Solid State Communications, Vol. 8, pp. 133—138, 1970. Pergamon Press.

Printed in Great Britain

EFFECT OF STATIC UNIAXIAL STRESS ON THE RAMAN SPECTRUM OF SILICON

E. Anastassakis,* A. Pinczuk and E. Burstein

Physics Department and Laboratory for Research on the Structure of Mattert
University of Pennsylvania, Philadelphia, Pa. 19104

and
F.H. Pollak and M. Cardona

Physics Department, Brown University, Providence, Rhode Island

(Received 1 December 1969 by E. Burstein)

We have performed the first experimental investigation of the effects

of static uniaxial stress on the frequency of the q ~ 0 optical phonons
in a diamond-type crystal. Application of uniaxial stress along
[001] or [iii] is found to cause splittings and shifts of the Raman
peaks of the q ~ 0 triply degenerate optical phonons. From the
observed splittings we have obtained experimental values for the
phenomenological coefficients which describe the changes in the
‘spring constant’ of these phonons with strain. Our results are in
reasonable agreement with lattice dynamical theory.

WE REPORT here the results of an experimental
investigation of the effects of static uniaxial
stress on the frequency of the q ~0 optical
phonons in silicon using Raman scattering. In
the absence of uniaxial stress, the first order
Stokes Raman spectrum of silicon exhibits a
single peak at w
8 — ~, where w1 and w~
are the frequencies of the incident and scattered
radiation, respectively, and W0 is the frequency
of the q~0 triply degenerate optical phonons.
* Present address: Department of Physics,
Northeastern University, Boston, Massa-
chusetts.
t Research
of Naval Research,
supported the
in part
ArmybyResearch
the U.S. Office
Office-
Durham, and the Advanced Research Projects
Agency.
~ Research supported in part by the Army Re-
search Office-Durham, the National Science
Foundation, and the Advanced Research
Projects Agency.
When a uniaxial stress is applied, the Raman
peak exhibits splittings and shifts which are
linear in the applied stress. From the observed
splittings of the Raman peak with applied
stress along [001] and [111] directions we
have obtained the first experimental values for
the phenomenological coefficients which
describe the changes in the spring constant
of the q ~ 0 optical phonons with strain. The
shift due to the hydrostatic component of the
strain yields a value for the mode Gruneisen
parameter for the q ~0 optical phonons
(y~= —8mW0 /8lnV where V is the volume of
the crystal) which is found to be essentially
the same as that for diamond as determined
1 fromby
Mitra, Brafman,
Raman scatteringDaniels,
measurements
and Crawford
of the shift
in frequency induced by hydrostatic pressure.
Our results are in reasonable agreement with
the lattice dynamical theory of the morphic
effects of strain on the first order Raman
spectra of diamond-type crystals developed by
Ganesan, Maradudin and Oitma.2

133
 134 STATIC UNIAXIAL STRESS ON THE RAMAN SPECTRUM Vol. 8, No. 2

In the presence of a strain ~ -~ ~ the One finds:

dynamical equations for the q ~ U triply de- 2 2
generate (F
20 symmetry) optical modes in = ~ + A~lh)+ = ~20 +1AQ
diamond-type crystals2 to terms linear in the = ~ + A~2f)— = — (3)
strain, has the form
= ~kUk = - [k~ii
1 +~ ~ ~_W~= (~2~
—~)—~AQ (4)
(1) (5)
where u~is the ith component of the relative -_ (p ~ 2q)(s + 2s12 )

displacement of the two atoms in the unit cell;

~i is the reduced mass of the two atoms; — q) (s ,~— s ~ ~// 0011
~0) = ~ is the effective spring constant of ~ (6a)
the F~ modes in the absence of strain; LI — =

(aK~k/8~~ )~~= ~ ~ ~,= ~ ~ ~, is the

change in the spring constant due to an applied
strain ~ ; and i, k, I and ,n designate x or ~‘
or z. Thermodynamic considerations require
that ~ = 1) = = k From
simple symmetry considerations on finds that
for a cubic crystal there are three independent
components
111 of the tensor namely,
K, 1 1 1 = K ~‘ 2= K ~ = ~p K = K
biq and K 1212 = K~3 = K ~. = ~ñr.
From the dynamical equations one obtains the
following secular equation whose solutions yield
the frequencies of the optical phonons in the
presence of strain:
~.L_ r s44 ; ~ [lii]
.~-o (6b)
where T is the magnitude of the uniaxial stress
s,1, s12 and s44 are the elastic compliance
constants referred to the cubic axes and the
suppressed subscript notation has beed used for
K,13 the stress—strain relationship * J~follows than
an experimental determination of ~1. or (~l~)
and A~2for the two directions of stress allows
one to determine p, q rand L\~2,. The consis-
tency of the results can be checked by comparing
the two values of (p -~- 2q) which are obtained
from equation (5) for the two directions of stress.

~ + q(~0~.
+ ~?)~ A 2r, 2r~~
~ ~ + q(~j2~
-r ~D-- A 2rr~2 = 0
~ 2r7~.2 p + q(j~~.
+ ~j:v)~A (2)
where A = ~2 ~ and ~2 ~ ± A’2~3is the
strain dependent frequency of the optical
phonons. The secular equation is referred to the
system of crystallographic axes, ~ = [100], *In the single subscript notation the stress
v = [010] and z = {00i]. Diagonalization of the strain relation is given by
secular matrix yields the set of three eigen-
vectors of the optical phonons in the presence = (i~ I = 1, 2 6)
of strain. The relation between single and double sub-
script notation is given by NYE J.F., Physical
For a uniaxial stress, ~ applied along either Pro pert/es of Crystals, p. 134, O.U.P. London,
the [001] or the [ill] directions, one finds that the (1957).
threefold degeneracy of the q 0 optical phonon
is split into a singlet ~ = 1l~)with eigenvector = 7 = In
parallel to the stress and a doublet (~l~ = R1) -.~ ii 2
with eigenvectors perpendicular to the stress. - 1 -r
There is also a shift in the frequency of the IL ~/2 /r~

optical phonons to ~l0 = + Aft, due to the 1

hydrostatic component of the applied stress. =
Vol. 8, No. 2 STATIC UNIAXIAL STRESS ON THE RAMAN SPECTRUM
The Raman scattering measurements were
carried out at room temperature using a 25 mW
He—Ne laser (6328 A) as source. Since silicon
is opaque at the laser frequency, the measure-
ments were carried out in the back-scattering
configuration~ The samples were in the form of
rectangular shaped bars approximately 2 cm long
and 1 mm x 1 mm in cross-section, having
polished and etched (2 cm x 1 mm) faces. Two
sample orientations were used designated as
x’y’z’ and x”y”z” . In the x#ylzI orientation the
long (z’) axis of the rod was parallel to [001]
and the short (x’ and y’) axes were parallel to
[110] and [110] respectively. In the x’y”z”
orientation the long (z”) axis was parallel to
[iii] and the short (x” and y’ ) axes were
parallel to [112] and [110] respectively. Negative
homogeneous uniaxial stresses were applied
along the long axes of the samples using the
5 by operating the Raman spectrometer (designed
Brown University uniaxial stress apparatus.
The homogeneity of the strain at the surface
produced by this apparatus has been demonstrated
by the fact that values of various parameters
(e.g. deformation potentials) as measured by
piezo-electroreflectance, where the penetration
depth of the light is approximately equal to that
in this experiment, are in good agreement with
those determined by bulk measurements (e.g.
transmission and cyclotron resonance).5
Raman scattering is a particularly useful
technique for observing the splitting of the
frequencies of the q ~ 0 optical phonons since
one can make use of polarization selection
rules6 to selectively observe scattering by a
given type of phonon. Since the strain induced
changes in the Raman tensor are relatively small,
the scattering is to a good approximation
determined by the first order Raman scattering
tensor of diamond-type crystals. On transforming
the Raman scattering tensor to the x’y’z’ axes
one finds that for the x’y’z’ samples with
uniaxial stress along z’ // [001] and the incident
and back-scattered
the singlet mode (eigenvector alongx z //
radiation along ) iS[110],
observed when the. incident and scattered radiation
are both polarized along y’ // [110], whereas one
of the doublet modes (eigenvector along y’ ) is
observed, with the same intensity, when the
incident radiation is polarized along z’ and the
135
scattered radiation is polarized along ~“ (or
vice versa). Similarly, on transforming the
Raman tensor to the x”y”z”axes, one finds that,
for x”y”z” samples with uniaxial stress along
z” // [1111 and the incident and back scattered
radiation along x // [112], the singlet mode
(eigenvector along z’) is observed when the
incident and scattered radiation are both polarized
along z” // [iii], whereas, one of the doublet
modes (eigenvector along ),“) is observed, with
one fourth of the intensity of the singlet mode,
when the incident radiation is polarized along
z” and the scattered radiation is polarized
along y’ (or vice versa). By switching the
polarization of the incident radiation between
z’ and y’ (or between z” and y”) leaving the
polarizer for the scattered radiation fixed
along y’ (or z’) one can optionally observe
either the singlet or the doublet. Furthermore,
by Dr. A. Filler) in a step scanning mode with
photon counting, and carrying out the scattering
measurements on the singlet and doublet in the
same run by switching the polarization of the
incident laser beam for each grating position, it
was in fact possible to condiderably reduce the
frequency reproducibility errors. The switching
of the polarization was accomplished by inserting
a A/2 plate into the path of the incident beam by
means of a mechanical device electronically
coupled to the grating drive system.
Typical spectra for the x’y”z” orientation
(uniaxial stress along [111]) are shown in Fig. 1.
The data were obtained for a uniaxial stress of
—11.5 x 10~dynes/cm2 and the slit widths
(0.3 mm) corresponded to an instrumental
resolution of 1.8 cm’. The counting rate for the
zero stress peak was 3/sec and the background
counting rate was ~5/sec. The Raman peak in
the absence of strain occurs at W
0 = 5230±0.2cm’
and its half width is 3.7 cm’. The position
of the zero4 strain peak
but was agrees with
somewhat higherthat reported
than that
by Russell
(520 cm ) reported by Parker, Feldman and
Ashkin.7 The width of the peak is somewhat
smaller than that (4.6 cm~)reported by Parker
and co-workers. No change in peak width with
applied stress is observed. The data of Fig. 1
show that for a negative uniaxial stress along
136 STATIC UNIAXIAL STRESS ON THE RAMAN SPECTRUM Vol. 8, No. 2

I I I I I
~ (z”z”);~Ilx’~r~o
5— 0 (Y~’Z’)~’Ux”; rlIZ” —

I • (Z”z”);~’lIx”;rIlz”
—4- 2 -
Slit Width ~ T~—ll.5xlO’dyne/cm

\/ \
I
~3- -~ ~—

~:

515 520 525 530 535 540

FREQUENCY IN crr~1
FIG. 1. The first order Raman spectrum of Si at 300°K with a uniaxial stress of
—11.5x l09dynes/cm2 applied along the [111] direction. The entries in the
parentheses i.e. (z’z” ) and (y”z”), designate the polarization direction of the
incident and scattered radiation. In each case, the direction of the incident and
scattered radiation is along x” and —x respectively.

[111], A~l= — 0d is positive. [In the case of values of the elastic compliance constants
the x’y’z’ orientation (negative uniaxial stress s, = 76.8, s,
2 = —21.4 and s~ = 126.0 (in units
along [001]) the sign of L\~2is found to be of 10_14cm2/dyne~we obtain using equations
negative.] The intensities of the singlet and (3)—(6) the following values (within 20 per
doublet peaks in Fig. 1 are uncorrected for cent) for the coefficients
2): p = —1.2, qp,= q, andand
—1.8 r (inr =units
— 0.63.

small differences
incident beams forinthe
thetwo
intensities of the When
polarizations.
the appropriate corrections are made, the ratio
of the singlet peak to doublet peak intensity is
found to be 4 as expected from the first order
selection rules. In recording the spectra the
counting time per grating step for the doublet
(400 sec) was chosen to be twice as long as
that for the singlet (200 sec) in order to partially
compensate for the unequal scattering intensities,
[In the case of the x’y’z’ orientation, the singlet
and doublet peaks are found to have the same
intensities as expected.]
of 102~
(The sec for p and q are obtained directly
values
from the data for the ~// [001]). The data for
the two orientations yield values of —4.7 and
—5.9 for the quantity (p + 2q) which determines
the shift in frequency with hydrostatic pressure,
indicating a self-consistency of about 25 per
cent. Our values for the coefficients agree in
sign and are in reasonable agreement in magnitude
with the theoretical values, p = —0.4, q —1.0
r = —1.5, which Ganesan, Maradudin and Oitmaa2
have obtained using a Morse potential and only
taking nearest neighbor interaction into account.

Curves of [l~, ~d and ~ = W

0 + A~2,,vs. The data also provide a value for the mode
uniaxial stress for the two orientations are shown Gruneisen parameter of the q 0 optical phonons’
in Fig. 2. From the slopes of the curves and the which is given by
Vol. 8, No. 2 STATIC UNIAXIAL STRESS ON THE RAMAN SPECTRUM 137

Lii -

——-—Li
0 -

‘E 526 —
C

— -.-- — —-.-.
-— —..
w
z
0
~
Ui 524 (//
-

—a——
/ ~ ~
-
~ -~- —

-ri [oo~] r II [iii]

I I 522 - I
-10 -5 0 -5 2 -10
UNIAXIAL STRESS IN ~ dyne /cm

FIG, 2. Shifts and splittings of the first order Raman peak of Si at 300°Kwith
uniaxial stress applied along the [0011 and [1111 directions.

— p_____
+ 2q (7) The present experiment demonstrates the
70 =

6W~ feasibility of using Raman scattering for obtaining

data on the strain dependent spring constants of
where V is the strain dependent volume of the optical phonons which are Raman active. The
crystal and V
0 is the zero strain volume. Using availability of such data should assist theorists
the average of the two values for (p + 2q) for the to develop improved theoretical models for lattice
two orientations, we obtain /~ = + 0.9. This dynamical phenomena. It should also be possible
value of % for silicon is essentially the same by means of Brillouin scattering measurements
as that for diamond, + 0.94, which Mitra, Brafman, to investigate the strain dependent elastic
Daniels and Crawford’ have obtained from Raman constants. The analysis of the strain dependent
scattering measurements of the hydrostatic dynamical equation and the associated Raman
pressure induced shifts in the q ~ 0 optical scattering polarization selection rules for the
phonon frequencies. diamond structure, can be readily extended to
other structures with Raman active modes.
Acknowledgment — We wish to acknowledge
valuable discussions with Professor A.A.
Maradudin.
138 STATIC UNIAX1AL STRESS ON THE RAMAN SPECTRUM Vol. 8, No. 2

REFERENCES
1. MITRA S.S., BRAFMAN 0., DANIELS W.B. and CRAWFORD R.K., (to be published).
2. GANESAN S., MARADUDIN A-.A. and OITMAA J., Annals in Physics (in press).
3. RUSSELL J., Appl. Phys. Lett. 6, 223 (1%5).
4. POLLAK F.H. and CARDONA M., Phys. Rev. 172, 816 (1968).
5. LOUDON R., Adv. Physics 13, 423 (1964).
6. PARKER J.H., FELDMAN D.W. and ASHKIN M., Phys. Rev. 155, 712 (1967).
7. KITTEL C., Introduction to Solid State Physics, p. 125 3rd edition, Wiley, New York (1966).

Nous avons effectué les premieres recherches expbrimentales des

effets de tension uniaxiales statiques sur la fréquence des phonons
opt iques avec q ~ 0 dans un crystal du type du diam ant. Nous avons
trouvê que l’application de tension uniaxiale dans les direction
[001] ou [iii] cause des divisions et deplacements des bande de
l’effet Raman des phonons optiques triplement dêgénêrês avec
q ~ 0. Des division observées nous avons calcul~ les valeurs
expérimentales pour les co~fficients phénoménologiques qui
decrivent les changements des constantes de forces de ces phonoris
avec le deformation. Nos r~sultatsconfirment raisonnablement Ia
theorie dynamique des reseaux.