Photoelectrolysis of water: Si in salt water

Rodica M. Candea, Marc Kastner, R. Goodman, and N. Hickok

Citation: Journal of Applied Physics 47, 2724 (1976); doi: 10.1063/1.322995
View online: http://dx.doi.org/10.1063/1.322995
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/47/6?ver=pdfcov
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Photoelectrolysis of water: Si in salt water*

Rodica M. Candea, Marc Kastner, R. Goodman, and N. Hickok
Physics Department and Center for Materials. Science and Engineering. Massachusetts Institute of
Technology. Cambridge. Massachusetts 02139
(Received 2 January 1976; in final form \3 February 1976)

Current-voltage measurements are reported for heavily p-type Si electrodes in NaCI solution. The zero
current voltage depends logarithmically on light intensity, indicating that photoelectrolytic devices are solar
cells in series with electrolytic cells. The catalytic efficiency of the electrode is enhanced by illumination,
but Si is a poor hydrogen electrode, probably because of its surface oxide.
PACS numbers: 72.40. + w, 82.6S.lv, 82.4S. + z, 84.60.Dn

The possibility of converting solar energy directly into chemical energy is attractive because it solves the
storage problem associated with photovoltaic solar energy conversion. Therefore, the recent discovery that
sunlight electrolyzes water in the presence of n-Ti0 2 1-5
is very exciting. The process involved is not yet understood, however, and it is not known how to improve the
poor conversion efficiency.
One should first ask whether it is, in principal, possible to make a photoelectrolytic cell (i. e., semiconductor electrodes in an electrolyte) which is more efficient than a solar cell in series with an electrolytic cell.
If the function of the semiconductor is that of a photovoltaic device supplying part or all of the electromotive
force for the chemical reaction, then it is probably better to optimize the photovoltaic cell and the electrolytic
cell separately. One could choose, for example, a Si
solar cell in series with an electrolytic cell with good
hydrogen and oxygen electrodes (e. g., Pt and Co,
respectively). In the latter case one relies on the semiconductor only for its photovoltaic properties and on
the electrodes only for their catalytic properties. On
the other hand, it is possible that exposing a semiconductor electrode to light might alter its catalytic properties as well as providing the photovoltage. If this
were the case, it might be possible to construct a photoelectrolytic cell which would be as efficient as the hybrid
photovoltaic-electrolytic cell. Of course, such a device
would be less expensive to construct than the hybrid
cell.
As discussed below it is very difficult to determine
whether the catalytic properties of Ti0 2 are altered by
light. However, we report here results using Si electrodes which indicate that the semiconductor becomes a
better catalyst for electrolysis of water when illuminated. We also find, however, that Si is not useful as a
hydrogen electrode because other chemical reactions
dominate near equilibrium.

The Si electrodes were etched in HF before being

placed in the electrolyte. It was found that in NaCI solution the current-voltage (1- V) curves were reproducible;
however, in other electrolytes (e. g., 1% H2S0 4), they
were not. The results are sensitive to the presence of
O 2 in the electrolyte. He or H2 was bubbled through the
NaCI solution to eliminate oxygen. Contact was made to
the Si by evaporating a thin layer of Al on the back of the
sample and connecting a copper wire to the Al film with
Ag epoxy. The entire contact was then covered with
epoxy to isolate it electrically from the electrolyte.
The 1- V characteristics were measured while the
electrode was exposed to different light intensities (L)
using a tungsten-iodine lamp (maximum intensity Lo
= 1. 4 W/cm 2) and neutral density filters. The 1- V
curves for a typical sample are shown in Fig. 1. The
point on each curve at which 1 = 0 is the thermodynamic
equilibrium, and the voltage at that pOint, Veq, measures the Gibbs's free energy of the chemical reaction
t:.G = eV eq For the dark 1- V curve, Veq = - 1 V (SCE),
whereas the reaction ~H2 =H+ + eO has Veq = - O. 65 V
(SCE). Therefore, some other chemical reaction determines the equilibrium voltage. This is discussed further
below. If the electrode is acting as a photovoltaic cell
in series with the electrolytic cell, then we expect6
Veq = (kT / e)(2. 303) logl0(1 + CL) + V;:'.

(1)

C is a constant that depends on generation and recombination rates. At high light intensities, Veq should be
proportional to 10gL, and at room temperature the slope

S, ELECTRODE POTENTIAL

-1.5

(S. C. E.)

(VOLTS)

-OA

-1.0

:2
u
"11.
~

:2

____________________~~~~~~~__~O

'"

p-type Si (5 x 1018 to 5 X 10 19 majority carriers) was

used as the hydrogen electrode (cathode) in O. 1M NaCl.
A bias voltage was applied between the Si electrode and
a Pt electrode, and the potential of the Si electrode was
measured relative to a standard (saturated) calomel
electrode (SCE). The current flowing through the Si
electrode was also measured. It was ascertained that
H2 gas was produced at the Si electrode by collecting a
large volume of the colorless odorless gas and igniting
it.

FIG. 1. I-V characteristics for p-Si (5 xl 01B to 5 xl 0 19 carriers) electrode in O.lM NaCI at various Ught intensities.

2724

Copyright 1976 American Institute of Physics

Journal of Applied Physics, Vol. 47, No.6, June 1976

5
6

7
8

140.00
14.00
7.00
4.40
1.40
0.70
0.14

>f-

-IO~
w
0

f-

-15

r;s

a:
a:
:::>
u

-20

2724

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14:14:42

-I

0.3
-(3

(fl

,..-~---

...J

>

CT

-0.8 >Q)

0.2

-5.0

./

(3

...J

<t

-5.5
_0

(B

'"

a.

011

-0.9 ~
w

-6.0

a:
a:
=>
u

a:
w

OO~-L

-4

LL_ _ _ _L-_ _ _- L_ _ _ _L -_ _ _--.J- 1.0

______~________l -______~______~
-3

-2
log

FIG. 2. Zero current potential Veq versus logarithm of light

intensity. Lo~1.4 W/cm2

-I

L/Lo

FIG. 4. Transfer coefficient (3 and the logarithm of the exchange current versus logarithm of light intensity from exponential portion of data of Fig. 3.

is expected to be 0.059 V. In Fig. 2, Veq is plotted

against 10gL and is linear with slope 0.06 0.005 V in
excellent agreement with Eq. (1). Preliminary measurements show that Veq is proportional to logLo for nTi02 also. !twas found that the photovoltage was larger
when the electrolyte contained oxygen than when H2 or
He was bubbled through it. When H2 is in direct contact
with the semiconductor surface, the photovoltage is
drastically reduced as has been observed previously. 6.1
For V much more negative than Veq, the current depends approximately exponentially on the overvoltage,
1)=V- Veq, as seen in Fig. 3. This exponential behavior

continues up to approximately 200 JlA/cm 2 at which current the effects of bubbles are seen.
As discussed below, the surface of the Si electrode is
probably covered with Si02 for V less than Veq. Therefore, the equations of the electrode kinetics are quite
complicated. 8-14 The exponential dependence of i on 1) indicates that the slow step in the chemical reaction has
an activation energy which is reduced by the applied potential. We therefore write the current as
i = io exp(- (3e1)/kT) ,

(2)

where (3e1) is the reduction of the activation energy and

io is the exchange current.
As shown in Fig. 4, {3 changes rapidly with light intensity at low intensities and saturates at higher intensities at 0.28. This should be compared with values of
[3 for other electrodes. For example, metals 15 have values of {3 typically in the range 0.4- O. 6. io is quite
constant at (1.6 0.7) x 10-6 A. This is surprising since
the increase of {3 should cause a large increase of i o. ns
is probably determined by the surface state density at
E F , and may increase or decrease depending on how that
denSity depends on E F

OVERVOLTAGE 11 = V-Veq (VOLTS)

-0.5

-0.4

- 0.3

-0.2

-0.1

;:::...-.=;---=::,..:.....--r=-;,rn:--...,----,:----,_ 4.7

-5.0

L ( 10-3x W: TTS)
M2
I

2
3

4
5
6
7
8

700.00
140.00
14.00
7.00
4.40
1.40
0.70
0.14

CI

-5.5

L-_ _ _ _ _---L---L_ _.-l....-_----lL--..l-l_ - 6.0

FIG. 3. Overvoltage. 11 = V - V 8Cl versus logarithm of current

for the data of Fig. 1. From currents between the knee at logi
~ - 5.5 (i ~ 3 I-IA/cm2 ) and i ~ 200 I-IA/cm2 the dependence is
exponential.
2725

J. Appl. Phys., Vol. 47, No.6, June 1976

We have made 1- V measurements on less heavily

doped (p = 1. 5-15 n cm) p-Si. These show a very small
dark current even at 1) = - 2 V, and a saturation current
under illumination. The saturation current is proportional to the light intensity and corresponds to approximately one HaO neutralized for each photon adsorbed
by the semiconductor. These results are similar to
those reported for n-Ti0 2 oxygen electrodes. 1.2 The
small dark current is probably the result of the large
space-charge region in the less heavily doped semiconductors which results in blOCking contacts. Because
of this blocking contact, it is difficult to determine the
parameters {3 and io for such materials. In our neardegenerate Si samples, electrons can tunnel through the
thin barrier.
Candea et al.

2725

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14:14:42

Since (3 increases with light intensity, we conclude

that the catalytic properties of the Si surface are improved in the presence of light. However, even at high
light intensities (3 for Si is not as high as for most
metals. This, on the other hand is not the most important reason why Si is a poor hydrogen electrode.
Rather, the fact that Veq is so large is evidence that
some other chemical reaction prevents hydrogen production at lower bias. It is possible that the oxide on
the Si surface must be reduced before H30+ neutralization can take place, or that near Veq the reduction of
Si0 2 to Si and neutralization of H30+ take place
simultaneously.
Our experiments on Si suggest that a successful and
efficient photoelectrolysis cell can be constructed if the
proper semiconductor-electrolyte combination can be
found. The semiconductor acts as a solar cell in series
with an electrolytic cell as indicated by the logarithmic
dependence of Veq on light intensity. Thus, one must
choose a semiconductor which has a high photovoltage
(i. e., a relatively large-gap material). However, as
with all solar cells, if the gap is too large, most of the
solar energy will not be adsorbed. This is probably the
reason for the low efficiency of Ti0 2 The most important electrochemical requirements are the following:
the reaction H+ + e- =iH2 must be able to come to equilibrium at the semiconductor hydrogen electrode or the
reaction = = io 2 + 2e- at the oxygen electrode and the
electrodes must be chemically stable in the electrolyte.
These requirements can be tested even on lightly doped
material. However, the measurement of the effect of
illumination on catalytic efficiency can be carried out

2726

J. Appl. Phys., Vol. 47, No.6, June 1976

only with heavily doped semiconductors. We have shown

using heavily p-type Si that light-induced enhancement
of catalysis can take place.
We gratefully acknowledge the support and encouragement of Pierre Aigrain and the Luce Professorship in
the early stages of this work.

*Supported in part by NSF grants.

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Candea et al.

2726

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