Minoritycarrier lifetime study of the pressure induced X crossover in GaAs

M. Leroux, G. Pelous, F. Raymond, and C. Verie

Citation: Appl. Phys. Lett. 46, 288 (1985); doi: 10.1063/1.95661
View online: http://dx.doi.org/10.1063/1.95661
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Minority-carrier Ufetime study of the pressure induced r-x crossover in GaAs
M. leroux, G. Pelous, F. Raymond, and C. Verie
Laboratoire de Physique du Solide et Energie Solaire, Centre National de la Recherche Scientifique, Sophia
Antipolis, Rue Bernard Gregory, 06560 Valbonne, France
(Received 13 September 1984; accepted for pUblication 12 November 1984)
Room-temperature continuous and time-resolved (on a nanosecond scale) photoluminescence
experiments have been performed on p-type GaAs. Observation of indirect luminescence in GaAs
above 4 GPa aUowed a direct determination of the room-temperature pressure coefficient of the
X valleys. A new set of pressure dependence parameters for both r and X energy gaps in GaAs
has been determined. These pressure coefficients, together with the intensity ofIuminescence as a
function of pressure, yielded an estimate of the electron lifetime ratio confirmed by subsequent
time-resolved experiments. A threefold enhancement of electron lifetime is observed above the r-
X crossover.
High pressure experiments have proved to be a valuable
tool for studying the influence of variations of band structure
parameters on the electronic properties of semiconductors
materials. In particular, due to the large difference in pres-
sure coefficients of direct and indirect energy gaps, it is possi-
ble to induce a direct to indirect transition in materials such
as GaAs.
l
-4 In this letter high pressure photoluminescence
at room temperature has been used to study the recombina-
tion of minority electrons in p-type GaAs up to 8 GPa (80
kbar). The influence of the band structure on their lifetime is
analyzed quantitatively using two independant sets of ex-
periments carried out on the same sample: continuous pho-
toluminescence to monitor the pressure dependence of the
band gaps and the overall intensity, and pulsed photolu-
minescence study of minority photocarrier lifetime. To our
knowledge, indirect luminescence at room temperature is
observed for the first time, leading to a direct determination
of the pressure dependence of the X band gap. Since this
letter is mainly concerned with minority electrons, a two-
band model (r ,x ) is used for fitting experimental data.
In order to avoid surface recombination effects,5 the
sample studied in this work is a molecular beam epitaxy
grown,p-type Gao. IS Ala.8S As/GaAs/Gao.ls As double
heterostructure. The 4-pm-thick active layer is Be doped to
p = 1.5 X 10
1M
cm -3. A l000-A-thick heavily p-type top lay-
er of GaAs, which is used to protect the reactive AI-rich
window, gives a negligible contribution to photolumines-
cence due to high surface recombination velocity of bare
GaAs. The sample, thinned down to 50 pm and cleaved in a
small bit of about 100 pm, is placed together with ruby pow-
der in a NationallBureau of Standards type diamond anvil
cell. Pressure is monitored by the wavelength of the R I lumi-
nescence line ofruby.6
Continuous photoluminescence experiments were car-
ried out using the 488-nm hne of a 10-mW argon laser fo-
cused on a 50-pm-diam spot. Detection is performed
through a 1.15-m spectrometer by a cooled GaAs photomul-
tiplier and a photon counting system. Luminescence decay
experiments were performed using a 20-nJ pulse of a N 2
pumped Coumarin 503 dye laser. The light pulse less than 1
ns in width was focused on a :::::::: lOO-,Um-diam spot and the
luminescence was analyzed through a 0.3-m spectrometer
with a 300-ps Si avalanche photodiode followed by a Boxcar
averager. Time-resolved spectra showed that only direct gap
luminescence could be measured during these pulsed experi-
ments.
Continuous luminescence spectra at various pressures
are displayed on Fig. 1. The average temperature of the sam-
ple under light excitation, deduced from the slope of the
high-energy tail of the luminescence, is about 345 K. Direct
band-gap luminescence exhibits a rapid shift towards high
energies with increasing pressure. A sudden decrease of the
luminescence intensity is observed past 3.5 GPa due to elec-
tron transfer from to conduction-band minima.
However, this decrease saturates due to the fraction ofpho-
toelectrons excited in r which recombine radiatively be-
fore thermalization to the X valleys.
4
In addition to r I umi-
nescence, a broad, low intensity band appears above 4 GPa.
We observed this band with nearly the same energy position
and the same pressure dependence in several bulk n-type
samples. We attributed this luminescence band to indirect
transitions from minima. This luminescence has also


'"
Q.
3
>-10
2
. .1.----'--
],02Ir-----'---'--
1'02l <JOG""

E
.3 T 5.0SGPa
101 I I
1 6.88GPa

8500 sero 7500 7000. 6500
Wavelength CAl
5500
FIG. I. Room-temperature luminescence spectra at various pressures for p-
GaAs (p = 1.5 X 10" em' 3).
288 AppL Phys. Lett. 46 (3). 1 February 1985 0003-6951/85/030288-03$01.00 @ 1985 American Institute of Physics 288
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-4
10 0'---'---.J
2
'---'------'-4---'---'-6--.l.----'a
P (GPo)
FIG. 2. (a) Pressure dependence of the maxima of the direct and indirect
luminescence bands. Data for an n-type sample are added as an illustration.
Solid lines: Eq. (I) and (2). (b) Pressure dependence of the normalized lumi-
nescence intensity for the p-type sample. Solid line: Eq. (3).
been observed in a previous work.
4
The shift of this emission
band is directly related to the pressure dependence of the X
band gap in GaAs.
Results of continuous photoluminescence are summar-
ized in Figs. 2(a) and 2(b). Figure 2(a) shows the pressure
dependence of the maxima of direct and indirect lumines-
cence bands. As an illustration, results for a bulk n-type sam-
ple with about the same doping level are also included.
Estimating roughly the position of the band gap to be 1/
2 kT below the luminescence maximum, a quadratic fit of
the pressure dependence of the maxima of direct lumines-
cence yields the following expression for the direct gap at 345
K:
E,{eV) = 1.40 0.01
+ (0.125 0.OO5)p - (3.7 0.5)10-
3
p2 (GlPa),
(1)
in good agreement with literature data. 2-4
A linear fit of the variation of the indirect luminescence
maxima with pressure yields the expression
Ex (eV) = 1.9O:!: 0.03 - (1.3 0.2)10-
2
P (GPa). (2)
Due to the uncertainty on the mechanisms of radiative
indirect recombination involved in our samples, which may
however be supposed not to vary with pressure, we shall use
this expression as a rough estimate of the X band-gap pres-
sure dependence. Note that the main uncertainty lies on the
absolute value of the band gap rather on the pressure coeffi-
cient. This coefficient is in good agreement with data ob-
tained at lower temperatures
4

7
but slightly lower than pre-
vious room-temperature determinations.
3

8
The estimated
crossover pressure is 4 0.2 GPa. A 20-meV temperature
289 Appl. Phys. Lett., Vol. 46, No.3, 1 February 1985

o 10
TIme (ns)
FIG. 3. Luminescence decays at various pressures inp-GaAs.
correction to the P = 0 band gaps in Eqs. (1) and (2) has to be
added to obtain 300-K values.
9
Figure 2(b) shows the pressure dependence of the inten-
sity of direct luminescence for our p-type sample. The rise of
intensity up to 3 GPa is due to the photomultiplier response
and variations of the absorption coefficient of the heteros-
tructure's top layers. No attempt has been done to fit this
portion of the experimental curve. Above 3 GPA, the lumi-
nescence intensity is described by the expression
4
{ [
(E, - Ex )] -- 1 'i,x}
1 = 10 1 + - -- exp + -- ,
'ix kT _ 'i
rad
(3)
where are the density of states effective masses of the
and minima, 'i, and 'ix are the recombination life-
times for and electrons, 'inc is an average intervalley
scattering time, and'i
rad
the radiative direct lifetime. Equa-
tion (3) is plotted on Fig. 2(b), using the band-gap variations
given previously, = 0.8Smo (Ref. 9); varies with pres-
sure according to k.p theory. The fitting parameters are
'i,/'ix = 0.35, 'i,,,/'irad = 2.5 X 10-
4
(4)
In order to determine directly the electron lifetime, integrat-
ed direct luminescence decay experiments have been per-
formed. The results are shown in Fig. 3 for various pressures.
'Ul1O
c
CII
E

>-5
o
:2
o
5
FIG.4. Pressure dependence of the luminescence decay time. Solid line: Eq.
(5).
Leroux I)t al. 289
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The decay exhibits an exponential behavior, as expected
when the interface recombination velocity is low. Although
the decrease in luminescence efficiency with pressure de-
creases the dynamic range of the experiment, a marked in-
t
crease in decay time is observed above 3 GPa, as shown in
Fig. 4.
Neglecting reabsorption effects, the decay time for di-
rect luminescence can be described by
1'-1 = 1'r- I + 1'
x
- I _x exp r x 1 + _x exp r x .
[ (
m*)3/2 (E -E )][ (m*)312 (E -E )]-1
m ~ kT m ~ kT
(5)
expressing that in direct gap configuration, the lifetime is
governed by the direct recombination time whereas above
direct to indirect crossover, the r population is the Max-
wellian tail of the X ~ electrons, and the lifetime is then gov-
erned by the indirect lifetime. Equation (5) is plotted on Fig.
4 with l' y = 4 ns and 1'x = l' y/O.35 = 11.5 ns following Eq.
(4).
The agreement is quite satisfactory. Due to low dynam-
ic in luminescence amplitude in time-resolved spectra, a pre-
cise determination of sample temperature is not possible
during pulsed experiments; a temperature of 345 K has been
used, as previously, but a temperature higher by a few tens of
degrees would give a slightly better agreement.
This self-consistency of various sets of experiments
strongly supports the identification of the low intensity band
arising at 4 GPa as indirect luminescence.
In conclusion, high pressure has allowed to monitor
changes in recombination parameters in a single GaAs crys-
tal when the band structure varies. The direct to indirect
transition results in an enhancement of minority-carrier life-
time. Since such a crossover happens as a function of compo-
sition in III-V alloys such as GaAIAs, GaAsP, GalnP, high
pressure experiments allow to simulate the band structure of
these aHoys, together with the attractive feature of band-gap
variations monitored on a single crystal, free from structural
or chemical disorder. This indicates that Alx Gal _ x As with
290 AppL Phys. Lett., Vol. 46. No.3, 1 February 1985
x ~ O . 4 with adequate quality could present a large electron
lifetime. Therefore, these GaAs-related alloys could be of
major interest to the realization of minority-carrier devices
having improVed performance with larger electron lifetime.
This is an attractive feature for large gap solar cells for multi-
spectral conversion.
This work is supported by the Energy Program
(P.I.R.S.E.M) of the Centre National de la Recherche Scien-
tifique and by the French Agency of Energy Management
(A.F.M.E). The authors gratefully acknowledge C. Chaix
(ISA RIBER) and 1. P. Contour for growing the sample
studied in this work, and 1. M. Besson and 1. P. Pinceaux for
their help with high pressure equipment.
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