Journal of Electroanalytical Chemistry, 367 (1994) 27-30 27

Study of the Schottky barrier and determination of the energetic

positions of band edges at the n- and p-type gallium indium phosphide
electrode 1electrolyte interface

Shyam S. Kocha l

Department of Mechanical Engineering, University of Hawaii at Manoa, Honolulu, HI 96822 (USA)

John A. Turner l * and A.J. Nozik

National Renewable Energy Laboratory (formerly the Solar Energy Research Institute), 1617 Cole Boulevard, Golden, CO 80401-3393 (USA)

(Received 5 August 1992; in revised form 11 June 1993)

The ternary semiconductor GaInPz (or Ga,,sIn,,5P) was studied as a single-crystal electrode in contact with various aqueous
electrolyte solutions (pH range 2.0-12.0). The photoelectrochemical properties of the epitazially grown GaInP, layers were
characterized using techniques of current-voltage, capacitance-voltage and photocurrent spectroscopy. The results of capaci-
tance-voltage measurements carried out at discrete frequencies from 100 Hz to 10 kHz demonstrate the presence of a depletion
zone over the voltage range studied. This allowed the experimental determination of both the flat-band potential and the energetic
positions of the band edges for both n- and p-doped GaInPz at the semiconductor lelectrolyte interface. These studies reveal the
applicability of this relatively new material for the photoelectrochemical decomposition of water.

1. Introduction tions for water splitting were reported at that time. As

The thermodynamic potential for splitting water into
hydrogen and oxygen is 1.23 eV at 25°C. Since a
cathodic overpotential of 100 mV and an anodic over-
potential of 200 mV are typical values for water elec-
trolysis, an effective semiconductor-based photoelec-
trolysis device should produce a photopotential of at
least 1.6 V. Most well-known semiconductors for pho-
toelectrolysis applications are unsuitable for water
splitting, as a result of large band gaps, stability prob-
lems or band edges that do not span both redox poten-
tials of the hydrogen and oxygen evolution reactions.
The ternary semiconductor alloy system Ga,In,_,
(0 <x < 1) has been the subject of an earlier study [l].
The band gap varies from 1.35 eV (direct) for InP to
2.25 eV (indirect) for GaP. Favorable band edge posi-
l Present address: National Renewable Energy Laboratory,
Cole Boulevard, Golden, CO 80401 3393, USA.
l * To whom correspondence should be addressed.
a result of the presence of indium in the material, it is
thought that a surface layer of InO, would form, stabi-
lizing the surface in much the same way that that oxide
stabilizes indium phosphide [2-51. Thus, it was consid-
ered a promising candidate as a photoelectrolysis elec-
trode, as well as an interesting material for characteri-
zation. Our study focuses on single-crystal n and p
electrodes, where x = 0.5.
GaInP, has been studied at the National Renewable
Energy Laboratory (NREL) as a promising material for
solid state photovoltaic applications [6,7]. The band
gap of the material ranges from 1.83 to 1.89 eV,
depending on the growth conditions. In this paper, we
report the results from impedance studies carried out
in various aqueous electrolyte solutions spanning a
wide pH range. Values for both the flat-band potential
and band edge potential of GaInP, were determined.
1617 In addition, photocurrent measurements were also per-
formed to determine direct and indirect band gaps for
the material.

0022-0728/94/$7.00 0 1994 - Elsevier Sequoia. All rights reserved

SSDZ 0022-0728(93)03020-P
28 S.S. Kocha et al. / Schottky barrier and band edges of GaIP,

2. Experimental CH,COOH + 0.05 M CH,COONa, pH 4.8; 1 M KC1

GaInP, wafers were grown in house at NREL, in a
vertical, air-cooled reactor at ambient atmosphere, us-
ing the metallo-organic chemical vapor deposition
(MOCVD) technique [6,8]. Samples were used as re-
ceived from the MOCVD reactor; no etching was car-
ried out. The group III source gases were trimeth-
ylindium, trimethylgallium and trimethylaluminum; the
group V source was phosphine and the dopant sources
were diethyl zinc (DEZ) and hydrogen selenide. The
carrier concentrations ranged from 1 X lO”j to 1 x lo’*
cmw3. The GaInP, epilayers were 2-3 pm thick. The
electrical contacts were made by scratching the back
surface to create defects and then fusing indium wire
at 300°C for 3 min in an atmosphere of 9 : 1 nitrogen +
hydrogen mixture.
The epilayer samples with ohmic contacts were
mounted on an electrode tip (a stainless steel screw
covered with Teflon on the sides) coated with silver
epoxy. This assembly was then heated to 140°C for 1 h
to set it. Epoxy resin was then applied, covering the
electrode tip in such a way that only the sample surface
was exposed and the electrical contact was insulated.
The sample surface areas were determined using a
photographic technique. The electrode thus prepared
was screwed onto a stainless steel shaft covered with
Teflon. A three-electrode system was used with plat-
inum mesh as the counterelectrode, a saturated calomel
electrode (SCE) as reference electrode and the semi-
conductor mounted on the stainless steel shaft insu-
lated with Teflon as the working electrode.
The apparatus used for the capacitance-voltage
measurements consisted of a PAR 5204 lock-in, a PAR
173 potentiostat, a Tektronix function generator and a
+ 0.1 M Na,B,O,, pH 9.1; 1 M KC1 + 0.01 M NaOH,
pH 12.0. All the pH values were verified with a pH
meter.
Distilled water, further purified by passing through
an ion exchange system, was utilized for electrolyte
preparation and sample rinsing.
3. Results
The current-voltage curves obtained for p-type sam-
ples were as expected and showed a low cathodic
current density below the open-circuit voltage down to
about - 1.0 V; the n-type crystals showed a low anodic
current density above the open-circuit voltage up to
about 1.0 V. The reverse currents increased when the
samples were exposed to light with an energy above its
band gap.
The capacitance measurements were carried out by
scanning over a voltage range in the regions where the
current flow was nearly zero. Typically, the measure-
ments were carried out at frequencies between 100 Hz
and 10 kHz. Figure 1 shows typical Mott-Schottky
(M-S) plots (l/C* us. V) of n- and p-type semiconduc-
tors at 5 kHz. The data at other frequencies almost
coincide with those shown, so have not been plotted
for clarity. The plots show a linear relationship over
most of the voltage range. Practically no hysteresis was
seen in any of the samples that were biased in the
voltage range where negligible current flowed. If a
p-type sample was biased to a voltage that was positive
of its flat-band potential, for example, then oxidation
of the surface occurred (pits were seen under the
1s ,,,,,,,,,,~,,,,,~,,,,,,,r,,,,-300

PDP11/23 computer. The data acquisition is semi-au-

tomated. The computer scans a voltage range (forward 14 -
f :250
and reverse), acquires in- and out-of-phase data from i
the lock-in, does a linear least-squares fit, analyzes the 12 - e
0
q
on
B
flat-band potential and dopant density data, and plost, 0 - 200
prints and stores the data on disk. “: IO- 0
0 /
IL 0 0 p-type _
The apparatus used to carry out the photocurrent “E
0 8
q n-type
p 8.0 -
0
q
0 - I50
spectroscopy consisted of a 250 W Oriel tungsten halo- 0
i, 0
gen quartz lamp, a monochromator, a chopper, some I r$
0 6.0 - B
optical filters to eliminate second-order light, an IBM - 100
c- sg-
PC, and a PAR 5204 lock-in.
4.0 -
All chemicals were reagent grade. Before commenc- 88

ing the electrochemical measurements, the electrolyte - 50

2.0 -
in the cell was purged of air by bubbling through with
high purity nitrogen. During the measurements, nitro-
gen was passed over the cell to prevent any disturbance
at the interface. Aqueous solutions of the following
compositions were used: 1 M H,SO,, pH 0.0; 1 M Fig. 1. Mott-Schottky plots (f = 10 kHz) for n- and p-type GaInP, in
KC1 + 0.01 M HCI, pH 2.0; 1 M KC1 + 0.05 M aqueous electrolyte of pH 2.1.
 S.S. Kocha et al. / Schottky bam’er and band edges of GaInPz 29

9.0 6.0

300m 8.0
5.0
250 - 7.0

6.0- - 4.0
N
N 200-
-‘? 5.0- 5
L _? -3.0 “H
0)
“; 4.0- 0
‘5
: 150 -
u I 3.0- -2.0
7
0 8 2.0-
loo- 8 -1.0
‘E ‘, 1.0
B 8
8 8
0.0 1.5
50 -
1.65 1.7 1.75 1.8 1.85 1.9 1.95
Energy/eV
o.or, I I I1 I I I I,15 0 3 1 I cs 1 I”““(
Fig. 4. Band gap analysis of GaInP, for direct (Z’) and indirect
-1.2 -I -0.8 -0.6 -UA -0.2 0 0.2
(1”‘) gaps.
E/V vs. 6cE
Fig. 2. Mott-Schottky plots of a p-type GaInP, sample at pH values
of 2.0, 4.8, 9.1 and 12.0 (all at 5 kHz). Forward and reverse sweeps
are shown. same relative to the redox potential of hydrogen evolu-
tion and oxygen evolution at different pHs.
Photocurrent spectroscopy was carried out on the
microscope), and the M-S plots became non-linear and samples to determine their band gaps. A potassium
showed hysteresis. The doping densities calculated from ferro-ferricyanide redox couple was added to the elec-
the M-S plots were of the same order as that obtained trolyte to a concentration of 1 mM each before carry-
from Hall measurements. ing out the measurements. The electrode was exposed
Figure 2 shows M-S plots of a p-type sample at to light that scanned wavelengths of 600-900 nm
various pH values (for simplicity, only one frequency through an optical window (in the cell) in steps of l-2
was plotted). It was found that, as expected [9-121, the nm. Figure 3 shows a plot of the photocurrent versus
flat-band potential shifts positively with decreasing pH, wavelength for a p-type GaInP, electrode under re-
indicating a surface oxide layer. The pH dependence of verse bias. Assuming that the current flow near the
the flat-band potential was linear, with a slope of band gap is proportional to the absorption coefficient,
approximately 60 mV per unit of pH for most samples, one can use the photocurrent response to obtain the
so that the position of the band edges would be the optical transition modes [13]. By plotting a function of
the current versus the energy of the incident light, and
extrapolating to zero, the direct band gap was found to
121
be about 1.83 eV (Fig. 4). An indirect gap of 1.78 eV
was also found upon further experimental analysis. An
indirect gap for this material has not previously been
IO-
reported. The explanation for this result awaits more
a
detailed analysis and band structure calculations, which
2 8.0- is beyond the scope of this publication.
!
3
,o 6.0- 4. Discussion
e
P
x
“9 4.0-
Based on the measured values of the flat-band po-
tential (US. SCE) and the band gap, the conduction and
valence band edges were determined. The effective
2.0-
density of states (based on electron and hole effective
masses) and carrier concentrations (Hall measurements
1.65 1.7 1.75 1.8 1.85 1.9 1.95 2 2.05 2.1
and M-S plots) were used to calculate the position of
Energy/eV
the Fermi level relative to the conduction band (n-type
Fig. 3. Photocurrent spectroscopy of p-GaInP, in H,SO, with 1 mM samples) and valence band (p-type samples) [14,15].
each of Fe(CN),-3 and Fe(CN),-4. The energy difference between the Fermi level and the
 S.S. Kocha et al. / Schottky barrier and band edges of GalnP,
:I
---
-- _ ---- --> HZ
EHZO
0.0
>
tw
I Acknowledgments
H
w
1
+1 .o EH~O -> 02
----
+2.0
t 1 A.M. Redon, J. Vigneron and J. Chevallier, J. Electrochem. Sot.,
Fig. 5. Band gap edges calculated from flat-band potentials for
different samples of GaInP, in electrolytes of pH 2.1: 1, [n] = 2.0~
10” cmm3; 2, [n]= 2.0X10” cm-3; 3, [n]= 7.7X lOI6 cmw3; 4,
[p] = 5.0 x 10” cmm3; 5, [p] = 6.0 x 1Or6 cmw3; 6, [p] = 2.0 x 10”
cme3; 7, [p] = 4.5 X lOI6 cme3; 8, [p]= 5.0X 1015 cmd3; 9, 2.8X lOI6
cmm3.
valence band edge is only a few millielectronvolts. The
band edge potential and the redox potentials for hy-
drogen reduction and oxygen evolution are shown in
Fig. 5 for pH 2.1.
Although the position of the band edge potentials
seems to shift with the carrier concentration, a more
reasonable explanation for the variation would be dif-
ferent surface morphologies caused by different growth
conditions. These samples were used as received and,
because of the thinness of the epilayers (about 2-3
pm>, were not etched. The shift in Fermi levels with
pH is linear, with a slope of about 60 mV per unit of
pH for most of the samples, except sample 5, which has
a slightly greater slope.
One of the n-type ‘samples has band edges that
encompass the hydrogen and oxygen redox levels. This
indicates that it may be possible to split water using
n-GaInP, if the proper etching procedure is found and
the surface of the material is modified by depositing a
catalyst for oxygen evolution [16] (e.g. RuO,). The
stability of such electrodes will also have to be investi-
gated.
Similarly, the p-type samples will perform better as
photocathodes if a catalyst [17,181 for hydrogen evolu-
tion is used on the electrode. Preliminary work on the
deposition of platinum films on p-type GaInP, and
RuO, deposition on n-type GaInP, is currently being
carried out.
The authors wish to thank Jerry Olson, Sarah Kurtz
and Alan Kibbler for the GaInP, samples. This re-
search was supported by the Hydrogen Program of the
US Department of Energy.
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