Thin Solid Films 673 (2019) 104–111

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Thin Solid Films

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Yttrium ultra-thin films on the Si(100)2 × 1 surface and their in situ T

oxidation process
⁎
D. Vlachos , M. Kamaratos
Department of Physics, University of Ioannina, PO Box 1186, GR-451 10 Ioannina, Epirus, Greece

A R T I C LE I N FO A B S T R A C T

Keywords: Yyttrium ultra-thin films (coverage < 4 ML) and their interaction with oxygen on the Si(100)2 × 1 surface have
Yttrium been investigated in situ by Auger electron spectroscopy, low energy electron diffraction, thermal desorption
Silicon spectroscopy, and relative work function measurements. The results show that yttrium develops in amorphous
Oxygen successive layers, interacting strongly with silicon at the interface, causing an early surface YeSi intermixing and
Silica
disruption of the silicon 2 × 1 symmetry. Yttrium increases drastically the oxygen sticking coefficient on silicon
Yttrium silicate
Auger electron spectroscopy
surface. It is surprising that even residual oxygen on the yttrium covered surface, induces a partial oxidation of
Work function silicon even at room temperature. By providing more oxygen, an Y-silicate compound (Y-O-Si) develops si-
Thermal desorption spectroscopy multaneously with silica (SiO2) in a competitive way to each other. The silicate is thermally promoted by post-
annealing process, probably due to the enhanced yttrium-silicon intermixing and/or inter-diffusion. Both of the
silica and silicate are thermally stable compounds, which dissociate and desorb from the surface only at high
temperatures (> 1100 K). Desorbing species such as Y2Si and SiO were recorded and attributed to the cracking
of silicate and silica respectively. A significant amount of yttrium always remains and/or diffuses into the silicon
substrate, even after strong annealing. Such a procedure caused the appearance of a newly observed 3 × 1 phase
corresponding to submonolayer yttrium coverage.

1. Introduction
Adsorption of rare earth metals (REM) on silicon substrates is a vital
topic, since it leads to the formation of interfaces with important ap-
plications especially in the microelectronics technology. REM on silicon
surfaces mostly form silicides of the type MSi2−x, (where M is the
metal), which exhibit significantly low Schottky barrier, a very desir-
able property for developing source-drain contacts in MOSFETs [1,2]
and infrared detectors. Among REM, yttrium is established as a good
candidate for producing a low Schottky barrier height (0.5–0.3 eV) on
n-type silicon substrates [3,4]. In addition, the relatively low electrical
resistivity of the developed yttrium silicides (YSi2−x), is crucial for low
parasitic resistance requirements of MOS devices [5,6]. Another es-
sential parameter for efficient performance of microelectronic devices,
is the good re-epitaxy of Si on the yttrium silicide surface, owing to the
excellent lattice match between YSi2-x and the Si(111) surface [6–8].
Regarding the yttrium silicide formation, YeSi interaction seems to
depend on the substrate symmetry, since the Si(111) plane requires
about 100 °C higher temperature than the Si(100) to form yttrium si-
licide [9].
Although the Si(111) surface shows supreme compatibility for
epitaxial yttrium silicide development, the Si(100) surface is more at-
tractive from a practical point of view. Therefore, it is necessary to
obtain a detailed insight of yttrium development on the Si(100)
2 × 1 surface. Previous studies by x-ray photoemission measurements,
showed that depending on coverage, a three-step mechanism of YeSi
interaction takes place on the surface [10,11]. Specifically, at low
coverage (< 2 ML), an ionic bonding occurs, while from 2 to 5 ML, Si
diffuses into the Y overlayer making the interface unstable. Finally, for
coverage > 5 ML the adsorbate becomes metallic. The Si diffusion into
the Y overlayer at relatively low annealing temperatures (< 300 °C),
has been also confirmed by Chiam et al. [12]. Concerning the YeSi
interaction, Huang et al. [3] demonstrated that YSi2−x silicide is formed
on the Si(100)2 × 1 surface after rapid annealing at 350 °C and remains
stable up to 950 °C.
An additional significant issue concerning the utility of the Y/Si
interface, is the interaction of yttrium with oxygen on the silicon sur-
face. This seems to be a complex interaction leading to the formation,
not only of yttria (Y2O3) [13–15] but also of Y-silicate (Y-O-Si) [14–21],
yttrium silicide (YSi2) [22,23], and silicon oxide, SiOx
[15,17,18,19,23,24,25,26,27]. Regarding the yttria-silicon interface, a
technological interest has been shown, because yttria among other

⁎
Corresponding author.
E-mail address: dvlachos@cc.uoi.gr (D. Vlachos).

https://doi.org/10.1016/j.tsf.2019.01.041
Received 27 July 2018; Received in revised form 21 December 2018; Accepted 18 January 2019
Available online 23 January 2019
0040-6090/ © 2019 Published by Elsevier B.V.
D. Vlachos, M. Kamaratos
high-k oxides, has been considered for years as a candidate for replacing
SiO2 as a gate material in the nanoscaled integrated circuits [28,29].
Although nowadays the research has designated HfO2 as the superior
gate oxide material [30–32], there is still scientific and practical in-
terest about Y2O3, since this oxide has shown excellent electrical per-
formance for applications in carbon based electronics [33,34]. The
reasons why yttria is a good candidate for a gate dielectric material are
mainly: a) the high-k value (13–18) [26,35–37], b) the thermodynamic
stability [38,39], c) the relatively high conduction band offset [40,41],
and d) the small lattice mismatch (~2.4%) with silicon, since the unit
cell of cubic Y2O3, 10.60 Å, is very close to the double unit cell of Si
(100), 10.86 Å [42]. The formation, however, of high quality sharp
yttria-silicon interfaces, requires our ability to control and minimize, or
even better to eliminate the interfacial silica [24,43], the Y-based sili-
cate or the silicide compounds. To succeed in this, we need to in-
vestigate the role of some growth parameters, such as the annealing
temperature and the oxygen exposure during the oxidation process of
yttrium on the silicon surface. This is the aim of this work, which
consists of two parts: in the first part, we study the initial stages of the
yttrium‑silicon interface formation (coverage < 4 ML), and its thermal
stability. In the second part, we investigate the interaction between Y
and O, for different oxygen exposures on different yttrium coverages on
the Si(100)2 × 1 surface. This part is important, because the oxidation
of the yttrium overlayer on the silicon surface, apart from yttria, also
leads to the formation of Y based silicate compound, material equally
important to yttria, as a high-k insulating material [14]. In addition Y-
silicate is a very promising material for thermal barrier coatings, due to
the low thermal conductivity and the high temperature stability
[44,45]. The investigation took place in ultra-high vaccum (UHV)
conditions by Auger Electron Spectroscopy (AES), Low Energy Electron
Diffraction (LEED), Thermal Desorption Spectroscopy (TDS) and re-
lative Work Function measurements (WF).
2. Experimental
All the experiments were performed in a conventional UHV
chamber with a base pressure of the order of 10−8 Pa. The chamber is
equipped with a four grid LEED optics, a cylindrical mirror analyzer
(CMA) with energy resolution 0.3% for AES measurements, a quadru-
pole mass spectrometer (QMS) for gas analysis and TDS measurements,
and an electron gun for relative WF measurements. The chamber is also
equipped with an Ar+ ion sputtering system and heating facility for
sample cleaning. The AES measurements were recorded in the first
derivative mode and the intensities of the electron signals were mea-
sured from the peak to peak height (Ap-pH). The energy of the primary
electron beam for AES measurements was 2 keV. The relative WF
measurements were performed in the diode mode with the sample
acting as the anode and the electron gun as the cathode. The accuracy
of the WF change measurements is ± 0.02 eV. The TDS measurements
were carried out by performing a linear annealing of the substrate, with
a rate of ~15 K/s. The estimated uncertainty of the recorded tem-
perature in the TDS spectra is about ± 20 K.
Yttrium was evaporated from a well degassed homemade evapora-
tion source, which consists of a resistively heated yttrium filament
1 mm in diameter. The evaporation rate was controlled by the current
through the yttrium wire, which during the deposition was kept con-
stant at 12.5 A. During deposition the source was 5 cm away from the
silicon substrate to ensure a homogeneous atomic flux. The filament
assembly was outgassed repeatedly until no significant oxygen or
carbon contamination was detected in the Y film, right after the de-
positions. The pressure in the chamber during depositions did not rise
above 3 × 10−7 Pa, while the sample temperature was always kept
near room temperature (RT), unless otherwise specified. The Y dosing
on the silicon surface was measured by the deposition time, defining 1
dose (1 D) equal to the corresponding deposited yttrium quantity in
0.5 min. As we further discuss below, the absolute Y coverage
105
Thin Solid Films 673 (2019) 104–111
corresponding to 1 D was estimated equal to 0.128 ML.
The substrate was a Si(100)2 × 1 sample with dimensions
(10 × 10 × 1) mm3, which was polished on one side. The sample was
mounted into a tantalum case with a Ta foil strip uniformly pressed
between the case and the sample. In that manner the rear side of the
sample was heated by passing current through the Ta foil strip. The
temperature was measured by a CreAl thermocouple, spot welded onto
the back side of the case and calibrated with an infrared pyrometer. The
silicon surface was cleaned by heating at 1200 K for several hours.
However, a very small amount of carbon contamination was always
detected by AES. The substrate was considered clean, when the carbon
C(273 eV) to Si(92 eV) Auger peak height ratio was < 5%.
Regarding the oxidation experiments, yttrium covered silicon sur-
faces were exposed in situ at ambient pressure of O2, by providing high
purity (99.998%) oxygen gas into the UHV chamber through a leak
valve. The oxygen exposure was measured in Langmuirs (L), where
1 L = 1.33 × 10−4 Pa × 1 s.
3. Results and discussion
3.1. Yttrium adsorption on the Si(100)2 × 1 surface
Our first step was to investigate the growth of yttrium on the silicon
surface mainly for reference purpose. Fig. 1 shows the Ap-pH intensity
of the Y(127 eV)MNN and Si(91 eV)LMM Auger electron transition lines
(AETL), as a function of the Y doses on the Si(100)2 × 1 at RT. As it is
seen, the intensity of the Y(127 eV) AETL increases linearly up to ~10
D. Above that dosage the same AETL increases linearly too, but with a
much lower rate, while above ~19 D the intensity almost levels off. In
this manner, the plot of the Y(127 eV) AETL intensity versus dosing of
Y, presents two clear breaks at ~10 and ~19 D respectively. However,
examining carefully the plot, a weak break can be distinguished at ~5
D. Such kind of weak breaks has been previously observed for growth of
metallic adsorbates such as Cs [46,47] and Ba [48] on the Si(100)2 × 1
surface, and are known as pre-monolayer breaks (p-ML), since they
occur before the completion of the first monolayer (ML). Most likely the
p-ML breaks are related to selective adsorption sites and the surface
atomic symmetry of the substrate. Such kind of breaks may also be
related to changes in the sticking probability, often occurring during
the very early stages of adsorption [49]. In general, the appearance of
successive breaks in the plots of the AETL intensity versus coverage,
Coverage (ML)
0 0.64 1.28 1.92 2.56 3.20 3.84
120
Y/Si(100)2x1) Si (91 eV)
100 Y (127 eV)x2
A p-p H (arb. units)
80
60 p-ML
40
20
0
0 5 10 15 20 25 30
Y doses
Fig. 1. The Ap-pH of the Y(127 eV)MNN and Si(91 eV)LMM Auger electron
transition lines, as a function of the yttrium coverage on the Si(100)2 × 1
surface at RT.
D. Vlachos, M. Kamaratos
indicates a layer by layer growth (Frank van der Merwe mode, FM)
[49]. Therefore, it is reasonable to attribute the break at 10 D to the
first Y physical layer completion, while that at 19 D to the second one.
Based on the Si(100) surface atomic density, we define 1 ML of Y equal
to 6.80 × 1014 atoms/cm2. Taking into consideration that metallic Y
with hcp structure presents a surface atomic density 8.68 × 1014 atoms/
cm2, we estimate the absolute coverage of the first Y layer equal to
about 1.28 ML. A coverage uncertainty of ~0.15 ML was estimated,
mainly due to the inaccuracy of defining the exact deposition time of
the first Y layer. From the above we conclude that 1 D of Y deposition
corresponds to ~0.128 ML coverage.
On the other hand, looking at the Si(91 eV) AETL versus coverage,
we observe an initial rapid decrease, while as the coverage approaches
the 1.28 ML, it almost levels off. Further dosing causes a second drastic
linear reduction and a break appears at ~2.56 ML. At higher coverages,
a new linear reduction of the Si(91 eV) AETL occurs, resulting in the
near disappearance of this line. Based on the usual AES analysis for the
FM mode, the intensity of the Si(91 eV) AETL shows a peculiar behavior
between 0.64 and 1.28 ML, because instead of presenting a linear de-
crease it nearly levels off (Fig. 1). Similar silicon Auger signal at-
tenuation has been recorded for Gd growth on Si(111)7 × 7 surface and
has been attributed to an early intermixed monolayer stage between the
atoms of adsorbate and substrate [50]. Likewise, we assign the slow
substrate signal attenuation (less than the exponential rate) to an sur-
face YeSi intermixing. According to that, a significant number of Si
atoms moves on average above the Y adatoms, reducing the masking
effect caused by yttrium, and thus giving higher Si(91 eV) AES signal
than that expected in the normal FM mode. This early surface YeSi
intermixing, and as the second half of the first Y layer is formed
(0.64–1.28 ML), likely induces the disruption of the silicon surface
symmetry. The latter is corroborated by LEED observations, where as
we describe later, the silicon symmetry 2 × 1 disappears at coverage
near to 1 ML. In addition, the start of the AES Si (91 eV) signal leveling
off, almost coincides with the p-ML break appearance, making possibly
the latter one a result of the YeSi intermixing. Another unusual ob-
servation concerning the silicon AETL behavior, is that it keeps on at-
tenuating even when the Y(127 eV) AETL has been saturated after the
second layer completion (~2.56 ML). The cause of that inconsistency
might be the significant residual amount of oxygen adsorbed on the
yttrium covered silicon surface. As we present in the second part of the
current work, Y increases dramatically the sticking coefficient of
oxygen, causing the partial oxidation of silicon even by residual oxygen.
We will discuss this issue later on.
In Fig. 2 we depict the work function change ΔΦ of the Si(100)2 × 1
surface versus yttrium coverage at RT. We observe a negative ΔΦ var-
iation as yttrium overlayer grows, which means that Y reduces the WF
of the surface. Considering that the WF of the clean Si(100) p-doped
surface equals to 4.9 eV [51], the WF of the surface drops to ~3.7 eV
after 1 ML of Y deposition. Then the WF decreases even more, down to
~3.4 eV at 2.3 ML, and finally seems to stabilize at ~3.2 eV after 3.2
ML of Y deposition. This value is near to the work function of the
polycrystalline metallic yttrium, equal to ~3.1 eV [52,53]. Pellissier
et al., by performing photoemission measurements recorded a devel-
oping Fermi level edge for coverages higher than 1 ML [54]. The initial
abrupt decrease of WF is consistent with the ionic character of Y during
chemisorption at low coverage [10], giving a strong dipole character in
YeSi bonding [11]. As Y coverage increases and the intermixing with Si
atoms takes place, the surface dipole moment may become less direc-
tional, causing a smaller WF decrease thus producing the first plateau,
which almost coincides with the leveling off of the Si(91 eV) AETL (see
Fig. 1). When the second layer formation starts, the newly adsorbed Y
atoms induce a second WF decrease, which in turn results in a second
plateau. The new WF reduction may be attributed to the electropositive
nature of Y adatoms relaxed on the YeSi mixed layer, while the new
plateau could be assigned to a Si diffusion through the Y overlayer. This
silicon atomic “outwards” diffusion has been previously documented
106
Thin Solid Films 673 (2019) 104–111
Fig. 2. The work function change ΔΦ of the Si(100)2 × 1 surface, versus yt-
trium coverage at RT.
[10–12,54]. The same scenario can be proposed for the third WF low-
ering and plateau respectively. Another reason for these plateaus for-
mation, might be the residual oxygen contamination caused by yttrium
due to the relatively long experimental time. Based on the above de-
scription, it seems reasonable to separate the WF reduction into three
areas (see Fig. 2). In all of these three areas, the WF initially drops
rather intensively, while as the coverage increases it levels off to a
constant value. Looking at the ΔΦ curve, we observe that the corre-
sponding WF decrease in each area, is smaller as the area number in-
creases. This might be due to the intensive three-dimensional Si diffu-
sion as the Y overlayer becomes thicker, which however maximizes and
finally ceases at higher coverages [54]. The Si diffusion through the Y
overlayer may be promoted by the presence of significant residual O on
surface as the AES measurements verified (not shown). The same con-
clusion has been reported by Chiam et al. [12]. As we will discuss
further below, this residual oxygen reacts with silicon by forming silica
even at RT. It is noteworthy, that the coverage ranges of the WF areas
are quite similar to those of the first and second layer completion, such
as those are defined by the AES measurements in Fig. 1. Similar WF
decrease with plateaus formation has been recorded by Pellissier et al.
[54], without giving however a clear explanation.
To investigate the thermal stability of the Y/Si(100) interface, we
annealed the substrate at several temperatures. Fig. 3 shows the in-
tensity of the Y(127 eV)MNN, Si (91 eV)LMM and O(510 eV)KLL AETL
of the Y(3.84 ML)/Si(100)2 × 1 surface versus the post-annealing
temperature. In all the cases, we annealed the sample at a certain
temperature for ~2 min annealing time, then we left the sample to cool
down near to RT, and finally we recorded the AES spectrum. Out of
Fig. 3, the intensities of all the AETLs remain almost constant up to
~450 K. Above this temperature, the Y(127 eV) line decreases slowly up
to 1100 K. In contrast, within the same temperature range, the Si(91 eV)
line significantly increases almost linearly. On the other hand, the O
(510 eV) line shows an almost stable intensity with fluctuations due to
the noisy signal. Stronger substrate annealing, from 1100 to 1350 K,
causes a substantial decrease of the Y(127 eV) AETL, and a corre-
sponding abrupt increase of the Si(91 eV) AETL. Within the same
temperature range, the O(510 eV) AETL drastically decreases and fi-
nally diminishes down to zero at 1350 K. It is noteworthy that a rela-
tively large amount of Y (estimated at about 0.45 ± 0.15 ML) remains
on the silicon surface, which could only be removed by ion sputtering.
This might be due to the extended inter-diffusion between Y and Si at
D. Vlachos, M. Kamaratos
Fig. 3. The Ap-pH of the Y(127 eV)MNN, Si(91 eV)LMM and O(510)KLL Auger
electron transition lines, as well as the work function change ΔΦ of the Y(3.84
ML)/Si(100)2 × 1 surface versus the post annealing temperature.
the interface, which is likely promoted by the post-annealing process
[12].
We also recorded the change of the WF, ΔΦ, versus annealing and
the results are shown in Fig. 3 too. The post-annealing of the Y(3.84
ML) overlayer causes a ΔΦ increase almost reverse to the ΔΦ decrease
during Y deposition at RT. Some plateaus or steps are forming in cor-
respondence to those presenting in Fig. 2. In general, the recorded Ap-
pHs and WF changes versus post-annealing, indicate that several kinetic
phenomena take place on surface, which might be rather complex due
to the oxygen presence.
In order to elucidate further the kinetics of Y on the silicon surface,
we performed TDS measurements. First we tried to detect desorbing Y
but the result was negative. Then we focused the QMS on the YSi and
the YSi2 compounds, but again we did not record any signal. Instead,
when we tried to detect Y2Si, a series of TDS spectra were recorded, as
they are shown in Fig. 4. A sharp symmetrical peak appears at about
1100 K, which steadily increases in intensity with Y coverage. This is an
indication that Y interacts strongly with Si forming a type of chemical
compound, probably silicide. In principle, the desorbing silicide should
Y/Si(100)2x1
Y2Si
QMS signal (arb. units)
Y coverage (ML)
2.56
19
12
0.6
550 800 1050 1300
Temperature (K)
Fig. 4. The TDS measurements for Y deposition on the Si(100)2 × 1 surface at
RT. The recorded Y2Si (206 amu) QMS signal is shown at different coverages.
Desorbing SiO (44 amu) was also recorded.
107
Thin Solid Films 673 (2019) 104–111
be detected by the AES measurements, recording a weaker Y(127 eV)
AETL. In Fig. 3, indeed, the Y(127 eV) signal shows a substantial de-
crease from 1100 to 1250 K, which can be correlated with the TDS
results.
To the best of our knowledge, the Y2Si silicide has not been reported
previously. The most often reported silicides are of YSi2-x type
[3,7–9,54]. An arising question is if the Y2Si silicide forms at RT or
during the annealing process. The present work can not give a clear
answer. Most of the related studies support that yttrium and other REM
silicides develop sufficiently after substrate annealing [3,5,7–9,55].
Thus the formation of Y2Si at RT is rather unexpected. In contrast,
substrate annealing promotes the YeSi intermixing making more likely
the formation of the Y2Si silicide, or even some polymorphs of yttrium
silicates such as Y2Si2O7 or Y2SiO5 [56]. In the latter cases the deso-
rbing Y2Si should be considered more likely as a cracking product.
Apart of Y2Si, as Fig. 4 shows, we recorded SiO too, at about 1350 K.
This observation in combination with AES measurements (see Fig. 6
below) additionally support a partial oxidation of silicon caused by the
oxygen contaminants. As we mentioned before, this substrate oxidation
may be related to the recording plateaus in the ΔΦ curve, shown in
Fig. 2.
We also performed LEED observations during Y deposition at RT.
Gradually a background increase of the Si(100)2 × 1 LEED pattern was
observed, while at the same time the diffraction spots became diffuse.
At about 1.28 ML coverage the silicon 2 × 1 LEED pattern disappeared.
As we noticed earlier, this can be ascribed to the surface symmetry
disruption due to the YeSi intermixing. When annealing of the Y(3.84
ML)/Si(100)2 × 1 surface took place, a new 3 × 1 pattern was ob-
served at ~1300 K, as it is shown in Fig. 5a. Substrate annealing at even
higher temperature of 1350 K, restores the silicon 2 × 1 symmetry. We
tried to interpret the 3 × 1 phase, by proposing the simplified atomic
model depicted in Fig. 5b. In that model, we ignore the existence of the
O contaminant atoms and assume a 1 × 1 unreconstructed silicon
surface, with the Y adatoms relaxed at four fold adsorption sites.
3.2. Oxygen adsorption on yttrium covered Si(100)2 × 1 surfaces
Once we characterized the Y/Si(100)2 × 1 surface, our next step
was to investigate the interaction of oxygen with that system.
Therefore, we exposed several Y covered silicon surfaces to oxygen
pressure (×10−5 Pa). The AES spectra during oxygen exposure of a
0.50 ML yttrium pre-covered silicon surface, are illustrated in Fig. 6.
The oxygen adsorption changes drastically the lineshape of the AES
curve, decreasing both the Si(91 eV) and Y(127 eV) AETLs. On the other
hand, two new AETLs appear, the first at ~78 eV attributed to the
oxidation of silicon, SiO2 [57–59], and the second one at ~124 eV to
the oxidation of Y. Although Campisi et al. [60] associated a similar
Auger line with Y2O3, the 124 eV AETL, probably is due more to an
yttrium silicate compound, Y-O-Si, than to the stoichiometric yttria.
Fig. 5. (a) The 3 × 1 LEED pattern taken with electron energy 62 eV after an-
nealing of the Y(3.84 ML)/Si(100)2 × 1 surface at ~1300 K. (b) The proposed
atomic model with the unreconstructed silicon surface (empty cycles), and the
yttrium adatoms relaxed on four fold sites (full cycles).
D. Vlachos, M. Kamaratos Thin Solid Films 673 (2019) 104–111

160
O/Y/Si(100)2x1
140 Y (0 ML)

O (510 eV) A p-p H (arb. units)

Y (0.10 ML)
120 Y (1.28 ML)
Y (2.56 ML)
100

80

60

40

20

0
0 5 10 15 20 25 30
Oxygen exposure (L)
Fig. 7. The Ap-pH of the O(510 eV) AETL as a function of the oxygen exposure
at different yttrium precovered Si(100)2 × 1 surfaces.

180

Fig. 6. The AES spectra for different oxygen exposures on the Y(0.50 ML)/Si 160 O(1.5L)
(100)2 × 1 surface at RT. O (510 eV) A p-p H (arb. units) O(3L)
140 O(5L)
O(10L)
This assumption is supported firstly by previous x-ray photoelectron 120 O(20L)
measurements [11,12,14,21], and secondly by enthalpy calculations,
100
O(30L)
which suggest a greater stability of silicate against yttria [61].
Thus, on the basis of the Auger lineshape results, we conclude that
80
the presence of Y on the silicon surface acts catalytically for the oxi-
dation of silicon at RT, while simultaneously an Y-silicate compound 60
develops. The oxidation of silicon happens not only at submonolayer
stage (0.50 ML), but also at much higher coverages, which occasionally 40
could correspond to more than one physical layers of Y (see for example
20
the silica peak for 2.80 ML coverage in Fig. 11 below). This observation
indicates that O atoms incorporate through the Y overlayer by oxidizing 0
silicon. Moreover, this abrupt silicon oxidation may be promoted by the 0,0 0,5 1,0 1,5 2,0 2,5 3,0
silicon inter-diffusion through the Y overlayer [10–12,54]. With addi-
tional oxygen exposure, the silica AETL further increases, while that of
Y coverage (ML)
silicon decreases. The more oxygen we provide on the surface, the Fig. 8. The Ap-pH of the O(510 eV) AETL as a function of Y coverage for certain
stronger silica and silicate AETL we get. At high oxygen exposure (30L) oxygen exposures.
both Si(91 eV) and Y(127 eV) AETL almost disappear. This is a strong
experimental indication that almost all the diffused silicon and that at In all the cases, the oxygen Auger signal increases almost linearly with
the YeSi interface, finally interacts with oxygen forming silica and Y coverage. In general, the slope of the line is analogous to the average
yttrium silicate. sticking coefficient of oxygen on the Y pre-covered silicon. Based on
It is quite intriguing that the 78 eV AETL appears without deliberate Fig. 8, we conclude that Y increases the sticking coefficient of oxygen
oxygen exposure and even without any annealing of the yttrium cov- on the surface, promoting the oxidation of silicon. The latter is sup-
ered silicon surface. This observation points out that residual oxygen ported by recording the variation of the SiO2 (78 eV) AETL, versus the
can partially oxidize the substrate even at RT. We consider this result oxygen exposure on several Y precovered Si(100)2 × 1 surfaces, as it is
quite important, since although it has been known for some time, that depicted in Fig. 9. The more predeposited Y on the surface, the more
alkalis such as Cs and Na can also catalytically act for the silicon oxi- intense the silica AETL, which means that the adsorbate enhances the
dation, this could happen only after deliberate oxygen exposure and formation of SiO2 even at RT. Τhe silica signal develops abruptly at
thermal post-annealing [62,63]. small exposures and finally almost saturates at about 5 to 10 L of
In order to investigate further the oxidation process at RT, we ex- oxygen, independently of the Y coverage.
posed several yttrium covered silicon surfaces in oxygen ambient It is also interesting to study how the yttrium silicate Auger peak
pressure. Fig. 7 shows the Ap-pH of the O(510 eV) AETL versus oxygen develops with the oxygen concentration on the surface. Fig. 10 shows
exposure for different Y covered Si (100)2 × 1 surfaces at RT. It is ob- the intensity of the Y-silicate (124 eV) AETL versus oxygen exposure at
vious that the presence of Y on silicon increases enormously the amount different Y pre-covered Si(100)2 × 1 surfaces. Again we note that, the
of the adsorbed oxygen. Indeed, the higher the Y coverage, the stronger more predeposited Y on the surface, the more intense the silicate Auger
the oxygen Auger peak. A similar behavior was observed for oxygen peak. In addition, the intensity of the peak increases drastically at re-
adsorption on cesium pre-covered Ar+ sputtered silicon surfaces [63]. latively low oxygen exposures (< 5 L) and saturates at higher ones (5 to
The proportionality between the oxygen adsorption and yttrium cov- 15 L). It is important to point out that silicate starts to develop even at
erage is better evident in Fig. 8, where the Ap-pH of the O(510 eV) submonolayer coverages, implying silicate formation at the interface. In
AETL is shown as a function of Y coverage for certain oxygen exposures. contrast, Chiam et al. [12], by investigating the ex situ oxidation of a

108
D. Vlachos, M. Kamaratos Thin Solid Films 673 (2019) 104–111

160
O(50L)/Y(2.80ML)/Si(100)2x1 RT
O/Y/Si(100)2x1
SiO2 (78 eV) A p-p H (arb. units)

140 800 K

120 1100 K

AES signal (arb. units)

100
1200 K
80 Y (0 ML)
Y (0.10 ML)
60 Y (0.50 ML) 1300 K
Y (1.28 ML) Y-Si-O
40 Y (2.56 ML)
SiO2 1350 K

20

0 Si Y
0 5 10 15 20 25 30
O2 exposure (L)
60 70 80 90 100 110 120 130 140
Fig. 9. The Ap-pH of the SiO2 (78 eV) AETL, versus the oxygen exposure on
several Y precovered Si(100)2 × 1 surfaces. Kinetic energy (eV)
Fig. 11. The AES spectra for O(50 L)/Y(2.80ML)/Si(100)2 × 1 surface after
160 annealing at several elevated temperatures.
Silicate (124 eV) Ap-pH (arb. units)

140
(few hours). Although in that case the silicate 124 eV peak was not so
strong, as such in the oxygenated surface (see Fig. 6), AES measure-
120
ments showed that the post-annealing process up to 1150 K promotes
100 the formation of the Y-silicate compound, probably due to the enhanced
YeSi interdiffusion [12,14]. This result is demonstrated in Fig. 12,
80 where both the silicate 124 eV and silica 78 eV AETL intensities are
shown versus the post-annealing temperature of a heavily oxygen
60 contaminated Y-covered silicon surface. In fact, we recorded almost
three times stronger yttrium silicate peak after annealing at ~ 1050 K
40
Y(0.25ML) compared to that recorded at RT. On the other hand, the silica 78 eV
Y(0.50ML) peak does not seem to be substantially intensified by the post-annealing
20
Y(2.80ML) process. Annealing at higher temperatures than 1150 K causes the
0 gradual decrease of both silica and silicate AES peaks, indicating the
0 5 10 15 20 25 30 onset of the dissociation of these compounds. In agreement, Wang et al.
O2 exposure (L) [16] showed a continual Y-silicate growth versus the post-annealing
temperature of an ultrathin yttrium epilayer on silica/Si(100) surface.
Fig. 10. The Ap-pH of the yttrium silicate (124 eV) AETL, versus the oxygen Finally, other studies report the coexistence of silica and Y-silicate at
exposure on several Y precovered Si(100)2 × 1 surfaces. the interface during yttrium oxide deposition on silicon [15,17].

thicker Y overlayer (2 nm), did not observe silicate compound at the Y/

Si interface. From Figs. 9 and 10, we observe a similar behavior of silica 120
and silicate AETLs, with both peaks developing simultaneously. In that
sense, it is concluded that in situ oxidation of ultra-thin yttrium films 100
Ap-pH (arb. units)

(coverage < 4 ML) at RT, both compounds of silica and silicate are
forming being mutually competitive. Similar results have been obtained 80
by an ex situ oxidation study of yttrium overlayers after annealing [14].
We also investigated the thermal stability of the developed com-
pounds on the surface. Therefore, by following the usual post annealing 60
process in this work (see the described process in section 3.1, Fig. 3), we
performed AES measurements. The AES spectra for the O(50 L)/Y 40
(2.80ML)/Si(100)2 × 1 surface after annealing at several temperatures
are shown in Fig. 11. Both silica and yttrium silicate (Y-O-Si) remain on
20
the surface even after strong annealing up to 1300 K. However, some SiO2(78eV)
part of silicate seems to dissociate or even desorb from the surface as Y/Si(100)2x1 Y-O-Si(124eV)
Y2Si. This deduction is supported by similar TDS results as those pre- 0
400 600 800 1000 1200 1400
sented in Fig. 4 (not shown). Silica also dissociates and desorbs from the
surface, as SiO at temperatures higher than 1300 K (see Figs. 4 and 11).
A similar desorption mechanism of silica was observed for oxygen ad-
Annealing temperature (K)
sorption on Cs-covered Si(111) surfaces [64]. Fig. 12. The Ap-pH of the silicate (124 eV) and the silica (78 eV) AETLs of a
It is noteworthy to mention that silicate traces were detected even heavily oxygen contaminated Y covered Si(100)2 × 1 surface versus the post-
with residual oxygen on the yttrium covered silicon due to waiting time annealing temperature.

109
D. Vlachos, M. Kamaratos
4. Conclusions
In this work, we investigated the growth of ultra-thin yttrium films
on the Si(100)2 × 1 surface, and their in situ interaction with oxygen.
The experiments were carried out by typical surface analytical techni-
ques such as AES, LEED, TDS, and relative WF measurements. Yttrium
develops in amorphous successive layers interacting strongly with si-
licon and disrupting the silicon surface symmetry as a result of a pre-
monolayer stage of intermixing. Yttrium increases drastically the
sticking coefficient of oxygen on silicon. This results in the partial
oxidation of the substrate at room temperature, even by residual
oxygen. Providing more oxygen on the yttrium covered silicon surfaces,
besides silica, an Y-silicate compound is also formed. Both silica and
silicate compounds seem to develop simultaneously at the YeSi inter-
face, in a competitive way to each other, being thermally stable up to
~1300 K. Post thermal annealing promotes the formation of Y-silicate,
probably because of the enhanced YeSi intermixing and/or inter-dif-
fusion. During such a procedure and at relatively high temperatures,
desorbing species of Y2Si and SiO were recorded and attributed to the
dissociation of silicate and silica, respectively. A significant amount of Y
always remained on the surface even after strong annealing, while a
new 3 × 1 phase was observed corresponding to submonolayer yttrium
coverage.
Acknowledgements
The authors wish to thank Dr. S.D. Foulias for the critical reading of
the manuscript. This research did not receive any specific grant from
funding agencies in the public, commercial, or not-for-profit sectors.
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