Journal of the Korean Physical Society, Vol. 51, No. 3, September 2007, pp.

10321037
Formation and Characterization of Manganese Silicide
on Si(111) and Si(100) Substrates
K. H. Kim,

J. D. Lee and J. J. Lee

Department of Physics and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701
S. W. Han
Nano Surface Group, Korea Research Institute of Science and Standards, Daejeon 305-340
J.-S. Kang

Department of Physics, The Catholic University of Korea, Buchon 422-743

(Received 13 November 2006)
The electronic structure of the interface formation at Mn/Si at room temperature (RT) and the
growth of manganese silicide were studied by using photoemission spectroscopy (PES) and X-ray
absorption spectroscopy (XAS) with synchrotron radiation. The Mn coverage dependence of the
Si 2p and the Mn 3p core-level spectra revealed that the growth of Mn on Si(111)-7 7 at RT
started in a layer-by-layer growth at a coverage of less than 0.5 ML (monolayer). Mn 2p XAS
spectra also showed no reaction between Mn and Si at RT. Three thin manganese silicide samples
were prepared by using solid phase epitaxy at 610

C (MS
S
), reactive deposition epitaxy at 290

C
for Si(111) and at 350

C for Si(100) (MS
R
) and post annealing the MS
R
sample at 610

C (MS
P
)
on the Si(111) and the Si(100) substrates. The LOW ENERGY ELECTRON DIFFRACTION
(LEED) pattern and the ne structure in the Mn 2p
3/2
XAS spectra showed that the phases of
the MS
S
, the MS
R
, and the MS
P
samples were the same. Emissions at the Fermi energy in the
valence-band (VB) PES spectra and the line shape of Si 2p core-level photoemission spectra also
showed the formation of metallic MnSi.
PACS numbers: 73.20.Dx, 68.35.a, 79.60.D
Keywords: Mn/Si interface, Electronic structure, PES, XAS, MnSi
I. INTRODUCTION
Recently, manganese-based compounds have been
studied extensively for narrow band gap semiconduc-
tors [13] or diluted magnetic semiconductors (DMS)
[4]. Among them, manganese silicide, e.g., MnSi
1.73
and
MnSi, has attracted much attention. MnSi
1.73
, belongs
to the higher manganese silicides (HMS, MnSi
2x
, x =
0.25 0.27) and is a narrow-band-gap semiconductor. It
has a tetragonal structure (a
0
= 5.531

A, c
0
= 65.311

A)
in the space group I

42d. The electrical and the optical

properties of MnSi
1.73
have been reported [58].
On the other hand, MnSi has a cubic B20 structure in
the space group P2
1
3 with a lattice constant a = 4.558

A. MnSi is a weak itinerant ferromagnet and lacks a cen-

ter of symmetry, leading to a left-handed ferromagnetic
spiral in the ordered phase along the [111] direction [9].

E-mail: khokim@gnu.ac.kr;

E-mail: kangjs@catholic.ac.kr
Hence, the growth of ultra-thin epitaxial MnSi lms on
Si substrates may solve the problem of impedance mis-
match at the metal/semiconductor interface, as well as
the demand for miniaturization. MnSi has been reported
to be formed by a diusion-controlled reaction of a Mn/Si
diusion couple at low temperature (400

C); on the
other hand, MnSi
1.73
is formed by an interface reaction at
higher temperature (600

C) [10,11]. For device appli-
cations, the interface reaction is more favorable than the
diusion couple for the growth of a silicide on Si. Due to
demand in nano-technology, controlled growth of nano-
sized MnSi or MnSi
1.73
on a Si substrate is favorable for
the practical applications. Many eorts have been de-
voted to understanding the initial stage of interface for-
mation at Mn/Si substrate and the growth of ultra-thin
manganese-silicide lms on Si substrate, but the results
show discrepancies [1215]. In this study, we present
the electronic properties of the Mn/Si(111) interface and
ultra thin manganese silicide, which was obtained from
photoemission spectroscopy (PES) and X-ray absorption
spectroscopy (XAS) using synchrotron radiation.
-1032-
Formation and Characterization of Manganese Silicide on Si(111) K. H. Kim et al. -1033-
II. EXPERIMENT
Phosphorous-doped n-Si(111) and n-Si(100) wafers
were used as substrates. The wafers were cleaned in a
diluted HF solution and rinsed in deionized water. Then
it was dried by blowing dry N
2
and loaded in the prepa-
ration chamber (base pressure 2 10
10
Torr) at the
2B1 VUV beamline of Pohang Accelerator Laboratory
(PAL).
Mn was deposited in the preparation chamber by sub-
liming high purity (99.99 %) Mn lump which had been
extensively out-gassed prior to sublimation. The deposi-
tion rate was about 0.25 0.5 ML/min for Si(100) and
1 ML/min for Si(111) substrate. 1 ML of Mn corre-
sponds to 1

A-thick Mn lm [14]. Nominal thickness
(or coverage), , was determined by the exposure time
of Mn ux to the sample surface. We used as the
thickness of Mn lm throughout the paper. Three kinds
of manganese silicide samples were prepared: (1) Mn de-
position at RT followed by annealing at 610

C for 10
min (MS
S
), (2) Mn deposition on hot (T
sub
= 290

C
for Si(111) and 350

C for Si(100) substrate) substrates
(MS
R
) and (3) Mn deposition on hot substrate followed
by post annealing at 610

C for 10 min (MS
P
).
After preparation, samples were transferred to the
analysis chamber. All spectra were taken at RT and the
base pressure in the chamber was lower than 5 10
11
Torr range during measurements. The Fermi level, E
F
,
was determined from the valence-band spectrum of an
Au-foil in electrical contact with the sample. The overall
instrumental resolution was about 200 meV at a photon
energy h 30 60 eV and about 300 meV at h
120 160 eV. All spectra were normalized to the incident
photon ux. The X-ray absorption spectroscopy (XAS)
spectra were obtained by employing the total electron
yield method. The experimental energy resolution for
the XAS data was set to 100 meV at the Si 2p and Mn
2p absorption thresholds (h 500 600 eV).
III. RESULTS AND DISCUSSION
We monitored the low energy electron diraction
(LEED) pattern as a function of on a Si(111)-7 7
surface at RT. The Si(111)-7 7 pattern was easily ob-
tained by ash heating the substrate at 1150

C. This
7 7 pattern weakened and a 1 1 pattern began to de-
velop just after reached 0.2 ML. With increasing ,
only the 7 7 patch remained at the center of the pat-
tern, and it was visible up to 1.5 ML. Figure 1 (a)
shows the LEED pattern obtained at 1 ML. The 1
1 pattern was fully developed at 2 ML. As was in-
creased, the 1 1 pattern began to weaken with a bright
background. No LEED pattern was observed at 4
ML. The variation of the LEED pattern with indicates
that Mn forms an ordered state at low , but changes
to a disordered state as increases. Upon annealing the
Fig. 1. LEED pattern: (a) Si(111)-1 1 pattern with a 7
7 patch and (b)

3-R30

+ 1 1 pattern.
Mn lm of 8 ML at 610

C for 10 min (MS
S
sample),
a

3-R30

+ 1 1 LEED pattern, as shown in Fig-

ure 1 (b), developed. When 8 ML Mn was deposited
on a hot substrate (T
sub
= 290

), which is the MS
R
sam-
ple, no LEED pattern was observed, but the same LEED
pattern developed after post annealing the MS
R
sample
at 610

C for 10 min (MS
P
sample). The

3-R30

LEED pattern shows that manganese silicide was grown

in the MS
S
and the MS
P
samples. The appearance of the

3-R30

+ 1 1 LEED pattern had been reported

[1315]. Shivaprasad et al. [13] reported that deposition
of Mn on a Si(111) substrate at very low rates (0.15
ML/min) resulted in the formation of an epitaxial struc-
ture even at RT. Upon further deposition up to 2 3
ML, Mn atoms accumulated in a layer-by-layer (Frank-
van der Merwe) growth mode, which resulted in a 1
1 LEED pattern. A very sharp 1 1 phase was de-
veloped upon annealing the RT-deposited Mn(1 < <
2 ML)/Si(111) at 350

C whereas, annealing the RT-
deposited thick Mn( > 3 ML)/Si(111) resulted in a
sharp

3

3 phase, which corresponded to the for-

mation of manganese silicide. Kumar et al. [15] showed
evidence of an island growth mode. They observed a
pseudo-1 1 LEED pattern when Mn was deposited on
a Si(111)-7 7 surface at low coverage ( < 1.5 ML) at
RT, which they attributed to island formation due to the
metal-silicon reaction at RT. By annealing the Mn lm
(1.5 3 ML) at temperatures up to 400

C, they were
-1034- Journal of the Korean Physical Society, Vol. 51, No. 3, September 2007
Fig. 2. Component peaks obtained by the best t for Si
2p core level PES spectra: (a) clean Si(111)-7 7 sample
and the (b) MS
S
, (c) MS
R
and (d) MS
P
samples measured
at h = 130 eV.
able to observe the

3 LEED pattern of manganese

silicide.
To better understand the electronic properties of the
interface formation, we analyzed Si 2p core level PES
spectra by means of component lines. For the extraction
of component lines contributing to the Si 2p core level,
PES spectra were analyzed by using a least-squares t-
ting procedure. A simple t of the line shapes of the Si-
2p peak was obtained by using Gaussian and Lorentzian
peaks, along with the asymmetry parameter introduced
by Doniach and Sunjic [16]. For curve tting, the Gaus-
sian width, the spin-orbit splitting, and the branching
ratio were set to 0.22 eV, 0.608 eV, and 0.50, respec-
tively, for all spectra. We used the Si 2p core level spec-
tra recorded by using h = 130 eV. Figure 2 shows the
curve tting result for Si 2p core level spectra of the clean
Si(111)-7 7, MS
S
, MS
R
and MS
P
samples. All spec-
tra were well decomposed into three lines labelled by P
1
(dashed line), P
2
(dotted line), and P
3
(solid line). The
measured spectrum () could well be reproduced by the
sum of the three component lines. The P
1
line, the main
peak for all spectra, originates from the bulk Si-sp
3
state.
The P
2
and P
3
lines of Si(111)-7 7 are emissions from
the back-bond atoms and rest atoms of the reconstructed
surface [17,18]. The relative weight (W
P
i
) and the posi-
tions of the P
2
and the P
3
lines in the MS
S
, MS
R
, and
MS
P
samples may reect dierent electronic properties.
Especially, the P
3
line seems primarily to be related with
the disordered state. W
P
i
is dened by the intensity of a
component line divided by the sum of the intensities of
all the component lines. The P
1
lines of the MS
S
, MS
R
and MS
P
samples were located at 99.1 eV, 99.16 eV and
Fig. 3. VB PES spectra measured at h = 35 eV for the
(a) Si(111)-7 7, 4-ML Mn deposited on Si at RT, MS
S
, MS
R
and MS
P
amples and (b) Si(100)-2 1, 5-ML Mn deposited
on Si at RT, MS
S
, MS
R
and MS
P
samples.
99.3 eV, respectively. The energy dierences between
the P
1
and the P
2
lines (E
P
2
P
1
) for the three samples
were nearly the same (0.3 eV). The line shapes for the
MS
R
and the MS
P
samples were almost the same, but
the line shape for the MS
S
sample was rather similar to
that of clean Si. The positions of the main peaks (P
1
line) of the MS
S
and the MS
R
samples shifted by about
0.2 eV to lower binding energy compared to the position
of the P
1
line of Si(111)-7 7, while the P
1
line of the
MS
P
sample shifted by only 0.1 eV to the lower binding
energy. The ratios of W
P
1
and W
P
2
for the MS
S
and the
MS
P
samples were nearly the same (W
P
1
: W
P
2
72 :
28), which was almost the same ratio for Si(111)-7 7
(W
P
1
: W
P
2
70 : 27), but the ratio of W
P
1
: W
P
2
for
MS
R
was 56 : 43.
The valence band (VB) spectra for a clean Si sub-
strate, Mn( = 4 ML)/Si, MS
S
, MS
R
and MS
P
samples
prepared on Si(111) and Si(100) substrates are shown in
Figures 3 (a) and (b), respectively, measured for 35-eV
Formation and Characterization of Manganese Silicide on Si(111) K. H. Kim et al. -1035-
photons. In the Si(111)-7 7 spectrum, the shoulder
S
1
and the peak S
2
at about 0.15 eV and 0.9 eV below
E
F
are the surface state peaks originating from half-lled
dangling bonds of adatoms and lled dangling bonds of
rest atoms, respectively. The other known surface state
peak from back-bond of adatoms, which is known to have
a binding energy of about 1.8 eV, was not well resolved
[17, 19]. The broad features centered at about 3.5 eV
and 7.5 eV below E
F
(labelled A and B) are emissions
from bulk Si. The features labelled S
2
, S
3
, A and B in
the clean Si(100)-2 1 spectrum in Figure 3 (b) are the
surface state peaks and the bulk Si peaks. A relatively
sharp peak, M1, at 0.4 eV and the broad feature M2
at 1.9 eV below E
F
in both Figures 3 (a) and (b) are
emissions from silicide. Kumar et al. [15] also previ-
ously reported the same peaks. By comparing with pho-
toemission studies on other 3d transition-metal silicides
[20], M1 is possibly derived from the Mn 3d non-bonding
states while M2 is derived from the Mn 3d - Si 3sp bond-
ing states. The line shapes of MS
S
and MS
R
in Figure 3
(a) and MS
P
in Figure 3 (b) are almost the same, which
suggests that those samples have the same phase. In ad-
dition, the line shapes of MS
R
and MS
S
in Figure 3 (b)
are qualitatively identical to MS
P
. All MS spectra show
a sharp increase at E
F
, indicating a metallic nature.
Irizawa et al. [21] found a sharp peak near E
F
and
broad peaks at about 1.3 and 3.0 eV below E
F
from
the VB spectrum of Mn
5
Si
3
. Son et al. [22] observed a
sharp peak near E
F
, followed by a weak feature at 2 eV
below E
F
from the VB spectrum of bulk MnSi sample.
By comparing the VB spectra of our MS samples with
those in the references, the phase of the silicide grown
here are assigned to MnSi rather than Mn
5
Si
3
. Only the
line shape of the VB spectrum of MS
P
in (a) seemed, at
a glance, dierent from that of MS
S
or MS
R
. The VB
spectrum of MS
P
consisted of a broad at feature with a
width of about 4.4 eV, a small peak (S
2
) at about 0.9 eV
below E
F
and a broad small feature (B) at about 7.3 eV
below E
F
. B and S
2
were located at the same binding
energy positions as those in the clean spectrum.
The similarity and the dierence in the Si 2p core level
(Figure 2) and the VB spectra for MS
P
and MS
R
of
Figure 3 (a) can be understood by assuming that a Si
overlayer is formed on top of the silicide grown on the
Si(111) substrate. Manganese silicide was rst formed
when Mn was deposited on the hot substrate (290

C).
Upon further annealing at high temperatures (over 600

C), Si atoms beneath the silicide can diuse out to

the surface and rearrange as an ordered structure, but
the thickness might be limited to a few atomic layers.
To test the assumption, we compared the measured Si
2p core-level and VB PES spectra with the numerically
generated spectra, which were produced by adding the
clean Si(111)-7 7 spectrum and the MS
R
spectrum.
As Figure 4 (a) shows, the best-t result for the core-
level spectrum was obtained by adding 45 % of the clean
Si(111)-7 7 spectrum and 55 % of MS
R
spectrum,
which implied that a Si overlayer of about 1 ML was
Fig. 4. Numerically reproduced Si 2p core level and VB
spectra by adding the measured Si(111)-7 7 and MS
R
spec-
tra: (a) Si 2p core level spectrum and (b) VB spectrum for
35-eV photons.
formed on the silicide surface. Figure 4 (b) shows the
resultant VB spectrum generated by using clean and
MS
R
spectra recorded with h = 35 eV. The proportions
of the component spectra are given in the gure. It is
well known that in a couple of transition metal/Si sys-
tems, Si atoms that out-diuse during thermal annealing
form an ordered overlayer on the silicide surface in the
form of an epi-Si/epi-silicide/Si double hetero-epitaxial
structure [2325]. Choi et al. [23] reported that the
Si(111)/C49-TiSi
2
/Si(111) double hetero-epitaxial struc-
ture was formed by deposition of a thin Ti lm on a
Si(111)-7 7 surface at RT, followed by in-situ anneal-
ing in UHV. Hinkel et al. [24] reported out-diused Si
atoms during annealing epitaxial Ni lms on Si(111)-2
1 substrates formed an epitaxial Si layer on top of the
NiSi
2
surface.
Figure 5 shows the Mn 2p XAS spectra for the = 2-
-1036- Journal of the Korean Physical Society, Vol. 51, No. 3, September 2007
Fig. 5. XAS spectra obtained from 2-ML and 4-ML Mn
deposited samples and those obtained from MS
S
, MS
R
and
MS
P
samples. The arrow () in the gure represents the
ne structure induced by the silicide formation. The XAS
spectrum for the bulk Mn sample was reproduced from Ref.
25.
ML and 4-ML samples and for the MS
S
, MS
R
and MS
P
samples prepared on Si(111) substrate. As a reference,
the Mn 2p XAS spectrum for bulk Mn metal was re-
produced from the work of Yonamoto et al. [26]. The
spectra for = 2 ML and 4 ML are very similar to that
of bulk Mn metal, but those of the MS
S
, MS
R
, and MS
P
samples are quite dierent. The overall line shapes of
the spectra for MS
S
, MS
R
and MS
P
samples are simi-
lar. The Mn 2p3
2
peaks of the MS
S
, MS
R
and MS
P
are
broader than that of the bulk Mn metal. The positions
of Mn 2p3
2
and Mn 2p1
2
peaks of the MS
S
, MS
R
and MS
P
samples are shifted by about 1.5 eV to the higher energy
compared to that of the bulk Mn metal. A small shoul-
der peak ( in the gure) at 1.5 eV below the main Mn
2p3
2
peak was well developed in the MS
R
and the MS
P
samples. We believe this is a characteristic line shape of
the MnSi phase.
IV. CONCLUSION
In summary we have shown the electronic structure
of MnSi prepared on a Si(111) or a Si(100) substrate.
The growth of Mn on Si(111)-7 7 at RT started in a
layer-by-layer manner at a coverage, , of less than 0.5
ML, but it changed as increased. At a coverage of 4
ML, the VB PES spectrum revealed a metallic Mn band
with no Si-derived states. The Si 2p core-level and the
VB spectra of the MS
S
, MS
R
and MS
P
samples showed
the same metallic MnSi phase. The Si 2p core level and
VB spectra of the MS
P
sample were generated by nu-
merically adding the clean Si(111)-7 7 and the MS
R
spectra, and a Si overlayer of about 2 3 ML was esti-
mated on the silicide. By comparing the VB spectra of
the MS
S
, MS
R
, and MS
P
samples, only metallic-phase
manganese silicides were formed by reactive deposition
at either 290

C for Si(111) or 350

C for Si(100) and
by solid phase deposition at 610

C, for low Mn coverage
(8 ML) on a Si(100) or a Si(111) substrate.
ACKNOWLEDGMENTS
This work was supported in part by a Korea Research
Foundation (KRF) grant (KRF-2003-005-C00014) and
a Korea Science and Engineering Foundation (KOSEF)
grant (R05-2003-000-10201-0). The experiment at PAL
was supported by MOST and POSCO.
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