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Cite This: ACS Appl. Mater. Interfaces 2019, 11, 39315−39323 www.acsami.org

Interfacial Silicide Formation and Stress Evolution during Sputter

Deposition of Ultrathin Pd Layers on a‑Si
Bärbel Krause,*,† Gregory Abadias,∥ Clarisse Furgeaud,∥ Anny Michel,∥ Andrea Resta,⊥
Alessandro Coati,⊥ Yves Garreau,⊥,# Alina Vlad,⊥ Dirk Hauschild,†,‡ and Tilo Baumbach†,§
†
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie, Eggenstein-Leoplodshafen
76344, Germany
‡
Institut für Technische Chemie und Polymerchemie (ITCP), and §Laboratorium für Applikationen der Synchrotronstrahlung
(LAS), Karlsruher Institut für Technologie, Karlsruhe 76131, Germany
∥
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Institut PPrime, UPR 3346, Université de Poitiers-CNRS-ENSMA, Chasseneuil-Futuroscope 86960, France

⊥
Synchrotron SOLEIL, Gif sur Yvette 91192, France
#
Laboratoire Matériaux et Phénomènes Quantiques, Université de Paris, Paris 75013, France
Downloaded via 27.53.253.135 on September 29, 2022 at 06:16:58 (UTC).

ABSTRACT: Synchrotron experiments combining real-time stress, X-ray diffraction,

and X-ray reflectivity measurements, complemented by in situ electron diffraction and
photon electron spectroscopy measurements, revealed a detailed picture of the
interfacial silicide formation during deposition of ultrathin Pd layers on amorphous
silicon. Initially, an amorphous Pd2Si interlayer is formed. At a critical thickness of 2.3
nm, this layer crystallizes and the resulting volume reduction leads to a tensile stress
buildup. The [111] textured Pd2Si layer continues to grow up to a thickness of ≈3.7 nm
and is subsequently covered by a Pd layer with [111] texture. The tensile stress relaxes
already during Pd2Si growth. A comparison between the texture formation on SiOx and
a-Si shows that the silicide layer serves as a template for the Pd layer, resulting in a surprisingly narrow texture of only 3° after
800 s Pd deposition. The texture formation of Pd and Pd2Si can be explained by the low lattice mismatch between Pd(111) and
Pd2Si(111). The combined experimental results indicate a similar interface formation mechanism for Pd on a-Si and c-Si,
whereas the resulting silicide texture depends on the Si surface. A new strain relaxation mechanism via grain boundary diffusion
is proposed, taking into account the influence of the thickness-dependent crystallization on the material transport through the
silicide layer. In combination with the small lattice mismatch, the grain boundary diffusion facilitates the growth of Pd clusters,
explaining thus the well-defined thickness of the interfacial silicide layer, which limits the miniaturization of self-organized
silicide layers for microelectronic devices.
KEYWORDS: in situ, real-time, X-ray reflectivity, X-ray diffraction, stress, silicide, sputter deposition, XPS

1. INTRODUCTION Due to their low crystallization temperature, Ni- and Pd-based

Silicide layers have two important functions in silicon-based
microelectronic devices:1−3 They lower the thermal budget for
the production of polysilicon, and they are employed as ohmic
contact and local interconnect. The layers are typically produced
in a two-step process. A metal layer is deposited on silicon and
subsequently annealed. However, already during deposition, a
nanometer-scale silicide interlayer might develop at the
interface.3 Such a layer can serve as a seed for the annealing-
induced silicide growth, influencing thus its microstructure and
resulting electronic properties. Furthermore, the naturally
forming interlayer represents a lower limit for the accessible
silicide thickness.
Numerous studies focus on the silicide formation during post-
growth annealing including, e.g., refs 1, 4−6. With the ongoing
miniaturization of microelectronic devices, however, the inter-
face formation during deposition becomes increasingly relevant.
In the following, we will present a detailed in situ and real-time
study of the chemical interface reaction and structure formation
during sputter deposition of palladium on amorphous silicon.
silicides are of great interest for microelectronic applications.1,3,7
The model system Pd/Si forms only one silicide phase (Pd2Si)
over a wide temperature range, reducing thus the number of
competing structure formation mechanisms.8,9 Bulk Pd has an
fcc unit cell with a = 3.891 Å,10 whereas Pd2Si is hexagonal with a
= 6.496 Å and c = 3.433 Å.11 Our study focuses on the interfacial
silicide formation and its influence on the structure during
subsequent metal growth. This includes the stress buildup and
relaxation during deposition, which is a key factor for all
industrial applications.
The silicide formation during thin film deposition is difficult
to access. Depending on the envisioned application, the metal
films are thermally evaporated or deposited by magnetron
sputtering on amorphous (a-Si) or crystalline (c-Si) silicon
surfaces. Only few authors report on the deposition of Pd on a-Si
Received: July 5, 2019
Accepted: September 24, 2019
Published: September 24, 2019

© 2019 American Chemical Society 39315 DOI: 10.1021/acsami.9b11492

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Figure 1. Measurement geometry (left column) and simultaneous real-time measurements (right column) during deposition of Pd on a-Si: (a) Stress
measurements, (b) diffraction data, and (c) X-ray reflectivity measurements (black) and fit curve (red). The deposition periods of a-Si and Pd as well as
the observed Bragg peaks of Pd and Pd2Si (yellow bars) are indicated. tc indicates the onset of crystallization. The scale of F/w was optimized to the Pd
signal. The inset of (a) shows the signal during Si deposition, and the red circle marks a weak but reproducible stress change at t = 180 s.
at room temperature.9,12−15 It was found that the chemical
reaction between Pd and c-Si occurs instantly during
deposition16 and is already activated at 150 K.16,17 During
early growth stages, several reports propose the formation of
amorphous silicide on c-Si.18−21 For thicker Pd layers, epitaxial
Pd2Si(001) was found on Si(111).4,20,22,23 Layers with gyroaxial
texture were observed on Si(100).6
The reported silicide thickness varies significantly. The main
reason is that the Pd2Si formation can also be induced by ion
beam irradiation24 as used, e.g., for X-ray photoelectron
spectroscopy (XPS) depth profiles and transmission electron
microscopy (TEM) sample preparation. However, for both
evaporation and sputter deposition of Pd, the lowest reported
values are in the range of 3−5 nm.16,18,25,26
To cover different aspects of the Pd/a-Si interface formation,
the here presented study combines real-time growth experi-
ments, performed at the beamline SIXS of the synchrotron
SOLEIL,27 with lab-based in situ electron spectroscopy and
reflection high-energy electron diffraction (RHEED) measure-
ments. During the real-time measurements, we monitored
simultaneously the X-ray diffraction (XRD) signal, the reflected
X-ray beam, and the evolution of the sample curvature, which
reflects the stress buildup during deposition.28 As we will show,
the stress signal is highly sensitive to microstructural changes
within the deposited film and is thus ideally suited as low-cost
growth monitor. However, its interpretation in terms of
microstructure is often ambiguous. This problem is overcome
by simultaneous X-ray measurements at grazing incidence,
which give information about phase formation, layer thickness,
roughness development, grain growth, and texture formation.
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Detailed information about the electronic and chemical
enrivonment of Pd close to the interface was revealed by XPS
and Auger electron spectroscopy (AES).
The combined experimental in situ and real-time approach
provides an encompassing picture of the structure formation
processes during deposition. In the following, this will be
demonstrated for the complex Pd/a-Si interface, which exhibits
a competition between high interface reactivity and crystal
growth.
2. EXPERIMENTAL SECTION
All samples were prepared in a modular and portable sputter deposition
chamber designed for in situ X-ray experiments.29 For the real-time
growth studies, the chamber with a base pressure of 10−6 Pa was
installed on the multi-environment diffractometer (MED) of the SIXS
beamline (synchrotron SOLEIL, France).27 For the lab-based growth
studies, the chamber was docked to a UHV cluster with a base pressure
10−8 Pa.
The grounded Si(100) substrates were covered by native oxide. Pd
films with up to 40 nm thickness were sputter-deposited on a-Si buffer
layers with thicknesses of 4.5 and 9 nm. Within the experimental error,
the results were independent of the selected buffer layer thickness.
Therefore, in the following, we will focus on the results for 9 nm a-Si.
For comparison, several Pd reference layers were deposited without a
buffer layer. During preparation, no additional sample heating was
applied. Due to the requirements of the stress measurements, the real-
time experiments were performed on unclamped Si wafers with 100 μm
thickness. All other samples were deposited on clamped Si wafers with 1
mm thickness. The palladium and silicon sputter targets with a diameter
of 50 mm were mounted at a deposition angle of 18° and target−
substrate distances of 325 and 129 mm, respectively. The a-Si buffer
layer was deposited with an RF power of 60 W, resulting in a deposition
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rate of 0.032 nm/s. Pd was deposited at 40 W DC power, corresponding reproducibility of these changes was verified by monitoring the
to a deposition rate of 0.021 nm/s. The process gas, argon, had a flow deposition of several samples using the same growth condition.
rate of 0.8 sccm, corresponding to a pressure of 0.365 Pa. In the following, the observations will be analyzed in detail.
During sputter deposition, the samples were simultaneously studied The deposition of Si is accompanied by a compressive stress
by a combination of three in situ and real-time methods: X-ray
reflectivity (XRR), XRD, and optical stress measurements. A detailed
signal (Figure 1a), as already reported in ref 28. The deposition
description of the experimental approach can be found elsewhere.28 of Pd, however, leads to several rapid stress changes, which can
The measurement geometry is schematically shown in Figure 1 (left only be understood taking into account the phase evolution
column). For the here presented data, a photon energy, E, of 12 keV and during deposition probed by XRD (Figure 1b). The time-
an incident beam angle, αi, of 1.88° were employed. Under these dependent diffraction signal is constant during deposition of a-Si
conditions, the reflected X-ray beam is expected to oscillate with a but evolves rapidly during the initial 300 s of Pd deposition. Line
period of 1.6 nm during Pd deposition.30 The XRR signal was measured scans along q and t, shown in Figure 2, highlight the
with a Cyberstar YAP scintillation detector, mounted at 1 m distance to
the sample with a detector slit of 0.5 × 2 mm2 (vertical × horizontal).
The XRD signal was recorded with a 2D pixel detector (XPAD). Both
detectors were protected against overexposure by automatic filters.31 At
the optimized sample−detector distance 283 mm, the 2D detector
covered the 2θ range 20−32°. Due to the grazing incidence of the
incoming X-ray beam, the resulting momentum transfer q = 4π/
λ sin(θ) was tilted by ∼14° with respect to the sample surface normal.
The intrinsic (growth) stress was monitored using a multiple (3 × 3)
laser beam optical stress sensor (k-Space Associates) with a curvature
sensitivity better than 2 × 10−4 m−1. The film force per unit width (F/
w), equivalent to the stress × thickness product, σ × h, was derived from
the change in curvature Δκ using the Stoney equation.
Before and after deposition, wide-angle diffraction patterns were
collected by scanning the detector in horizontal and vertical direction.
Approximately 3000 images were taken during 10 continuous
horizontal detector scans at different vertical detector angles. From
this, reciprocal space maps were reconstructed, which show the
measured X-ray intensity as a function of q∥ and qz (the components of
q parallel and perpendicular to the sample surface). All presented maps
are corrected by the scattering background measured before deposition.
In addition to the real-time study, an in situ surface characterization
study was performed on a second sample series. The atomic ordering
close to the surface was studied by RHEED measurements with an
REG30 electron gun (Dr Gassler Electronic Devices) and an electron
energy of 20 keV. The chemical structure at the surface was
characterized by XPS using a nonmonochromated XR-50 Mg Kα X-
ray source and a Phoibos 150 analyzer (SPECS). The energy axis was Figure 2. Line scans extracted from the real-time diffraction data during
calibrated with a Ag reference sample. The XPS and AES peak positions deposition of Pd on a-Si (shown in Figure 1b), at (a) different Pd
were determined with an experimental error of ±0.1 eV. The estimated deposition times with an integration range of ±1 s and (b) different q
error for nominal composition (assuming a homogeneous material with an integration range of ±0.03 Å−1. The selected q values are
distribution) is 10%. indicated in (a) by dashed lines.
Sputter deposition is a nonequilibrium process, and the thin film
growth might be significantly influenced by the kinetic energy of the
deposited atoms. To exclude these effects, we performed ballistic characteristic features. During initial growth, a broad intensity
simulations of the entire transport process, from the ejection of the Pd distribution is observed at q = 2.76 Å−1 (black line in Figure 2a),
atoms at the target, simulated by SRIM,32 to their deposition on the indicating the formation of an amorphous or nanocrystalline (in
sample, using SIMTRA33 and TRIDYN34 (not shown here). The the following called “amorphous”) layer. At the Pd deposition
simulations confirmed that under the here used sputter conditions time t = tc ≈ 80 s (1.6 nm Pd), the broad peak suddenly
substrate heating and ballistic contributions to intermixing at the decreases. Simultaneously, narrow Pd2Si(111) and Pd2Si(201)
interface can be neglected. For the here discussed samples, the sputter
deposition process is dominated by surface and bulk diffusion peaks appear (Figure 2a, red line). For tc ≤ t ≤ 130 s, the intense
processes, similar to thermal evaporation and e-beam deposition. Pd2Si(111) Bragg peak reveals the dominant formation of Pd2Si
crystallites with [111] texture. A narrow size distribution of the
crystallites is confirmed by weak Kiessig fringes (Figure 1b, the
3. RESULTS inclined light-blue stripe marked by an arrow). The onset of
In the following, we will present real-time data measured during silicide crystallization, tc, is indicated by a dashed line in Figure 1.
sputter deposition of Pd on a-Si, complemented by post-growth During further Pd deposition, a Pd(111) peak appears in
RHEED and XPS measurements. between the silicide peaks (gray arrow). The intensity at the
3.1. Real-Time Observations during Sputter Deposi- Pd(111) position increases continuously up to t ≈ 300 s. Due to
tion. Figure 1 summarizes (a) the film force, (b) the XRD, and the peak overlap, it is very difficult to determine precisely the
(c) the XRR data measured simultaneously during deposition of onset of Pd growth. The line scan extracted at a slightly offset
Pd on a 9 nm thick a-Si buffer layer. The deposition time t = 0 s position, q = 3.1 Å−1, (Figure 2b, dashed green circle) shows first
corresponds to the onset of Pd deposition. The schematics show the reduction of the broad peak due to silicide crystallization,
the respective signal path (indicated by red arrows). During Pd then a clear intensity increase for t ≥ 100 s, indicating a change in
deposition, the characteristic features of all signals are highly structure formation already before t = 130 s. Possible
correlated and indicate significant structural changes. The explanations for this will be discussed in Section 3.4.
39317 DOI: 10.1021/acsami.9b11492
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For t ≤ 120 s, i.e., before the appearance of the significantly However, a steady-state regime is not observed with increasing
overlapping Pd(111) peak, the intensity distribution along q was film thickness, suggesting an evolving film microstructure, which

ÄÅ É2
yÑÑÑ
fitted by
ÅÅ i D
continuously alters the stress formation/relaxation processes.

I(q) = ∑ aiÅÅÅsincjjj (q − qi)zzzÑÑÑ e−(q − qi) σD

The real-time data indicate a competition between the silicide
ÅÇ k 2π {ÑÑÖ
i = 1,2 Å
2 2
formation at the interface and a Pd layer covering this interlayer.
For t ≳ 300 s, the XRD intensity saturates, whereas the XRR data
2a w clearly show that the Pd film is still growing. This can only be
+ 3 understood taking into account the texture formation during
π 4(q − q3)2 + w 2 (1) deposition, which is discussed in the following.
The first term describes the (111) and (201) silicide Bragg peaks 3.2. Texture Formation. The texture at different Pd
at the positions q1 and q2, using the same average crystallite size deposition times t was studied by post-growth XRD and
D and size distribution σD for both crystal orientations. The RHEED measurements. Figure 4a−c shows selected reciprocal
second term, a Lorentz peak at q3 with the width w, describes the space maps. Due to the measurement geometry, the reciprocal
broad intensity distribution observed during initial growth. space region around the surface normal (the qz axis) is not
Figure 3 shows D and σD (visualized as a gray region), plotted as accessible. The corresponding RHEED images (Figure 4e−g)
are presented in the right column. In agreement with the real-

Figure 3. Vertical size D of the silicide crystals, plotted as a function of

the nominal silicide thickness. For the fit, a size distribution (visualized
as a gray region) was taken into account. The red line corresponds to a
complete conversion of Pd into crystalline Pd2Si.

a function of the nominal silicide thickness, which is obtained by

converting the entire deposited Pd to Pd2Si. The error bar
indicates the fitting error of D. The fitting error of σD (not
shown) is below 0.1 nm for nominal thicknesses larger than 2.6
nm and increases up to 0.3 nm for lower values. Assuming bulk
densities, the formation of 1 nm Pd2Si requires 0.48 nm Si and
0.70 nm Pd. Up to the nominal Pd2Si thickness of 3.5 nm at t =
120 s (i.e., the entire plotted range), D is close to the red line
corresponding to a complete conversion of the deposited Pd to
crystalline silicide.
The silicide crystallization is accompanied by a sudden
increase of the force per unit width (Figure 1a). The tensile
stress observed for tc ≤ t ≲ 100 s increases up to 4.2 GPa and is
related to the volume reduction due to crystallization.28
However, already at t ≈ 100 s (2 nm Pd), the force per unit
width abruptly decreases and nearly the entire stress built up
during crystallization is relaxed. During further deposition, a low
compressive stress develops (−510 MPa at t = 350 s, −310 MPa
at t = 600 s), preceded by a characteristic and reproducible stress
change at t = 180 s (marked by a red circle).
The structural changes are also visible in the XRR signal.
Around t = 100 s, the oscillation period τ of the XRR signal
increases after two narrow oscillations from τ = 56 ± 3 s to τ = 79
± 2 s. These wider oscillations are related to the Pd growth. For t Figure 4. (a−c) XRD maps and (e−g) RHEED measurements for Pd
≳ 200 s, i.e., after the small stress feature, the oscillation deposition on a-Si with different deposition times. The red square in (e)
amplitude decreases continuously as expected for increasing corresponds to the XRD region. (d) and (h) show measurements of a
surface roughness. The Pd growth is accompanied by a slowly Pd film deposited on a Si substrate covered by native oxide. In (a) and
developing compressive stress (Figure 1a), which is typically (c), selected diffraction peaks of [111] textured Pd2Si (red dots) and Pd
observed for high-mobility polycrystalline metallic films.35 (white squares) are indicated.

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time measurements, all Bragg peaks can be attributed to [111]
textured Pd and Pd2Si. The calculated Bragg peak positions of
Pd2Si are indicated by red dots, and the Pd peaks are shown as
white squares (Figure 4a,c). Selected Pd2Si Bragg peaks are
labeled in Figure 4a. The labels in Figure 4c correspond to [111]
textured Pd. At t = 150 s (3 nm Pd), only Pd2Si peaks with a
mosaicity of 10° are observed (Figure 4a). The diffraction rings
are very narrow along q∥ but much broader along qz. This is
related to the anisotropic shape of the silicide crystallites.
Neglecting small strain effects, a disk shape with a diameter of
9.0 ± 1.0 nm and a height of 3.9 ± 0.3 nm was determined from
the peak width. At t = 225 s (4.5 nm Pd), additional Pd peaks can
be distinguished (Figure 4b). The Pd peaks replicate the
interlayer mosaicity, indicating an orientation relationship
between the Pd film and the Pd2Si interlayer. After t = 800 s
(16 nm Pd), however, the orientation distribution of the Pd layer
reduces to 3° mosaicity (Figure 4c). Note that the deposition of
800 s Pd on SiOx (Figure 4d) results in a much larger mosaicity
of 25°.
For t ≥ 225 s, the crystallization of Pd was also confirmed by
RHEED measurements. Examples are shown in Figure 4e−g.
The streaky RHEED images observed for t ≥ 225 s are quite
distinct from the typical transmission image of a textured film, as
found, e.g., for the Pd film on native oxide (Figure 4h). The
reason for this is the comparatively narrow texture, which is not
common for polycrystalline thin films. For t ≤ 180 s, however,
the RHEED intensity is very diffuse, and only one intensity ring
is visible. The Pd2Si formation, which is unequivocally proven by
XRD, is not detectable by RHEED.
The XRD and RHEED measurements show that the Pd
texture narrows during deposition. The real-time measurements
are performed at grazing incidence and cannot access the
angular region close to the surface normal. This explains why the
time-dependent XRD signal (Figure 1b) does not change
significantly for t > 300 s.
3.3. Simulation of the XRR Data. The real-time XRD data
suggest the following growth scenario: For t ≤ tc = 80 s, an
amorphous phase is formed. For t > tc, this phase is converted to
crystalline Pd2Si with [111] texture and continues to grow.
Above t ≈ 130 s, a [111] textured Pd layer is deposited. A
simplified fit model for the XRR data was developed, assuming a
sequential formation of Si, Pd2Si, and Pd layers with bulk
densities. The manually optimized layer model is summarized in
Figure 5, and the calculated XRR is shown as a red line in Figure
1c. For the here presented data, the deposition of a-Si and Pd is
described by constant deposition rates FPd = 0.0207 nm/s and
FSi = 0.032 nm/s. For t ≤ 127 s, the formation of Pd2Si is
described by a complete conversion of the deposited Pd to
Pd2Si, reducing the Si layer accordingly. The time-dependent
surface roughness σ is shown in Figure 5b. For t ≤ 210 s, the Pd
roughness is in the range 0.25 ± 0.05 nm. For t ≥ 210 s, however,
the roughness increases continuously up to 0.55 nm at t = 600 s.
The fitting error for the deposition rates is ±0.0005 nm; the
fitting error of the roughness values is ±0.05 nm.
Combining the XRR model and the real-time XRD data, we
propose that the initially forming amorphous phase has already a
composition close to stoichiometric Pd2Si.
3.4. XPS Study of the Pd/a-Si Interface. For a more
detailed picture of the interface formation, post-growth in situ
XPS measurements were done at different Pd deposition times.
To avoid changes induced by repeated growth interruptions,
each measurement was performed on a new sample.
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Figure 5. (a) Time-dependent layer thickness and (b) surface
roughness employed for the simulation of the real-time XRR data
during deposition of Pd/a-Si.
Figure 6a shows exemplary measurements of the Pd 3d5/2
photoelectron peak. For t ≤ 120 s, the binding energy 336.6 ±
0.1 eV is characteristic for the Pd−Si bonds in Pd2Si36,37 and is
attributed to a Si 3p−Pd 4d hybridization.38 For increasing
deposition time, the Pd 3d5/2 peak shifts to lower binding
energies, and at t = 360 s, Pd is in a metallic phase, indicated by
an asymmetric line profile with the maximum intensity at 335.0
± 0.1 eV.36,39 In between, the Pd 3d5/2 peak shape and position
(Figure 6b, black dots, left scale) change continuously, and the
peak becomes slightly broader. The gray background in Figure
6b,c indicates regions with dominant covalent or metallic bonds,
respectively.
Figure 7 shows the Si 2p XPS peak as a function of the Pd
deposition time. For t = 40 s, the most intense peak is observed.
The peak intensity decreases with increasing deposition time.
Excluding t = 40 s (1.1 nm Pd2Si) where the signal is dominated
by the a-Si contribution, Si 2p is found at 99.8 ± 0.1 eV, which is
in agreement with the Pd−Si bond formation.36
A peak shift with increasing Pd deposition time was also found
for the Pd MVV Auger signal, which has a higher surface
sensitivity. The position of the main peak is plotted in Figure 6b
(red stars, right scale). The strongest changes of the XPS and
AES peak position occur in the regions 120−150 and 200−260
s, respectively. As a guide to the eye, the nominal composition
(assuming a homogeneous material distribution) is shown in
Figure 6c. The composition was determined from high-
resolution scans of the Pd 3d5/2 and Si 1s peaks, excluding a
small Si−O contribution of less than 2 %. At t = 40 s, the nominal
composition is still dominated by the a-Si buffer layer. For 100 ≤
t ≤ 200 s, the slightly increasing nominal composition is close to
Pd2Si. The increase of the Pd content accelerates for t ≥ 200 s
and saturates after t ≈ 360 s at ≈100% Pd.
The XPS and AES peak shifts for Pd on a-Si are in agreement
with results reported for Pd evaporation on crystalline Si(100)
and Si(111) surfaces.16,36,40 As already observed by Grunthaner
et al., the XPS peaks cannot be reproduced by a simple
superposition of Pd−Pd and Pd−Si reference peaks. The peak
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Figure 6. Results of X-ray electron spectroscopy measurements. (a)
Selected Pd 3d5/2 photoelectron peaks after subtraction of a Shirley
background. (b) Position of the Pd 3d5/2 XPS peak and the main MVV
Auger peak as a function of the Pd deposition time. For the XPS peak,
the binding energy is plotted and for the AES peak the kinetic energy.
The composition (assuming homogeneous material distribution) is
shown in (c). The red line indicates the composition of stoichiometric
Pd2Si. The XPS data were fitted with a two component model. The two
components were attributed to Pd−Pd and Pd−Si. The corresponding
peak positions are shown in (b) and the Pd−Pd fraction in (c).
Figure 7. Si 2p XPS peak as a function of the Pd deposition time. The
dashed lines indicate the two observed peak positions.
shift was attributed to a chemical gradient. However, ab initio
calculations show similar peak shifts for elemental metal/metal
interfaces, affecting a thickness range of ±5−6 monolayers
around the interface. Assuming intermixing, this region is further
broadened.41 Taking into account possible peak shifts, the data
were fitted assuming a Shirley background and two peaks
corresponding to the Pd−Pd and the Pd−Si bond. The peak
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shape was fixed using a Gaussian/Lorentzian product form for
Pd−Si and an asymmetric variation of this function for Pd−Pd.
The width of both components was limited to the range 1.2−
1.25 eV estimated from the Pd−Si peak at t < 130 s and the Pd−
Pd peak for t = 360 s. Examples for the peak fit are shown in
Figure 8. The fitted peak positions and the Pd−Pd fraction are
Figure 8. Two-component fit of the Pd 3d5/2 photoelectron peaks
shown in Figure 6a. The data are shown as dots, the Pd−Si component
as a thick blue line, the Pd−Pd component as a thin blue line, the
background as a black line, and the fit result as a red line. The dashed
lines indicate the peak positions at the Pd deposition times 120 and 360
s.
plotted in Figure 6b,c (blue symbols). The core-level peak shift
of both peaks is ≈0.7 eV, which is similar to the interface-
induced peak shifts observed for elemental metals.41
The XRD signal suggests structural changes already for 100 < t
< 130 s (Figure 2b, green circle), but the XPS and AES signals
exclude the formation of a stable Pd layer for t < 120 s. A likely
explanation is the surface nucleation of less ordered Pd2Si
crystallites in addition to the continued growth of the [111]
oriented Pd2Si crystals. Alternatively, the formation of transient
Pd clusters might occur, which is not anymore detectable by
post-growth measurements. For 130 ≤ t ≤ 200 s (1.5 nm or 6.5
monolayers of fcc Pd), two shifted components are required to
fit the XPS peak. For t > 200 s, the Pd−Pd component moves to
the position expected for bulk Pd and increases with film
thickness. This is in agreement with the formation of a sharp or
slightly intermixed Pd/Pd2Si interface at t ≈ 130 s, followed by
six monolayers Pd where the electronic state is still influenced by
the interface. For t ≥ 200 s, an increasing layer of unperturbed
metallic Pd grows.
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4. DISCUSSION
4.1. Structure Formation Mechanisms and Stress
Development. The relation between structural development
and stress evolution is summarized in Figure 9. Combining real-
Figure 9. Schematic of the structural development during Pd
deposition on a-Si, visualizing the relation between structure and stress
buildup. Before crystallization, the diffusion through the amorphous
silicide is dominant; after crystallization, the silicide formation is
controlled by grain boundary diffusion (indicated by arrows).
time and post-growth studies of the Pd/a-Si interface, we found
that for t < tc ≈ 80 s, the deposited Pd is instantly converted to
amorphous Pd2Si [Figure 9(1)]. At tc, the amorphous layer with
a nominal thickness of d(Pd2Si) = 2.3 nm begins to crystallize
[Figure 9(2)]. The volume reduction due to crystallization
results in a sudden tensile stress, building up during tc ≤ t ≤ 100
s. At t ≈ 100 s, the entire silicide film is crystallized [Figure
9(3)]. The [111] oriented Pd2Si crystallites continue to grow up
to d(Pd2Si) ≈ 3.7 nm at t ≈ 130 s, accompanied by the
nucleation of randomly oriented Pd2Si crystallites and/or
transient Pd clusters. Simultaneously, the tensile stress is
released [Figure 9(4)]. For t ≳ 130 s, the Pd growth dominates.
The Pd/Pd2Si interface is formed, and at t ≈ 200 s, a
homogeneous [111] textured Pd layer covers the surface. The
subsequent Pd growth is accompanied by the development of
compressive stress (∼−310 MPa) [Figure 9(5)]. During silicide
growth and Pd/Pd2Si interface formation, the surface roughness
is very low, comparable to the a-Si buffer layer. During further
deposition, the roughness of the Pd layer increases and the
texture narrows.
It is well known that the grain boundary diffusion plays a
major role for the silicide formation during annealing.42 During
the early stages of thin film growth, however, these grain
boundaries do not yet exist. As long as the surface is only
partially covered by Pd2Si, the required material transport might
occur via surface diffusion. Once a continuous silicide layer is
formed [Figure 9(1)], Pd2Si growth can only proceed via Pd
and/or Si diffusion through a-Pd2Si. For t > 100 s, the entire
layer is crystallized and the grain boundary diffusion known from
annealing processes can take place [indicated by arrows in
Figure 9(4)]. The onset of metallic Pd formation indicates that
the material transport via grain boundaries is significantly
reduced compared to the transport through a-Pd2Si. The bulk
diffusion within c-Pd2Si is not expected to contribute to the
interlayer formation since it is even lower than the Pd2Si grain
boundary diffusion.42
A thickness-dependent crystallization at tc, accompanied by a
tensile stress buildup, was also observed during deposition of Mo
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on a-Si.28 For Mo, the bcc metal crystallizes, whereas for Pd,
significant intermixing occurs during deposition, favoring
crystallization of silicide. The tensile stress occurring during
crystallization of Mo is propagated via homoepitaxy into the
continuously growing metal film. For the deposition of Pd on a-
Si, the limited thickness of the silicide prevents the propagation
of tensile stress over larger thicknesses but does not explain the
complete relaxation directly after stress buildup. It is likely that
the grain boundary diffusion, which distinguishes the Mo/a-Si
and Pd/a-Si interface formation, facilitates the relaxation of the
tensile stress, which is maintained only by the contact area
between neighboring grains.
4.2. Relation between Interface Formation and Pd
Texture Evolution. Comparing the structure formation during
deposition of Pd on SiOx and Pd on a-Si, it is obvious that the
silicide formation at the interface is crucial for the texture
formation of the Pd layer. For both substrates, the [111]
orientation of Pd (i.e., the stacking direction of the close-packed
lattice planes) is favored. On native oxide, the weak interaction
with the substrate surface results in a nearly random orientation
distribution of the crystallites. On a-Si, the well-oriented Pd2Si
interlayer serves as a template for the Pd nuclei. This can be
imagined as a “head start” for the overgrowth process and
explains the surprisingly narrow orientation distribution of thick
Pd films deposited on a-Si.
The question that remains is why Pd2Si improves the texture
of the Pd film. Figure 10 compares the atomic ordering of
Figure 10. Epitaxial relationship between Pd2Si(111) and Pd(111).
The atomic positions of Pd2Si(111) are represented by balls, and the
crossing points of the black lines correspond to the atomic positions of
Pd(111). The green triangles indicate tetrahedrons formed by three Pd
and a central Si atom.
Pd2Si(111) and Pd(111). The [11̅0] directions of both lattices
are aligned. The lattice spacing of Pd(11̅1) is slightly larger,
resulting in a misfit of 2.2%. In the orthogonal direction, the
Pd2Si(111̅) and Pd(112̅) lattice planes are nearly parallel and
have a projected mismatch of −0.8%. Several authors report
[001] textured Pd 2Si after annealing of Pd/a-Si layer
systems.14,15 Compared to Pd2Si(001)/Pd(111), where an
isotropic lattice mismatch of 2.2% is found, the strain energy of
Pd2Si(111)/Pd(111) is slightly lower. This explains why in our
case the [111] texture of Pd2Si is favored.
The silicide texture can be explained by its small lattice
mismatch with Pd(111), but experimentally, Pd was detected
only after silicide crystallization. This might be due to the fast
reaction of the deposited Pd but might also be related to the
detection limit of the here used measurement techniques. A
DOI: 10.1021/acsami.9b11492
ACS Appl. Mater. Interfaces 2019, 11, 39315−39323
ACS Applied Materials & Interfaces
surface-induced crystallization, triggered by transient Pd
clusters, would be in agreement with the comparatively narrow
Pd2Si texture. A candidate for the nucleation sites might be
triangular Pd clusters. As shown in Figure 10, these clusters are
subunits of the close-packed Pd(111) layers evidenced during
later deposition. With a much lower density, they also occur in
the Pd2Si(111) plane (green triangles). Buckley et al. already
suggested that these triangular configurations play an important
role for the epitaxial growth of Pd2Si(001) on Si(111).4
4.3. Crystalline versus Amorphous Si Surfaces. The
deposition of Pd on a-Si and c-Si [referring mainly to the well-
studied Si(111) and Si(100) surfaces] shows many similarities:
in both cases, Pd reacts instantly with the Si surface atoms,
reducing thus the thickness of the underlying silicon layer.16,20
Independent of the substrate crystallinity, the minimum
thickness of the resulting silicide interlayer is around 3−5
nm,6,16,18,25 and XPS/AES measurements confirm that the
electronic environment at the Pd/c-Si16,36 and Pd/a-Si
interfaces is similar.
For Pd on a-Si, the crystallization of Pd2Si occurs at a critical
thickness. The crystallization of Pd2Si at the Pd/c-Si interface,
however, is less well understood. STM measurements on these
layer systems, with up to 8 ML deposited Pd, indicate the
formation of amorphous silicide.19,21,43 This is in agreement
with the initial growth of Pd on a-Si. Epitaxial silicide was found
after deposition of thicker Pd layers on c-Si4,6 but also during
real-time XRD measurements of Pd/Si(111): a relaxed silicide
peak appeared after deposition of 1.6 nm Pd.20,44 The structural
transition observed for Pd/Si(111) occurs at the same critical
thickness as the here observed amorphous/crystalline tran-
sition.44 The transition was explained with the relaxation of
epitaxially strained silicide. However, in the case of a-Si surfaces,
the transition cannot be driven by relaxation of an epitaxial strain
between film and substrate. The similar observations for Pd/c-Si
and Pd/a-Si interface formation suggest a general structure
formation mechanism, independent of the crystalline order of
the substrate. For a similar system, Ni deposited on Si(111), the
commensurate structure forming during initial deposition was
explained by long-range ordered interfacial silicide with large
atomic displacements with respect to the lattice positions,
covered by an amorphous silicide layer.45 Such a displacement
structure can be seen as an intermediate state between
amorphous and perfectly crystalline phase. Assuming a similar
growth model for Pd on c-Si, it is likely that in both cases the
structural transition at a critical thickness is mainly driven by the
disorder/order transition and the relaxation of epitaxial strain is
only a secondary effect.
5. SUMMARY AND CONCLUSIONS
We have shown that detailed information about complex growth
processes on the nanoscale is directly accessible for non-ideal,
comparatively weakly scattering polycrystalline layer systems.
Combining real-time XRD, XRR, and optical stress measure-
ments with in situ RHEED and XPS, the reactive interface
formation during deposition of Pd on a-Si was studied. It was
found that [111] textured Pd2Si crystallizes at a critical thickness
of 2.3 nm and continues to grow up to ≈3.7 nm, followed by Pd
formation with a surprisingly narrow [111] texture. The
structure formation on a-Si and c-Si is very similar, indicating
that the disorder/order transition is the driving force for the
formation of a crystalline interlayer.
The crystallization at a critical thickness seems to be a
fundamental aspect of metal/a-Si interface formation. The
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mobility and reactivity of the deposited metal atoms determine
the crystallizing phase (metal or silicide) and controls thus the
structure formation during further metal deposition. This is
crucial for the stress buildup during deposition: if the metal
phase crystallizes, the tensile strain due to crystallization of the
initially deposited amorphous phase can propagate to the
subsequently deposited metal layer via coherent crystal growth.
The crystalline silicide layer, however, grows via grain boundary
diffusion, facilitating the relaxation of the tensile stress. The
detailed understanding of these structure formation mechanisms
during deposition is essential for the miniaturization of silicide
interconnects and offers new paths for controlling the texture of
metal thin films.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: baerbel.krause@kit.edu.
ORCID
Bärbel Krause: 0000-0001-6288-0283
Dirk Hauschild: 0000-0001-9088-8944
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank the synchrotron radiation source SOLEIL for the
provision of beamtime within the standard proposal 20170440
and acknowledge the support of the synchrotron staff. We are
especially grateful for the technical support at the SIXS beamline
by Benjamin Voisin. For the technical assistance during
preparation of the synchrotron experiment we thank Annette
Weißhardt, Tobias Hilverling, and Andreas Breitenstein.
Furthermore, we acknowledge the general support provided
by the staff of the KIT institutes IBPT and IPS.
■
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