Evidence for Si diffusion through epitaxial NiSi2 grown on Si(111)

V. Hinkel, L. Sorba, H. Haak, K. Horn, and W. Braun

Citation: Applied Physics Letters 50, 1257 (1987); doi: 10.1063/1.97927
View online: http://dx.doi.org/10.1063/1.97927
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Evidence for 51 diffusion through epitaxial NiSi2 grown on 51(111)

v. Hinkel, L. Sorba, H. Haak, and K. Horn
Fritz-llaber-Institut der Max-Planck-Gesellschaft, D-IOOO Berlin 33, West Germany

W. Braun
BESSY GmBH, Lentzeallee 100, D-1000 Berlin 33, West Germany

(Received 15 December 1986; accepted for publication 2 March 1987)

Epitaxial nickel silicide films grown on Si( 111 )-(2X 1) surfaces have been studied by valence
and core level photoemission using synchrotron radiation. The different chemical binding
states of the nickel atoms were dearly identified in the valence-band spectra, and our data
demonstrate that NiSi 2 forms at lower temperatures than previously assumed. The growth of
these epitaxial layers is always accompanied by the outdiftusion of silicon atoms, which exhibit
an epitaxial arrangement on the silicide surface. By means of depth profiling using tunable
synchrotron radiation we were able to determine the thickness of the topmost silicon layer.

Epitaxial layers of transition metal silicides on silicon

surfaces are of great fundamental and practical interest,
since they provide a wen characterized model system for the
study of Schottky barrier heights and other properties of the
silicon-silicide interface. l-4 For the interaction of nickel with
silicon, Tung and co-workers have shown that continuous
and planar NiSi 2 single-crystal layers may be grown epitaxiallyon Si( 111) by evaporation and controlled annealing.
Using thi.n (5-10 A) template NiSi 2 layers on which subsequent nickel layers were evaporated, they were able to grow
rather thick layers of single domain (so-called B-type) orientation. 3 We have studied the valence and core level photoemission spectra of such layers at different stages of the
nickel-silicon reaction in order to identify the reaction products as a function of temperature.
The experiments were performed in an ultrahigh vacuum photoelectron spectrometer (VG Scientific, ADES 400)
at the electron storage ring BESSY using synchrotron radiation from beamHnes TGM 2 and TGM 3. Clean SiC 111)(2 Xl) surfaces were prepared by cleaving at a base pressure
of 6 X 10 11 mbar. Nickel films were evaporated from a liquid nitrogen cooled tungsten wire evaporator. Their thickness was measured by a quartz microbalance (VEECO
Inc.). During evaporation the pressure never rose above
2 X 10 - 10 mbar. In this letter, we only report on those silicide layers that were prepared as B-type layers according to
the recipe of Tung et al. 3
The chemical reaction of nickel with 8i may result in the
formation of the nickel-rich Ni2 Si, the monosilicide NiSi, or
the disilicide NiSi 2 These compounds give rise to different
valence-band photoelectron spectra as demonstrated by
Franciosi et al. 5 and Shiraki et 01. 6 The spectra are dominated by a peak located at 1.3, 1.8, or 3.2 cV, respectively. This
peak is related to Ni d-derived nonbonding orbitals as
shown by the calculations of Sis! and Calandra. 7 Thus, on
the basi.s of the valence-band spectra, recorded in normal
emission at a photon energy of 120 eV with an overall resolution of about 0.65 eV, we were able to distinguish between
the different phases. The top spectrum in Fig. 1 shows a 20-A
nickel layer evaporated at room temperature, which shows a
Ni d peak close to E F , indicative of a metallic Ni overIayer.
The situation is markedly different in the second spectrum
which was taken from a 1O-A Ni layer at room temperature.

Here, the peak occurs at 1.8 e V below E F. This shows that in

the latter layer, a room-temperature reaction has already
taken place. Upon annealing of this layer to 120C for 5 min,
a shoulder occurs at 3.2 eV binding energy. This shoulder
peak completely dominates the spectrum upon further annealing to 250 DC as evident from Fig. 1, whereas the low
binding energy peak is almost completely suppressed. Final-

Valence level photoelectron spectre. 5; (111) Ni

flt.!= 120eV

,,
:/,1
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,

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Er.ergy relctive to EF (eVl

FIG, 1. Valence-band photoelectron spectra of nickel Jayers evaporated

onto Si ( 111) surfaces cleaved in UHV, under the conditions as indicated ill
the figure. Spectra were recorded at 120 eV photon energy in nonnal emission. The traces in the bottom show the valence spectrum of bulk NiSiz
from Ref. 5 and the calculated density of states for this phase from Ref. 7,

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ly, upon annealing to 520C, only the peak at 3<2 eV binding

energy remains, which we attribute to the NiSi 2 phase by
comparison with previous work. 5,7
From the position of the main valence-band peak we
conclude that room-temperature reaction results in the formation of mainly NiSi. This is also true for the thinner layers,
and is in agreement with the findings of Grunthaner et al,8
for this system. It is in disagreement with the work of van
Loenen et at. who found evidence for Ni z Si formation in
such layers,9 and with the extended x-ray absorption fine
structure data of Comin et al.1O who report room-temperature formation of NiSi 2 The spectra further show that the
major part of the layer has reacted to Ni5i z already at a
temperature of 250C, much lower than values given in previous studies. 3 ,4 Since we observe a time-dependent increase
of the peak due to NiSi2 it is likely that, given a long enough
time for diffusion to take place, a complete reaction even at
220C would have been observed. After the final anneal, we
observed a sharp (1 Xl) low-energy electron diffraction
(LEED) pattern.
The variations in the valence spectrum may be compared with concomitant changes in the Si 2p core level spectrum as a function of deposi.tion and annealing. These are
shown in Fig. 2, recorded also at a photon energy of 120 eV,
but with a resolution (electrons plus photons) of about 0.35
e V. The top trace shows the spectrum of a cleaved 5i ( III )(2 X 1) surface. Upon room-temperature reaction, the region between the spin-orbit split peaks is filled; some intensity increase also occurs on the high binding energy side of the
peak. From difference spectra we conclude that a new set of
peaks exists which is shifted by 0.3 eV with respect to the

Si 2p

core level SI !111J 10 A Ni

liw.120eV

:1

.....

~oo

..r-i".

_.J

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: <\

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1

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heated to

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101

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99

98

Binding energy (eVJ

FIG. 2. Si 2p core level photoelectron spectra for a lOA nickel layer on

Si ( 111 ) with experimental conditions as indicated in the figure. The bottom
spectrum also shows the results of a Lorentzian fit with Gaussian broadening representing the instrumental resolution.

original Si 2p position, in agreement with chemical shift data

for NiSi by Franciosi et al., 5 supporting our conclusion from
the valence-band spectra< After annealing to 120C, there is
an increase in the intensity of the shifted component, caused
by further reaction to NiSi. The spectrum after annealing to
250C which, according to the valence level results, should
be due essentially to NiSi z , now clearly demonstrates the
existence of a different phase present on the surface. The
three-peak spectrum is composed of two spin-orbit split
Si 2p contributions, shifted relative to each other by about
0.55 eV. The decomposition of the experimental spectrum
into different constituents was obtained from a curve-fitting
procedure shown in the bottom spectrum, which was based
on Lorentzian lines broadened by a Gaussian representing
the instrumental resolution. Since the position of the leading
peak corresponds to that of the clean Si surface, we attribute
it to silicon atoms in a chemical environment as in a silicon
crystal, and will call it the "dean Si" peak The second doublet then corresponds to Si atoms in the NiSi z phase. Annealing to 520C leads to an increase in intensity of the
"clean Si" peak as shown by the bottom spectrum.
The appearance of a core level emission due to Si atoms
il1 a chemical environment corresponding to that in a Si crystal is puzzling, since the valence level spectrum indicates
that NiSiz has been formed at this stage. However, the valence level spectmm ofSi is about a factor of 20 weaker than
the d-derived peaks in the NiSi 2 spectrum, and valence photoemission from one or two monolayer equivalents or a silicon phase is difficult to detect when superimposed on the
strong silicide emission. In spectra recorded at higher annealing temperatures or longer annealing times, however,
the clean 5i valence-band features become apparent. A 10 A
layer of Ni metal leads to a 36-A-thick NiSiz layer. At an
escape depth of about 7 A for the Si 2p electrons under the
experimental conditions of the spectra shown in Fig. 2, observation of direct emission from the underlying Si substrate
is impossible unless the NiSi 2 grows in islands which would
leave certain parts of the Si surface in its original state, or
unless the thickness of the silicide layer varies greatly. Another possibility is the formation of Si clusters in the silicide
phase. On the basis of previous work on the morphology of
the epitaxial silicide layers 3 <9 both explanations seem unlikeAy. We also observe that the leading Si peak grows with higher annealing temperatures and longer periods. This behavior
is incompatible with the above explanations.
In order to test a third possibility of a mechanism which
gives rise to the clean Si signal, namely, the growth of an
epitaxial layer of pure silicon on top of the silicide phase, we
have performed two different experiments. When higher
electron take-off angles are used, the photoemission signal
originating from a surface layer should be enhanced when
compared with the corresponding bulk signal since a larger
part of the electron escape depth occurs in the overlayer. In
our spectra recorded at 60 electron take-off angle with respect to the surface normal, the dean Si component was
markedly increased, indicating that the crystalline S1-like
species resided in the top layer.
We have also used the tunability of synchrotron radiation in order to carry out a "nondestructive depth profil-

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iug." This is based on the fact that the escape depth of photoelectrons strongly depends on their kinetic energy. Thus,
with the Si 2p level at 99.5 eV binding energy, the escape
depth is only about 4.5 A at 130 eV photon energy, but more
than three times that value at a photon energy of 110 eV. I I
Photoemission from a surface species wiII therefore be
strongly attenuated when the photon energy is lowered from
130 to 110 eV. The corresponding spectra from a B-type
layer produced by evaporation of 12.5 A Nt are shown in
Fig. 3. It is obvious that the leading dean Si peak is strongly
attenuated relative to the silicide peak in the bulk-sensitive
spectrum at 110 eV photon energy. These findings are incompatible with the existence ofNiSi z islands and patches of
the bare SiC 111) surface. Since we observe a sharp (1 Xl)
LEED pattern after annealing above 250C, we conclude
that an epitaxial array of Si is formed on top of the NiSi 2
layer. Using a continuum moder1-14 for layer thicknesses we
are able to evaluate the thickness of the clean 8i overlayer. If
we use an electron escape depth of 4.5 A for a photon energy
of 130 eV, we derive a layer thickness of3-5 A, depending on
the preparation conditions. 15 This evaluation also allowed us
to determine independently the relative escape depths at different photon energies. 15
We propose the following mechanism for the formation
of such ordered Si "cap" layers, In the initial stages of silicide
formation, strong intermixing between Ni and Si atoms occurs along with the initial room-temperature reaction, as
shown by the medium energy ion scattering results of van
Loenen et aI.'} Upon reaction to NiSi 2 , Si atoms may be left
over, presumably in interstitial sites, and are then free to

FS1', w;

,~;., ~,'--N;S'L'O'N--

diffuse to the surface, where they arrange in an epitaxial

layer just as the silicide phase is built on top of the initial
Si ( 111) surface. The ordered arrangement in both cases is
made possible by the close match of the two lattices, Substi~
tutionaI diffusion may also occur. The magnitude of diffusion velocity obviously depends on the thickness of the NiSi 2
layer. By studying different layers (1-40 A nickel) we found
that in thin NiSi 2 layers the increase of the clean Si peak
proceeded much faster than with thicker layers. The diffu~
sion process can be understood in terms of the surface energy
of Si w hieh is only 52% of that of NiSi 2 ]6
A survey of the literature shows that the outdiffusion of
Si through silicide layers, and the formation of cap layers has
been speculated upon in a number of reports, but firm evidence has so far been missing. Thus Chang and Erskine reported evidence for Si segregation to the silicide surface from
their valence photo emission study of nickel silicide layers
annealed at high temperature. 17 ,IR Wu et al. noted in a
LEED study of NiSi z on SiC 100) that calculated LEED in~
tensity curves based on bulk termination models failed to
give good agreement with experimental data, whereas a Si
adatom-terminated structure gave best agreement. 19 Evidence for Si surface segregation and the formation of Si cap
layers was also found in epitaxial CoSi 2 layers. 20 The formation of such layers may explain why double epitaxy, i.e., the
growth of Si films on top of the NiSi 2 layers, is readily
achieved for the NiSi 2 (111) orientation?I,22
We gratefully acknowledge the excellent support by the
staff of BESSY , This work was supported by the Bundesministerium fur Forschung und Technology under grant 05241
HR, 05 390 FXB/390 FX4, 05 230 NU I, and by the
Deutsche Forschungsgemeinschaft through SFB 6,
1 Ao

'\/"

"'.,"i...~::".

..'.,.
.'

"hw

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:::130eV

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0

C
:J

-eCl

'0;.1>::-::
......

.,:

,:",,,"'c

he; =120eV

".

:.~::.:::~/:::\':t;:::~'

:....:.:~..~::'~/j.1.;<

."-,~."c
....
'.

,-

.,<'':.

to

.,

'-

hw:::l10eV

'.'

";".:

,: ..
I

101

Hiraki, Surf. ScL Rep, 3, 357 (1984).

2c. Calandra, O. Btsi, and G, Ottaviani. Surf. Sci. Rep. 4, 271

100

99

-------,-------.!
96

Binding energy (eV)

FIG. 3. Si 2p core level spectra from a layer ofNiSi1 , produced by evaporation of 12.5 A lS'i and annealing, recorded in normal emission with ditrerent
photon energies as indicated, The peak due to "clean Si" strongly decreases
in intensity in the bulk-sensitive spectrum at fu,) c.. 110 eV,

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