficient
character (there are insufficient electrons for a Lewis structure
to be written). These structures were also confirmed by three
dimensional periodic calculations with periodic boundary con-
ditions, using the SIESTA code.44 We used a double zeta ba-
sis set including polarization functions (DZP), the Perdew-
Zunger Local Density Approximation (LDA) and norm con-
serving pseudopotentials including scalar relativistic effects
according to the Troullier-Martin scheme.45 The equivalent
plane wave cutoff for the fast Fourier transform grid was set
to 200 Ry and a (4x4x1) k point mesh are used, allowing con-
vergence of the total energy of the system below 10 meV.
The modeled structure consists of a 2x1 reconstructed Ge sur-
face with six slabs of Ge layers, terminated by the structures
obtained from the cluster calculations.
FIG. 6. (Color online) Different isomers of the surface species formed after
TMA chemisorption reaction I with the Si7H8(OH)4 cluster: (a) intra-dimer
reaction, (b) inter-dimer reaction, (c) inter-dimer diagonal reaction.
J. Vac. Sci. Technol. A, Vol. 30, No. 1, Jan/Feb 2012
01A127-6
FIG. 7. (Color online) Structure after chemisorption reaction II of two TMA
molecules with cluster Si7H8(OH)4.
D. H2O reaction in the first TMA/H2O reaction cycle
Next, we investigated the H2O reaction in the first reac-
tion cycle, i.e., the hydrolysis of the CH3 groups formed in
the TMA reaction. If the CH3 groups formed after the first
TMA reaction are not reactive with H2O, the TMA chemi-
sorption in the 2nd reaction cycle can be inhibited. We
investigate the hydrolysis of SiCH3, GeCH3 and AlCH3
groups. Note that the calculations indicated that it is unlikely
that SiCH3 or GeCH3 groups are formed through the ligand
exchange reaction with surface OH or SH groups. They
23 August 2023 08:35:04
could however be formed through dissociative adsorption on
Si-O-Si (or Ge-O-Ge or Ge-S-Ge) bridges if present.
1. Hydrolysis of SiCH3 or GeCH3 surface species
The reaction of H2O with SiCH3 or GeCH3 groups has
been investigated using the small cluster models Si(CH3)
(SiH3)3 and Ge(CH3)(GeH3)3. The transition state is shown
in Fig. 8 and the reaction energetics are shown in Table II. In
agreement with the apolar nature of the GeCH3 and SiCH3
bonds, we could not find a stable complex between H2O and
the Si(CH3)(SiH3)3 and Ge(CH3)(GeH3)3 clusters.
The hydrolysis of the SiCH3 and GeCH3 bonds is kineti-
cally unfavorable. Energy barriers of 51.3 and 51.7 kcal/mol
are calculated for the SiCH3 and GeCH3 groups, respec-
tively. The penta-coordinated Si (or Ge) atoms in the transi-
tion state are unstable, similar as for the TMA ligand
exchange reaction. The reactions are exothermic but the
reaction energies are moderate. If SiCH3 or GeCH3 species
are formed, their hydrolysis will be kinetically hindered.
FIG. 8. (Color online) Transition state structure for the hydrolysis of SiCH3
bond of the Si(CH3)(SiH3)3 cluster.
01A127-7 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide 01A127-7

TABLE II. Energies (kcal=mol) for the H2O chemisorption reactions. The (or C) bonded to the same Al, whereas in a (1-4) H transfer
reaction pathways for the (1-2) and (1-4) H transfer reactions for the reaction, the H atom is transferred to O (or C) bonded to the
SiOMMA cluster are demonstrated in Fig. 9. BE ¼ binding energy for the
formation of the coordinative complex, EB ¼ energy barrier, RE ¼ reaction
neighboring Al atom in the cluster (Fig. 9).
energy. (1-4) H transfer reactions are strongly favored kinetically
over (1-2) H transfer reactions, similar as described previ-
BE EB RE ously for the H2O reaction with a-Al2O3 surfaces.46,47 (1-4)
H transfers proceed through a transition state structure with
SiCH3 (1-2) H transfer to CH3 — 51.3 –21.3
GeCH3 (1-2) H transfer to CH3 — 51.7 –11.4
Al in a four-fold coordination and the formation of a six-
membered ring. In contrast, (1-2) H transfers proceed
SiOMMA (1-2) H transfer to CH3 –17.2 24.5 –34.9 through a transition state structure with Al in a five-fold
(1-4) H transfer to CH3 –17.2 7.7 –39.9 coordination and the formation of a four-membered ring.
(1-2) H transfer to SiOAl –17.2 12.0 –28.7
The latter seems energetically less favorable, resulting in a
(1-4) H transfer to SiOAl –17.2 0 –28.7
higher energy barrier.
GeOMMA (1-2) H transfer to CH3 –15.3 25.7 –34.6 As a consequence, the Al-CH3 groups are hydrolyzed
(1-4) H transfer to CH3 –15.3 8.4 –38.0 faster by H2O adsorbed on a neighboring Al atom [Fig.
(1-2) H transfer to GeOAl –15.3 11.6 –26.0 9(a)]: with an energy barrier of 7.7 kcal/mol for the (1-4) H
(1-4) H transfer to GeOAl –15.3 0 –26.0 transfer, as compared to 24.5 kcal/mol for the (1-2) H trans-
GeSMMA (1-2) H transfer to CH3 –10.7 27.5 –34.2 fer, the (1-4) H transfer reactions are about 10E þ 8 times
(1-4) H transfer to CH3 –10.7 16.1 –23.2 faster than (1-2) H transfer reactions. The (1-4) H transfer
(1-2) H transfer to GeSAl –10.7 16.0 –16.5 reaction to CH3 is also thermodynamically more favorable
(1-4) H transfer to GeSAl –10.7 0 –16.5 than the (1-2) H transfer reaction (Table II). Thus, in order
a-Al2O3 (1-2) H transfer to AlOAl –23.3a 6.6a –33.2a to correctly describe the H2O reaction by means of cluster
(1-4) H transfer to AlOAl –23.3a 2.2a –32.5a models, at least two Al atoms should be present in the
cluster.
a
References 46 and 47. However, H transfer from H2O to the O atoms in the Si-
O-Al backbonds is much faster than H transfer to the CH3
2. Hydrolysis of Si7H8O4(AlCH3)2, Ge7H8O4(AlCH3)2 groups [Fig. 9(b)]. The (1-4) H transfer along the H bridge to

23 August 2023 08:35:04

and Ge7H8S4(AlCH3)2
As a model system for investigating the hydrolysis of
AlCH3 groups, we consider the Si7H8O4(AlCH3)2 structure
represented in Fig. 7, as well as the corresponding structures
obtained by replacing Si by Ge and O by S. The PESs are
shown in Fig. 9, while the corresponding energies are sum-
marized in Table II.
The H2O reaction starts with the formation of a complex
between H2O and the cluster (Fig. 9). In the most stable
structure, the H2O molecule binds by two interactions: a
coordinative bond between the O atom of H2O and Al, and a
H bond between the H atom of H2O and one of the O atoms
from the Al-O-Si backbonds. One of the shared Al-O bonds
is released by this interaction with H2O. As such, the coordi-
nation number of each Al atom remains four in the coordina-
tive complex with H2O. The binding energy of the complex
is –17.2 kcal/mol. The binding energy is less negative than
for the unimolecular adsorption on coordinatively unsatu-
rated surface atoms of an a-Al2O3 (0001) surface (–23.3 –
–25.7 kcal/mol46,47). The Al-CH3 bonds probably partially
hinder a stronger interaction. Other less stable complexes
(i.e., local minima on the PES) were also found, depending
on the orientation of the approaching H2O molecule.
Starting from the H2O complex, different H transfer reac-
tions are possible. A H atom can be transferred from the
H2O molecule to either the CH3 groups or the O atoms of the
Si-O-Al backbonds (Fig. 9(b), respectively). Two types of H
transfer reactions can occur, similar as described previously
for the H2O reaction with a-Al2O3 surfaces.46,47 In a (1-2) H
transfer reaction, the H atom is transferred from H2O to O
a neighboring Si-O-Al backbond occurs without energy bar-
rier. The OH group further rearranges without energy barrier
to a position in between the two MMA groups. An additional
H bond linking the O atoms of the backbonds further
stabilizes the structure. The result is a meta-stable structure
(–28.7 kcal/mol) with both MMA groups still present. Hy-
drolysis of the CH3 groups in this structure can become
problematic as it requires a (1-2) H transfer reaction from
either the Al-OH-Al linkage or from the Si-OH-Al linkage,
and therefore needs to cross energy barriers of 27 kcal/mol
or more. The adsorption of another H2O molecule to this
fragment is less favorable than the first H2O adsorption since
it requires breaking both the H bond and the Al-OH-Al link-
age. The binding energy of a second H2O molecule is there-
fore significantly lower than that for the first H2O molecule
(–8.5 kcal/mol as compared to –17.2 kcal/mol).
The reactivity of H2O is somewhat affected by the back-
bonds of the AlCH3 group. We compare the energetics of the
H2O reaction for the Si7H8O4(AlCH3)2, Ge7H8O4(AlCH3)2
and Ge7H8S4(AlCH3)2 clusters in Table II. For all systems,
the (1-4) H transfer reactions are strongly favored kinetically
over the (1-2) H transfer reactions, and H transfer from H2O
to either the Si-O-Al, Ge-O-Al or Ge-S-Al backbonds is
favored kinetically over the H transfers to the CH3 groups.
There are moderate differences in the reaction kinetics for O
versus S in the backbonds of Al. S in the backbonds of Al
generally results in higher energy barriers of the H transfer
reactions as compared to O in the backbonds of Al. The
(1-4) H transfer to CH3 and the (1-2) H transfer to Ge-S-Al
have about the same energy barrier and will therefore pro-
ceed with similar reaction rates. The thermodynamics of the

JVST A - Vacuum, Surfaces, and Films

01A127-8 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide 01A127-8

23 August 2023 08:35:04

FIG. 9. (Color online) PES calculated for H2O reactions with the Si7H8O4(AlCH3)2 cluster: (a) H transfer reactions from H2O to CH3; (b) H transfer reaction
from H2O to the Al-O-Si backbonds with subsequent rearrangement of the OH group to a position in between the two MMA groups. * We could not locate the
structure of the transition state, this typically indicates that the energy barrier is low (below 2 kcal=mol).

reactions is also slightly affected by the backbonds of Al:
with S in the backbonds, the (1-2) H transfer reaction to the
CH3 group becomes thermodynamically the most favorable
reaction, while with O in the backbonds the (1-4) reactions
are thermodynamically most favorable. Replacing Si by Ge
in the OAlCH3 backbonds results in minor differences of the
energetics of the H2O reactions (less than 3 kcal/mol).
V. DISCUSSION
The growth-per-cycle reduction in the second reaction
cycle implies that the sites at the starting surface itself are re-
active with the ALD precursors, but that the surface species
formed during the first reaction cycle are less reactive than
both the initial surface and Al2O3. This can mean either that
the surface species created during the TMA reaction are not
reactive with H2O, or that the surface species created during
the H2O reaction are not reactive with TMA.
Calculations indicated that on OH or SH terminated surfa-
ces TMA can react according to reactions I and II, resulting
in the formation of DMA and MMA surface species. This is
in agreement with an Al content of 4/nm2 in the first reac-
tion cycle (TXRF). The chemisorption of TMA occurs faster
than the ligand exchange, and is thermodynamically more
favorable. It is therefore not likely that SiCH3 or GeCH3
groups are formed in significant concentrations through
interaction with OH or SH sites. This could agree with
experimental results for Si and Ge substrates: little or no
removal of interfacial oxide (referred to as interfacial self-
cleaning) has been observed during the TMA reaction on
OH terminated SiO2 and SH terminated Ge7,11–13,48
(although removal of GeOx by TMA has been reported49).
The ligand exchange reaction was also considered previously
for -SiH sites also there it was found less favorable than
conventional chemisorption on -SiH.17,18
It is important to note that our present calculations focus
only on the reaction of OH or SH groups with TMA. In the
presence of Si-O-Si, Ge-O-Ge or Ge-S-Ge bridges, SiCH3 or
GeCH3 groups can be formed through dissociative adsorp-
tion of TMA, as reported in literature.7 We demonstrated

J. Vac. Sci. Technol. A, Vol. 30, No. 1, Jan/Feb 2012

01A127-9 Delabie et al.: Reaction mechanisms for atomic layer deposition of aluminum oxide
that the hydrolysis of the SiCH3 or GeCH3 groups is kineti-
cally hindered because of the five coordinated Si or Ge
atoms in the transition state structure. As such, these groups
can block TMA chemisorption in the second reaction cycle.
This provides a mechanism for growth inhibition from the
second reaction cycle on, in the case of starting surfaces that
contain Si-O-Si (or Ge-O-Ge or Ge-S-Ge) bridges.
Our calculations also reveal many reaction pathways for
H2O with an AlCH3 terminated cluster or surface. The (1-4)
H transfer reactions are strongly favored kinetically over the
(1-2) H transfer reactions in the presence of either SiO, GeO
or GeS backbonds. The Al-CH3 groups are therefore hydro-
lyzed faster by H2O adsorbed on a neighboring Al atom. H
transfer from H2O to the Ge-O-Al or Ge-S-Al backbonds are
also favored kinetically over the H transfers to the CH3
groups. H transfer to the backbonds results in the formation
of metastable Al species with remaining AlCH3 groups. The
presence of AlCH3 groups in these metastable species can
block TMA chemisorption in the second reaction cycle. This
provides a second mechanism for growth inhibition from the
second reaction cycle on.
VI. CONCLUSIONS
Both experiment and theory indicate that the surface
chemistry of the TMA/H2O ALD of Al2O3 is complex. For
the TMA/H2O ALD at 300  C on OH terminated SiO2/Si or
SH terminated Ge, growth inhibition occurs from the second
reaction cycle on, while the growth in the first reaction cycle
corresponds to the steady GPC (4 Al/nm2). The growth-per-
cycle reduction in the second reaction cycle implies that the
sites at the starting surface itself are reactive with the ALD
precursors, but that the surface species formed during the
first reaction cycle are less reactive than both the initial sur-
face and Al2O3.
Based on the DFT calculations, we propose two reaction
mechanisms that can account for growth inhibition from the
second reaction cycle on. For starting surfaces that contain
Si-O-Si (or Ge-O-Ge or Ge-S-Ge) bridges, SiCH3 or GeCH3
groups can be formed through dissociative adsorption of
TMA. The hydrolysis of the SiCH3 or GeCH3 groups is
kinetically hindered and will be unfavorable because of the
five coordinated Si or Ge atoms in the transition state struc-
ture. SiCH3 or GeCH3 groups can therefore block TMA
chemisorption in the second reaction cycle, and account for
growth inhibition from the second reaction cycle on. Our
calculations indicate that SiCH3 or GeCH3 groups will not
be formed through interaction of TMA with OH or SH sur-
face sites.
A second possible reaction pathway is that metastable
MMA-OH-MMA structures are formed during the H2O reac-
tion by H transfer reactions to the backbonds of Al-O(S)-
Si(Ge), which are much faster than the H transfer reactions
to the AlCH3 groups. Metastable MMA-OH-MMA with
unhydrolyzed AlCH3 groups can also block TMA chemi-
sorption in the second reaction cycle.
In addition, our calculations showed that the AlCH3
groups are hydrolyzed by H2O adsorbed on a neighboring Al
JVST A - Vacuum, Surfaces, and Films
01A127-9
atom, independent of the type of backbonds (Si-O, Ge-O, or
Ge-S) of AlCH3. The coordination of Al remains four-fold
after the first TMA/H2O reaction cycle.
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