Solid State Communications, Vol. 15, pp. 321—324, 1974. Pergamon Press.

Printed in Great Britain

RAMAN SCATFERING IN THE DEPLETION REGION OF GaAs*

R. Tsu, H. Kawamurat and L. Esaki

IBM Thomas J. Watson Research Center, Yorktown Heights, New York 10598, U.S.A.

(Received 18 January 1974 by J. Tauc)

We have obtained spectra for the LO phonon mode by Raman scattering

associated with surface quantization of the hole states in the depletion
layer of highly doped n-type GaAs samples. When semi-transparent metal
contacts are employed, the zone-center LO peak shifts to higher frequency
due to plasmon-phonon interaction. The observed effects are not sensitive
to the types of metal. The presence of the plasmon mode is thought to be
due to the steady-state carrier injection from the incident laser light. The
position of the peak is used to estimate the surface recombination rate of
the excited electron—hole pairs.

1. INTRODUCTION In conjunction with the explanation of their data for

IN AN n-type semiconductor such as GaAs, a large
density of surface states in the forbidden gap pins the
Fermi level within the gap, causing the electronic
energy bands to bend up towards the surface. ~ is
well known that a free surface is p-type for an n-type
GaAs, i.e., the Fermi level is closer to the valence
band. Mead and Spitzer’ have shown that the position
of the surface Fermi level for Ill—V compounds is
pinned at a value about one third of the gap energy
measured from the valence band edge. Furthermore,
the position of the Fermi level is rather insensitive to
the type of metal at a metal—semiconductor interface,
The absorption length for 51 45A laser light in GaAs is
only about 200A.2 Thus one does not expect to
observe the usual plasmon—optical phonon coupling
reported by Mooradian and Wright3 because the
absorption distance is less than the thickness of the
depletion layer.
Corden, Pinczuk and Burstein4 have discussed
some aspects of surface-field-induced Raman scattering,
____________
* Research sponsored in part by the Army Research
Office, Durham, N.C.
I’ Physics department, Faculty of Science, Osaka
University, Japan.
degenerate n-InAs—oxide—Pbjunctions, they suggested
that the wavevectors of those LO phonons participa-
ting in Raman scattering are determined by the thick-
ness of the space charge accumulation layer at the
surface (—‘ 50A), which is much less than the thickness
of the depletion layer. They argued that the position
of the LO peak should appear at the unscreened
frequency for LO, because the Debye length for
plasmons is longer. We present results for highly
doped n-type GaAs, actually giving a spectrum of the
LO phonons associated with surface state holes which
are localized by the large band bending. We call these
momentum nonconserving LO phonon scatterings
LOSQ, LO phonons associated with surface quantiza-
tion. These phonons usually have wavevectors much
greater than the wavevectors of the incident and
scattered lights, thus momentum is not conserved in
the process. When semitransparent metal contacts are
made, even more surprising results are obtained. In
addition to the LOSQ mode, a broad LO peak appears
at a higher frequency indicating interactions of
phonons with carriers.
2. SCATTERING FROM LO PHONONS
INVOLVING SURFACE QUANTIZATION
Figure 1(a) shows the spectrum for a low carrier

321
322 RAMM4 SCATTERING IN ThE DEPLETION REGION OF GaAs
I I I k
6cm’3
NrlO’ 269
~ N~2.9xI018cm3 269
291
310 300 290 280 270 260
FREQUENCY SHIFT (cm’)
FIG. 1. Raman spectra of LO and TO phonons. (a)
semi-insulating GaAs (111) orientation (b) highly
3, and
dopedorientation,
(111) n-type GaAs with N—2.9 X 101k cm
density n-type GaAs sample. An argon laser at 5145A
has been used in the back scattering geometry along
(111), and various polarizations between the incident
and scattered light beams are employed in the measure-
ments. However, for the case of highly doped n-GaAs
shown in Fig. 1(b), in addition to the usual LO and
TO peaks, the data clearly indicate that something
else is present. When cross-polarization is used for
crystal of Td symmetry with (111) orientation, the
measured spectrum shows only a TO mode with
Lorentzian line shape having its peak at 269 cnf’.
However, in measurements on samples with (100)
orientation only the LO mode is excited. The line
shape of the LO mode for the highly doped sample is
skewed, having higher intensity at the lower frequency
side of the peak located at 291 cm”. The spectrum of
the LOSQ mode is resolved by subtracting the LO and
TO peaks with symmetric line shapes. The peak of the
LOSQ mode is found to be 286 cm’. If we assume
that the scattering is due to the process shown in Fig.
2, where all but the hole states denoted by b are
plane wave states, momentum is not conserved. In
order to estimate the position of the peak in LOSQ,
we take the wave function for the state b to be5
~I~b= (b3/2)”2 z exp(—bz/2),
where b = (12 m*e2Nd/ch2)h/3, in which e is the
permitivity of the medium, m*, the hole mass, N, the
Vol. 15, No.2
q,w
(a) _________
- _
FIG. 2. Graph showing the momentum non-conserving
denoted by b are plane wave states.
(b) process in Raman scattering, all states except one
carrier concentration and d, the depletion thickness,
all in MKS units. Taking 3 X 1018 cm3 for N, 0.9 V
for the surface barrier potential for GaAs, we obtained
d = 200A and b = 2.1 X iO~cm’1. Stern and Howard~
250
have shown that this wave function gives excellent
results for the ground state energy as compared to the
self-consistent numerical computations. The average
extent of the electron wave function, z
determines the most probable value for0wavevector
= 3/b, of
the LO phonon, K
0 z~’= b/3 = 7 X 106 cm’. Using
‘~
6 we find
the scattering
that wLo(Ko)data
= 287
by cm’1,
Waughwhich
and Dolling,
is in good agreement
with our spectrum. Since the ground state energy is of
the order of a few kbTat room temperatures, effects
of surface quantization may be difficult to observe,
however, since the collision broadening is of the order
of a few meV, the quantized state should be well
defined. The calculated line shape for the LOSQ mode
based on our model gives good agreement with the
measured.7 As mentioned earlier, the absorption
depth is of the order of the depletion thickness, the
usual LO peak appears at 291 cm’1, which is the
position corresponding to an absence of carriers.
3. SPECTRAWITh METAL CONTACTS AND
BIAS VOLTAGES
We evaporated stannic oxide semi-transparent
electrodes on the same sample as well as other ones.
In addition to the LOSQ contributions broad peaks
appear at frequencies above 291 cm’ as shown in
Fig. 3(a)—(c). It is hard to maintain that the shift is
due to plasmon—phonon interaction, because the
reversed bias case should increase d, further depleting
the surface. We think that the shift is due to the inter-
action of LO phonons with plasmon excitations of
the steady-state carrier distribution induced by the
illumination. Furthermore, this shift is not present for
a free surface. Suppose i’~denotes the surface
Vol. 15, No.2 RAMAN SCATTERING IN ThE DEPLETION REGION OF GaAs 323

where the peak appears at 298.5 cm’. This value

corresponds to a value8 of n0 = 1017 cnf~.At
I I I I I I

I ~I0mA
equilibrium, w = noEgV/rrn, where the laser power
input, energy gap and the volume of the absorbed light
V~I.0vFORW4RD BIAS -
are respectively, w, E, and V. The best estimate for
these quantities are w = 0.1 W, Eg = 1.5 eV, and V=
200 pm X 400 pm X 200A, giving the value of Tm =
5 X 10’i~sec.For bulk GaAs, the recombination
I~0 (b) time TB is of the order of a few nanoseconds. Our
~ V~0.3vFORWARD BIAS
results then indicate a surface recombination time
shorter than the corre~spondingbulk value, which is
2985 286 / ~
consistent. If ~ < I0’bo sec., the steady-state carrier
density would be too low to show an appreciable
I-.
0 shift. Since TB > Tm, under forward bias condition,
(1) I
surface recombination time is increasing toward the
I ~-IOmA bulk value, resulting in a higher steady-state density,
N 29 18cm3298 BIAS 284
v~—EvERSE ,‘ /
and hence,
measure a larger
surface shift. Our model
recombination time.explains the
There appears to
x10 observed shift and possibly serves as a new means to
have a.shift in the position of the LOSQ mode to lower
frequencies when bias voltages are changed from
320 310 300 290 280 270 260 250 forward to reverse. This slight shift is thought to be
FREQUENCY SHIFT (cm~) due to the narrowing of the depletion layer, i.e.,
FIG. 3. Raman spectra for LO and TO phonons for the decreasing z
0, thereby increasing K0. Also, from the
same sample as in Fig. 1(b) but semi-transparent con- linewidth of the shifted LO peak, we obtain a value
tacts are deposited on the (111) face of the crystal. for the electronic relaxation time of 910—13 sec.,the
exceeds
assuming that the
phonon broadening. plasmon broadening
recombination time for the free surface and Tm~the
surface recombination for the case where metal con-
One of the purposes of this investigation was to
tact is present, if Tm ~ r~,the steady state carrier study the possibility of electron tailing into the semi-
concentration for the free surface will be too low to conductor from the metal surface~° Although our
show a shift. Let us estimate the value of Tm. We data do not rule out this possibility, we feel that it is
shall assume under equilibrium conditions, that the more likely that the observed changes are due to
free electron density and free hole density are equal, phonon interaction with plasmons formed by the
i.e., n
0 = Po~Due to the smaller electron mass, we steady state carrier injection.
may further assume that all of the shift in the peak
position is due to interaction with free electrons n0. Acknowledgement We are pleased to acknowledge
—

Consider, for example, the case shown in Fig. 3(b), many helpful discussions with W.E. Howard.

REFERENCES
1. MEAD C.A. and SPITZER W.G.,Phys. Rev. 134, A713 (1964).
2. PHILLIPS HR. and EHRENREICH H.,Phys. Rev. 129, 1550 (1963).
3. MOORADIAN A. and WRIGHT G.,Phys. Rev. Lett. 16,999 (1966).
4. CORDEN P., PINCZUK A. and BURSTEIN E.,Proc. 10th mt. Conf. Phys. ofSemiconductors (Edited by
KELLER S.P., HENSEL S.C. and STERN F.) p. 739. United States Atomic Energy Commission (1970).
324 RAMAN SCATTERING IN THE DEPLETION REGION OF GaAs Vol. 15, No.2

5. STERN F. and HOWARD W.E.,Phys. Rev. 163, 816 (1967).

6. WAUGH J.L.T. and DOLLING G.,Phys. Rev. 132, 2416 (1963).
7. To be published.
8. VARGA B.B.,Phys. Rev. 137, A 1896 (1965).
9. TSU R.,Phys. Rev. 164, 2, 380 (1967).
10. This idea was suggested to us by BARDEEN J.

Durch Ramanstreuung unter Beteiligung der quantisierten Locherzustande

in der Verarmungsrandschicht von hochdotiertem n-GaAs haben wir
Spektren für die LO-Phononen erhalten. Wenn semitransparente Metallkon-
takte verwendet werden, verschiebt sich als Folge der Plasmon—Phonon-
Wechselwirkung der Peak von LO-Phononen nahe der Mitte der Brfflouin-
Zone zu höherer Energie. Die beobachteten Effekte sind vom Elektro-
denmaterial unabhangig. Das Auftreten der Plasmamode wird den durch das
einfallende Laserlicht erzeugten stationaren Ladungstragern zugeschrieben.
Die Lage des Peaks kann für eine Abschatzung der Oberflächenrekombina-
tionsrate der angeregten Elektron-Loch-Paare verwendet werden.