Solid State Communications Vol. 12, pp. 253—257, 1973.

Pergamon Press Printed in Great Britain

RAMAN SCATTERING IN Ge-Si ALLOYS*

W.J. Brya

Sandia Laboratories, Albuquerque, New Mexico 87115

(Received 28 September 1972 by A.A. Maradudin)

Room temperature Raman spectra are reported for polycrystalline Ge—Si

alloys as a function of composition. The frequencies and linewidths of the
three main peaks show some disagreement with previously reported work;
the results are discussed within the theories of local and resonance modes
of impurities, where possible. Minor scattering peaks and second-order
spectra, as well as anomalous behavior in several inhomogeneous samples,
aie also reported and discussed.

THE VIBRATIONAL spectrum of the Ge—Si alloys
system has recently received considerable interest
because of its unusual multimode behavior. In particu-
lar, Raman studies14 show three main lines which
have been tentatively ascribed to the vibrations of
Ge—Ge, Si—Si and Ge—Si pairs. In this work, compre-
hensive Raman spectra for a large number of alloys
over the full range of composition are presented; the
frequencies and linewidths for the three main peaks
show several disagreements with previously reported
work.3 For the Ge-rich materials, the spectra are in
good agreement with theories of local-mode behavior
for isolated substitutional Si impurities in Ge; the Si-
rich materials show only fair correspondence with
the predictions for resonant and near-resonant modes
of the heavy Ge impurity in Si. The behavior with
composition of the minor scattering peaks and the
second-order spectra is also given. In addition, the ob-
served splitting of only one of the main peaks in in-
homogeneous samples appears to indicate preferred
local environments for the constituents.
For this study the Ge
1_~Si~samples were pre-
pared from undoped, polycrystalline materials. A
majority of the samples were fabricated from vacuum
hot-pressed (HP) slugs formed from fine powders of
* This work was supported by the U.S. Atomic Energy
Commission,
chill-cast alloy material;5 several samples of zone-
leveled (ZL) alloys were also studied for comparison
with the results obtained in the HP materials. The
alloy compositionx was determined primarily from
7-ray attenuation measurements and/or electron
microprobe analysis. The microprobe analysis also
showed the Si- and Ge-rich HP materials and all the
ZL samples to be quite homogeneous in composition;
the HP materials in the region x ~0.5 showed, how-
ever, large inhomogeneities,6 as will be discussed later.
All the samples were polished for several hours with
0.OSji alumina to remove surface damage.
The unpolarized Rarnan spectra were obtained
in a near-back-scattering configuration using an Ar-ion
laser, double spectrometer, and photon-counting de-
tection; all measurements were made at room tern-
perature. The positions of the stronger lines were de-
termined from an average of their Stokes and anti-
Stokes components, while the Stokes components of
weaker lines were located relative to these stronger
lines.
Typical spectra obtained for several alloy corn-
positions are shown in Fig. 1. The usual three promi-
nerit peaks are seen, along with additional minor
structure which we shall discuss shortly. Here, the
lines at 300 and 500cm’~are labelled Ge and Si,
respectively, since they are derived originally from the
zone-center phonon modes of the pure Ge and Si

253
254 RAMAN SCATTERING IN Ge—Si ALLOYS Vol. 12, No. 4

materials. The strong central line is labelled Ge—Si 52~ 15

since it is believed to be related to the vibrations of a Si line
pair of nei~iboringGe and Si atoms, at least in the 500
Ge- and Si-rich materails. In Fig. 2 are shown the pos-

itions
to
of the and
alloy linewidths
Si-line
composition;
_ of
in the HP these for
except
samples three
thepeaks
with as a 0.6,
multiple
0.3 ~x function
peaks ~a1O 5

-,
which arise from the large inhomogeneities in compos- ~
ition, the HP and ZL materials show essentially ident-
45C 0
ical behavior. Our results are generally in good agree- 4~ 16
ment with the work of Renucci eta!.3 (RRC) although
E
12 ~

X~02
1 Os
AGAIN I I 400
390 a 8 I
Ge-Si line
38C 4
310 Ge line

z
ILl
_______________________________________________________________

,. x O~5 :: ~ a
8

412

Z 450
~
55C
J 280
O
Ge
0,2 0.4
x
0.6 0,8
l~
1.0
Si
/

~ —~——--—~ ~ I ~ FIG. 2. Dependence on composition of the frequencies

LI 09
~ ~
L
~00
~
250 400
ENERGY SHIFT (cm~)
FIG. 1. Typical room temperature Raman spectra for
zone-leveled (ZL) and hot-pressed (HP) Ge i~xS~x
alloys. Inset for x = 0.5 shows splitting of the Si-line
at 500 cm’ observed in the inhomogeneous HP
materials,
there are several qualitative and quantitative differences.
In our case, the Ge-line typically occurs at a slightly
higher energy than that reported by RRC; more tin-
portantly, our data show a linear variation of line pos-
ition with composition as opposed to their observed
nonlinear behavior. For the Si-line (neglecting tempo-
rarily the multiple HP data) our line positions are
0
G4~’~
and linewidths for the three main scattering peaks in
Ge
1_~Si~alloys at room temperature. Open triangles
Ii
and circles show frequencies for HP and ZL materials,
respectively; solid symbols show linewidths for same.
Multiple data for the Si-line of the HP materails are
due to sample inhomogeneities (see text). Open
squares at x = 0 and I show line positions for single-
550
ition
crystalofGe
Ge—Si
and Si
peak
(reference
in Ge-rich
7) material
and extrapolated
(referencepos-
1).
generally in good quantitative agreement with the
RRC results; here also, our data indicates a linear
variation in peak position, even for the small x regime.
In addition, our linewidths are typically less than those
reported by RRC, with the Ge- and Si-linewidths show-
ing essentially linear behavior with composition and
the Ge—Si width showing a slight change at x 0.5.
Considerably more insight into the nature of these
lines, including the minor peaks and second-order
spectra previously mentioned, can be obtained by a
more detailed analysis of specific regions in the alloy
composition. For the Ge-rich materials the
7 a behavior
single
is fairly well understood. Pure Ge shows
Vol. 12, No.4 RAMAN SCAflERING IN Ge—Si ALLOYS
strong Ge-peak at 300.5 cnc’ which arises from the
q = 0 phonon mode. As Si impurities are introduced,
the Ge-peak slowly decreases in intensity and frequency
and a new line appears 389 cm” which increases in in-
tensity and frequency with increasing Si. This line was
first observed by Feldman eta!.1 in Raman scattering
and was associated with the local mode of an isolated
Si atom in the Ge lattice; more recently, this same
Ge—Si local mode has been observed in infrared ab-
sorption studies by Cosand and Spitzer8 (CS). The ob-
served frequency of the local mode is in good agree-
ment with the predicted value of 394 cm”1 determined
from the Dawber and Elliott theory9 for an isolated
substitutional Si atom in the Ge lattice; in addition,
Feldman er a!, show that the linear increase in the local
mode frequency and the decrease in the Ge-mode fre-
quency with increasing Si content is in qualitative
agreement with the theory of Xinh’°for Raman scat-
tering in crystals of the diamond structure containing
substitutional random-mass defects.
Forx ~ 0.1, a new pair of lines appears at —~445
and 460 cnf’. These peaks were seen by Feldman
et a!. and were tentatively attributed to localized
modes of nearest-neighbor pairs of Si atoms in Ge; CS
also see evidence for weak i.r. absorption bands in this
region. Our results and those of RRC show that the
460 cnf’ line increases in frequency and intensity
with increasing Si content, eventually becoming the
Si-line in the Si-rich materials; the 445 cm’ peak,
however, shows little change in frequency or intensity
with inclusion of Si. Possibly the 445 cm’’ line is
associated with isolated pairs of interacting Si atoms,
wheras the Si-peak results from larger clusters of Si,
With increased Si doping, the three main lines
develop marked asymmetries with long broad tails on
the low-frequency sides and sharp cutoffs on the high-
frequency ends; generally, this occurs because the
introduction of Si impurities breaks down the trans-
lational symmetry of the lattice (introduces disorder)
and phonons over the full Brillouin zone can make
contributions to the first-order Raman spectrum. In
the pure Ge sample one also observes a weak, broad
two-phonon band at 575 cm~which arises from
zone-boundary TO phonons. This band shows little
change with Si doping.
For the Si-rich materails the situation is slightly
different. Substitution of the heavy Ge atom for the
lighter Si is expected to produce in-band resonant
255
modes. For pure Si, the single strong Si-peak is ob-
served7 at 5205 cm” As Ge is introduced, well-
-
defined lines appear at 402 and 437 cm’’ and a weak
line occurs at 487 cnf’ on the shoulder of the Si-
peak. With increasing Ge, the Si-line decreases in fre-
quency and intensity while the Ge—Si peak at 402 cm’
slowly shifts to higher frequencies and gains in inten-
sity. The 437 and 487 cm” lines show little change
in frequency and only slight increases in intensity.
Ashkin er al. 2 report similar multiple peaks in the
R.aman spectra of the Si-rich materials; likewise, CS
also fmd evidence for i.r. absorption near these peaks.
Maradudin11 has calculated the frequencies of resonant
and near-resonant modes for an isolated Ge atom in
Si; his results indicate resonant modes near 453 and
490 cm’ and near-resonant modes around 116, 334
and 380 cm”~’.Xinh1°has calculated the Raman cross-
sections for these modes and shows that the 116 cm’
line should be weak; his results also indicate the Si-
line frequency should decrease with increasing Ge, as
is observed. The observed lines at 437 and 487 cnf’
show reasonable agreement with the calculated res-
onant modes at 453 and 490 cm’ ;however, Si pos-
sesses zone-boundary TO phonons in the region of
450—490 cm” and they might appear in the first-
order spectra as the 487 cm’ line because of the
lattice disorder produced with the inclusion of Ge
impurities. The 402 cm~line shows no obvious
correspondence with any of the predicted modes al-
though it might be assoicated with the near-resonant
modes at 350 cm’ It is well known, however, that
.
the calculated frequencies of these in-band resonances
are very sensitive to the details of the chosen phonon
density-of-states curve for the host material,
For x ~ 0.8 another new line appears at 285 cm’
which increases in intensity and frequency with in-
creasing Ge and eventually becomes the Ge-line in the
Ge-rich materials. l’his line probably results from
clustering of Ge and would not be predicted by the
previous theories which are applicable to isolated urn-
purifies.
In these Si-rich materials, the main lines again
develop the previously mentioned asymmetries for
x ~ 07, with the Ge—Si peak showing the largest
effect. In addition, one observes weak, broad two-
phonon lines at 260 and 965 cm~for pure Si
which result from zone-boundary TA and TO modes;
they show only slight changes with Ge content. The
285 cnf’ Ge-line occurs in the midst of the 260 cm’
256 RAMAN SCATTERING IN Ge—Si ALLOYS Vol. 12,No. 4

band, but it is not possible to determine if the Ge-line The HP materials in this range of compositions
actually has its origin in this band as suggested by show essentially the same behavior as the ZL materials
Ashkin et a!.2 with one notable exception for 0.3 x ~ 0.6, the Si-
—

peak appears as a doublet with the intensities and pos-

For alloys in the range x 0.5, where little is
known about the nature of the vibrational excitations,
the spectra show several features characteristic of both
the Ge- and Si-rich materials. In zone-leveled material
ofx = 0.5, the three prominent peaks are of corn-
parable intensity with the Ge—Si line showing a pro-
nounced asymmetry relative to the other peaks.
Further addition of Ge or Si causes the intensity and
frequency of the Ge—Si peak to decrease, whereas the
Si (Ge) line increases (decreases) in frequency and in-
tensity with Si doping. Both minor peaks are observed
at 430 and 445 cm’ which occured in the Si- and
Ge-rich materials, respectively; with increasing Ge (Si)
content the 430(445) cm’ line gradually disappears.
Weak, broad bands at 240, 565 and 995 cm’,
which are derived from the two-phonon bands of the
pure Si and Ge materials, are all present. However, one
observes a new band at 790 cm’ which is probably
a two-phonon line also. It is not possible to determine
whether this band arises from a combination of those
phonons responsible for the 565 and 955 cm’ bands
or whether it is associated with new excitation present
in the Ge0.5 Si0,5 alloy. The band is present only when
both the 565 and 955 cm’ bands occur.
itions of the lines showing only minor variations be-
tween samples of the same composition. As seen in
Fig. 2, the HP alloy atx = 0.5 shows Si-peaks charac-
teristic of x 0.3 and 03; a microprobe analysis of
one sample indicates sizeable regions of the material
with just such compositions. The surprising result,
however, is that this large inhomogeneity shows no
effect on the Ge and Ge—Si peaks; in several samples
of the x = 0.5 composition, the peak positions and
their linewidths are essentially identical for the ZL
and HP materials (see Fig. 2). Even though the nature
of the vibrational excitations in the x 0.5 materials
is not understood, our results do seem to indicate a
tendency for the constituents to favor preferred local
environments12 in samples of large macroscopic in-
homogeneity. Such behavior would appear to strength-
en further the arguments3’4 for the formation of an
ordered Ge
0,5 Si0.5 alloy and for the possible inter-
pretation of several of the observed lines in the x
0.5 materials as local and resonant modes of Ge and!
or Si impurities in the ordered Ge0.5 Si0~compound.
X-ray diffraction studies in single-crystal material of
x = 0.5 would be of particular interest in this regard.
Acknowledgements Thanks are extended to R.N.
—

Fortune for his technical assistance and to G.L.

McVay and E.H. Farnum for supplying the samples.

REFERENCES
1. FELDMAN D.W., ASHKIN M. and PARKER J.H., Jr.,Phys. Rev. Lert. 17, 1209 (1966).
2. ASHKIN M., PARKER J.H., Jr., FELDMAN D.W. and RUBENSTEIN M., Bull. Am. Phys. Soc. 14, 343 (1969).
3. RENUCCI M.A., RENUCCI J.B. and CARDONA M.,Light Scattering in Solids, p.326. Flammarion, Paris
(1971).
4. RENUCCI J.B., RENUCCI M.A. and CARDONA M., Solid State Commun. 9, 1651 (1971).
5. LEFEVER RA., BAUGHMAN R.J. and MCVAY G.L., (to be published).
6. This behavior results from a segregation of the initially homogeneous alloy during the chill-cast process. For
Si- and Ge-rich materials, the segregation is small enough that the subsequent vacuum hot-press technique can
restore the homogeneity; for x 0.5, the greater segregation is difficult to remove.
~-

7. PARKER J.H., Jr., FELDMAN D.W. and ASHXIN M.,Phys. Rev. 155, 712 (1967).
8. COSANDA.E. and SPITZERW.G.,J. appi. Phys. 42, 5241 (1971).
9. DAWBERP.G. and ELLIOTT R.J.,Proc. R. Soc. (London) 273A, 222 (1963);I~oc.R. Soc. (London) 81,
453 (1963).
Vol. 12, No.4 RAMAN SCAUERING IN Ge—Si ALLOYS 257

10. XINH N.X., Localized Excitations in Solids, p.167. Plenum, New York (1968).
11. MARADUDIN A.A., Solid State Physics, Vol. 18, p. 273, Academic Press, New York (1966).
12. Measurements of zone-boundary phonon energies in the Ge—Si system suggest that the minority atoms in an
alloy do not occupy neighboring lattice sites. See LOGAN R.A., ROWELL J.M. and TRUMBORE F.A, Phys.
Rev. 136, A175l (1964).

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