228 J'. F,lectrachem. Sac.

: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y January I980

15. S. Guha and F. Hasegawa, Solid-State Electron.,
20, 27 (1977).
16. T. Am b ri d g e, J. L. Stevenson, and R. M. Redstall,
To be s u b m i tt e d to This Journal.
17. D. L. Lile and D. A. Collins, Electron. Lett., 14, 457
(1978).
18. W. C. Jo h n so n and P. T. Panousis, IEEE Trans.
Electron DevLces, ed-18, 965 (1971).
19. K. Hesse and H. Strack, Solid-State Electron., 15,
767 (1972).
20. C. P. Wu, C. W. Mueller, and E. C. Douglas, IEEE
Trans. Electron Devices, ed-22, 319 (1975).

Observation and Analysis of Surface

States on TiO Electrodes in Aqueous Electrolytes
R. H. Wilson*
General Electric Company, Research and Development Center, Schenectady, N e w York 12301

ABSTRACT
W h e n a TiO2 e l e c tr o d e in an aqueous el ect r o l y t e is biased enough positive
of its flatband potential and then pt~otoexcited w i t h light of w a v e l e n g t h sh o r t er
than 400 nm, p h o t o c u r r e n t is observed. If the electrode is s u b s e q u e n t l y swept
to m o r e n e g a t i v e voltages in the d a r k a n e g a t i v e cu r r en t is o b s e r v e d w h i ch is
in excess of the n o r m a l dark c u r r e n t observed on a subsequent sweep w i t h no
p h o t o e x c i t a t i o n b e t w e e n sweeps. The excess c u r r e n t is o b s e r v e d to h a v e a
m a x i m u m at a voltage positive of the flatband potential. In this paper, the
g r o w t h and decay of this r ed u ct i o n peak ar e i n v e s t i g a t e d e x p e r i m e n t a l l y .
T h e p e a k is analyzed as a r e d u c t i o n by conduction band electrons of surface
states that w e r e oxidized by v al en ce band holes during the photoexcitation.
T h e observations f a v o r the i n t e r p r e t a t i o n that these states are i n t e r m e d i a t e s
of the reaction leading to 02 evolution. This interpretation, however, its not
u n e q u i v o c a l l y established. It is clear that the c o n d u c t i o n - b a n d electron r e -
duction of a state that was previously oxidized by a v a l e n c e - b a n d hole is in
effect an e l e c t r o n - h o l e recombination. This r e c o m b i n a t i o n controls t h e ' onset
of p h o t o c u r r e n t with voltage. T h e r e are 1013-1014 of these states p e r em 2 and
the cross section for e l e c t r o n i n t e r a c t i o n w i t h this surface state is estimated
to be 10-~6-10 - ~ cm 2 based on the analysis used to describe the peak.: The
usefulness of this analysis in i n v est i g at i n g these states and surface states due
to surface coatings is discussed.

Since t h e first report (1) of stable, p h o t o el ect r o -
chemical oxygen e v o lu ti o n on TiO2, a substantial effort
has been m a d e to i m p r o v e on those e a r l y results. This
w o r k has been the subject of several recent r e v i e w s
(2-5). The w o r k r e p o r t e d here is p a r t of a continuing
effort to u n d e r s t a n d the processes that occur on TiO2
during O2 evolution as a guide to the use of n a r r o w e r
bandgap semiconductors for that purpose.
In a previous r e p o r t (6) observation of a reduction
c u r r e n t peak produced by photoexcitation of a TiO2
electrode was discussed briefly. In this p a p e r the e x -
p e r i m e n t a l m e a s u r e m e n t of this peak is r e p o r t e d in
m o r e detail and a model to describe the effect is
developed. Data are p r e s e n t e d to support the v i e w
that this r ed u ct i on c u r r e n t is due to an electron t r a n s -
fer to a r e l a t i v e l y stable surface species that was
produced by a reaction w i t h a hole in the valence
band of the TiO2 during illumination. A m o d e l for
this process is presented. The possibility that this
stable surface species is an i n t e r m e d i a t e of the series
of reactions leading to o x y g e n evolution is discussed.
It is f u r t h e r argued that this reduction by a conduc-
tion band electron is a r e v e r s a l of a previous oxidation
by a valence band hole. The net results of these two
processes is an electron hole r e c o m b i n a t i o n and this
r e c o m b i n a t i o n is the controlling factor in the onset
of p h o t o c u r r e n t with increasing positive voltage ap-
plied to the n - t y p e TiO2 electrodes.
Experimental Procedures
All m e a s u r e m e n t s w e r e made using a cell w i t h a
4 m m diam opening to w h ic h a lar~er single crystal
TiO2 electrode was pressed using a thin silicone gasket
* Electrochemical Society Active Member.
Key words: photoelectrolysis, semiconductor, interfaces, photo-
electrochemistry.
as a seal. A sat u r at ed calomel electrode (SCE) con-
nected by a L u g g i n capillary was used as a r e f e r e n c e
electrode. The c o u n t e r e l e c t r o d e was a platinized pl a t -
i n u m electrode. Light to the TiO2 electrode e n t e r e d
the ceil t h r o u g h a v~treous silica w i n d o w and passed
t h r o u g h 1 cm of el ect r o l y t e before falling on the
electrode. Th e light source was a 150W x e n o n l a m p
with a Bausch and Lomb grating monochromator. The
m e a s u r e m e n t s w e r e m a d e using a P A R Model 173
potentiostat and a Model 175 u n i v e r s a l p r o g r a m m e r .
The c u r r e n t - v o l t a g e curves w e r e recorded on an X - Y
recorder. Th e TiO2 electrodes w e r e p r e p a r e d using
methods p r e v i o u s l y described (7). The electrolytes
w e r e p r e p a r e d using distilled w a t e r and r e a g e n t grade
chemicals.
Observations
The n a t u r e of t h e observations to be described is
i l l u st r at ed in Fig. 1 w h e r e the c u r r e n t - v o l t a g e charac-
teristics of a TiO2 electrode are shown w h e n the
voltage is swept f r o m zero volts (SCE) at --200
m V / s e c in 1M K O H u n d er the following conditions:
(i) in the dark w i t h no i l l u m i n a t i o n subsequent to
the previous n e g a t i v e voltage sweep; (it) i l l u m i n a t e d
w i t h 350 n m light; (iii) in the d a r k af t er 30 sec
i l l u m i n a t i o n w i t h 350 nm light at 0 volts (SCE). As
can be seen in cu r v e 3 of Fig. 1, additional cathodic
c u r r e n t occurs as a result of the short period of i l l u-
m i n a t i o n at 0 volts. The principal features of this
reduction peak are observed to be i n d e p e n d e n t of
the crystal face of the TiO2 (they are also observed
on SrTiO.~) and the doping density of the TiO2. Factors
that do affect the reduction peak will be discussed here.
The g r o w t h of the r e d u c t i o n peak as a function of
i l l u m i n a t i o n t i m e is i l l u st r at ed in Fig. 2 ( a ) . In each
case t h e r e is a 5 sec delay b e t w e e n the light-off and

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 Vol. I27, No. 1
- 40
/f
- 20
-10
1 I
-0.4 -0.2
VSCE (VOLTS)
Fig. 1. Current-voltage curves of a TiO2 electrode in 1.0M KOH
with - - 2 0 0 mV/sec scan from 0 volts (SCE). Curve 1, in dark;
curve 2, with 350 nm light on; curve 3, in dark after 30 sec illu-
mination with 350 nm light at 0 volts (SCE).
0 +08
(o) I I 1 I
6 b e t w e e n light-off a n d the b e g i n n i n g of the voltage
I
i/zo
VSCE (VOLTS)
0 *0.8
(b) I 1 I I
I
Fig. 2. Current-voltage curves of a TiO2 electrode in 0.SM H2SO4
with a - - 2 0 0 mV/sec scan from ~ 0 . 8 V (SCE) in dark (a) after
exposure to 350 nm light for curve 1, 0 sec; curve 2, 0.1 sec; curve 3,
1.0 sec; curve 4, 5 sec; curve 5, 30 sec; curve 6, 180 sec with 5
sec delay before initiating voltage sweep; and (b) after exposure to
350 nm light far 30 sec and curve 1, 5 sec; curve 2, 30 sec; curve 3,
120 sec; curve 4, 6000 sec delay before initiating voltage sweep.
the b e g i n n i n g of the sweep. As can be seen, t h e r e
is a rapid initial growth with a s u b s e q u e n t saturation.
The growth can be a p p r o x i m a t e d b y
N = No(1 -- e -t/y)
where t is the time of exposure to light, N is the area
u n d e r the peak (to be expressed as the n u m b e r of
electrons per u n i t electrode area), No is its s a t u r a t i o n
value a n d ~ is a time constant which is inversely
proportional to the p h o t o c u r r e n t density d u r i n g i l l u -
mination. A n approximate empirical relationship is
= 2 X 10 -4
cm 2
, j
where j is the c u r r e n t density d u r i n g illumination.
G r e a t e r precision i n this m e a s u r e m e n t is not considered
to be justified at this time. The value of No was ob-
served to be i n d e p e n d e n t of light intensity and c u r r e n t
density.
The decay of the peak for different delay times
before the sweep is initiated is shown in Fig. 2 ( b ) .
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AQUEOUS ELECTROLYTES 229
I n each case the electrode was i l l u m i n a t e d for 30 sec
before the b e g i n n i n g of the delay period. No functional
relationship was found to describe the r e m a i n i n g peak
size as a f u n c t i o n of time. It is readily seen from
the figure that the rate of decay decreases with time
I (Fa) and a substantial fraction of the peak is left after
100 min. The decay rate was the same at +0.8 or
+0.6V d u r i n g the delay period.
The rates of growth and decay of the peak were
i n d e p e n d e n t of the electrolyte, stirring of the electro-
lyte, a n d the presence or absence of dissolved O2 i n
the electrolyte. As will be discussed, some features of
the c u r r e n t d u r i n g the sweep do depend on the elec-
trolyte and stirring.
F i g u r e 3 shows the effect of scan rate on the r e d u c -
tion peak. The solid curves were made at --500 m V /
sec and the dashed curves were made at --50 m V / s e c
both i n 0.5M H2SO4. Note that the c u r r e n t scale differs
b y a factor of ten for the two sets of curves. Curves 1
were after i l l u m i n a t i o n with 350 n m light at +0.8V
for 30 sec and then a 30 sec delay before i n i t i a t i n g
the voltage sweep. Curves 2 were s u b s e q u e n t sweeps
in the dark with no i l l u m i n a t i o n at -F0.8V. It is
obvious that the area u n d e r the peaks is a p p r o x i m a t e l y
proportional to the scan rate, i.e., the a m o u n t of charge
t r a n s f e r r e d is i n d e p e n d e n t of scan rate. The shift i n
I peak position is n o t e w o r t h y and will be discussed
i n the n e x t section.
All of the following observations of the reduction
peak were made using a --200 mV/sec sweep rate,
30 sec i l l u m i n a t i o n with 350 n m light at 0 volts i n
1M KOH or +0.8V i n 0.5M H2SO4 with a 5 sec delay
sweep.
Figure 4 shows a series of m e a s u r e m e n t s made on
a TiO2 electrode. Figure 4(a) shows m e a s u r e m e n t s
made in 1M KOH. The solid curves were initial m e a -
surements and the dashed curves after 0.1C of charge
was passed b y i l l u m i n a t i n g the electrode with 350
n m light at 0 volts (SCE) ( c u r r e n t about 18 ~A).
I Curves 1 were made after 30 sec i l l u m i n a t i o n at 0 volts
after a previous sweep to --1.2V. Curves 2 were made
after curve 1 with no i n t e r v e n i n g illumination. Several
features can be noted i n these curves. One is the
development of a second peak at --0.95V after 0.1C.
This peak continues to grow with f u r t h e r passage
of photocurrent. Its rate of growth is n o n l i n e a r with
c u r r e n t density growing more per u n i t of charge
passed at higher c u r r e n t density. While this extra
reduction peak is interesting, it will not be discussed
in detail i n this report. As will be seen, it slowly dis-
appears in 0.5M H2SO4.
A n o t h e r feature is a shift of the initial peak at
--0.85V to a slightly more positive voltage. This shift
is p r o b a b l y due to a change in the fiatband potential
d u r i n g the 0.1C charge transfer, since a corresponding
Vsc E (VOLTS)
[1]
0 +0.4 +0.8
t t I t I
[2]
// I SOL,O I/za
DASHED 0. IFa
/
Fig. 3. Current-voltage curves of a TiO2 electrode in 0.5M H2SO4
in dark after curves 1, 30 sec exposure to 350 nm light with 30 sec
delay before initiating voltage sweep at: solid curve 500 mV/sec;
dashed curve 50 mV/sec; curve 2, no exposure before sweep.
 230 J. Electrochem. S'oc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y
(=l
-I.0 VSCs (VOLTS)
I I .t.........~_ I I I
~ ~
/ I II,o
L PEAK
~'-EXTRA PEAK
(C VscE (VOLTS)
-04 0 +08
I i I l I i
shift occurs i n the capacitance-voltage curve. The
shift is reversible in the dark. This can be seen i n
the position of curve 4 i n Fig. 2 (b). Again, this shift,
while interesting, will not be discussed f u r t h e r here.
I n addition, it should be noted that this shift and the
associated capacitance change come after long periods
of photocurrent. There is no change i n capacitance at
0 volts as a result of the 30 sec i l l u m i n a t i o n responsible
for the reduction peak.
The existence, location, and size oE the initial peak
are the features of interest here. These features will
be considered f u r t h e r in the discussion section.
After more use i n KOH d u r i n g which the extra peak
grew further, the electrode of Fig. 4(a) was m e a -
sured in 0.5M H2SOa. The results are shown in Fig.
4(b) and 4(c). The observations in Fig. 4(b) were
made shortly after the removal of KOH a n d the
addition of H2SO4. Note that a less sensitive c u r r e n t
scale is used in 4 ( b ) . Curve 1 is after 30 sec i l l u m i n a -
tion with 350 n m light at +0.8V with no stirring of
the electrolyte. Curve 2 is for the same conditions
b u t with the electrolyte stirred in the vicinity of
the electrode d u r i n g the 5 sec delay b e t w e e n i l l u m i n a -
tion and voltage sweep. Curve 3 was with no i l l u m i n a -
tion before the sweep. The c u r r e n t increase at more
negative voltages in curve 3 is a function of the a m o u n t
of dissolved oxygen in the electrolyte. Oxygen is
u n a v o i d a b l e since it is produced d u r i n g the period of
illumination. Figure 4(b) is i n t e n d e d to illustrate
the effect of stirring and the additional structure at
--0.3V and to point out *.hat these features are not
those u n d e r consideration here. In addition, some of
the extra peak that grew in KOH can still be seen
at +0.05V.
F i g u r e 4(c) shows the behavior of the same elec-
trode after sitting over a w e e k e n d in 0.5M H2SO4.
Curve 1 is an initial measurement. Curve 2 is after
0.018C passed through the electrode using 350 n m
i l l u m i n a t i o n at +0.8V, a subsequent sweep to --0.4V,
and then the usual 30 sec i l l u m i n a t i o n at +0.8V
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January 1980
(b} VSCE ( VOLTS)
0 -0.4 0 +0.8
I t i, i i I I
L PEAK
Fig. 4. Current-voltage curves of o Tie2 electrode in dark with a
--200 mV/sec scan from extreme positive voltage shown with either
30 sec exposure or no exposure to 350 nm light with 5 sec delay
before scan. All measurements on the same electrode with a series
I of uses between measurements: (a) in 1M KOH, curve 1, 30 sec
exposure; curve 2, no exposure; solid curves--initial; dashed
curves-after 0.1C photocurrent passed; (h) (note scale change) in
0.$M H2SO4 after extensive use in KOH since (a). Curve 1, 30 sec
exposure; curve 2, 30 sec exposure with electrolyte in vicinity of the
electrode stirred in the 5 sec delay period; curve 3, no exposure;
(c) in 0.5M H2SO4 after sitting 60 hr in that electrolyte since (b),
carve 1, initial; curve 2, 30 sec exposure after 0.016C photocurrent
passed; curve 3, 30 sec exposure after another 0.034C phetocurrent
passed; curve 4, after 3 but no exposure. Shaded areas in (a) and
(c) correspond to 6.7 1013 and 1.9 1013 electronsJcm 2 of
Ties respectively.
before the sweep. C u r v e 3 is after a n o t h e r 0.034C with
the same procedure. Curve 4 is a sweep with no
i l l u m i n a t i o n after curve 3.
Again, several features can be noted in Fig. 4(c).
One is the absence of the second peak that developed
in Fig. 4(a) and was still evident in 4 ( b ) . The states
responsible for the peak are a p p a r e n t l y removed b y
0.5M H2SO4.
A second feature is the shift in peak position to
more positive potentials similar to that seen in Fig.
4 ( a ) . It also is accompanied b y a corresponding shift
i n the capacitance-voltage curve and is p r o b a b l y due
to a change in flatband voltage.
A third feature is the variable b a c k g r o u n d c u r r e n t
from which the peak at +0.2V rises. This c u r r e n t is
a p p a r e n t l y the tail of some of the effects seen in Fig.
4 (b) at more negative voltages.
The features of interest i n this report are the size
and location of the peak itself. These will be dealt
with q u a n t i t a t i v e l y i n the discussion section. There is
an obvious difference i n the size of this peak in H2SO4
and KOH. When the 0.SM H2SO4 was removed after
curve 3 of Fig. 4(c) and was replaced by 1M KOH,
the peak was very similar to the initial peak shown
in Fig. 4 (a).
The behavior of the reduction peak described in
this section has been reproduced on m a n y Tie2 elec-
trodes with different p r e p a r a t i o n and different doping
densities. The peak, however, is not always as clean
and sharp as illustrated thus far. This is seen i n
Fig. 5 where initial m e a s u r e m e n t s on a Tie2 electrode
which had sat in the l a b o r a t o r y several weeks be-
t w e e n the time it was prepared and the time it was
first measured are shown i n the solid curves. No
cleaning procedure was used prior to the m e a s u r e m e n t .
The dashed curves are m e a s u r e m e n t s on the same
electrode after f u r t h e r use in 1M KOH, subsequent
m e a s u r e m e n t in 0.5M H2SO4, and then m e a s u r e m e n t
in 1M KOH. S h a r p e n i n g of the reduction peak (curves
3) is obvious. This s h a r p e n i n g developed gradually
 VoL IgT, No. I AQUEOUS ELECTROLYTES 231

relative to some reference in the electrolyte and Vfb

/ is the flatband potential of the semiconductor relative
/ to the same reference, q is the m a g n i t u d e of the
/ electron charge, T is absolute temperature, and Ir is
/ Boltzmann's constant. The discussion will be restricted
/-'---Z-

i
to V > Vfb where the value of Vfb will be considered
/ lOF.o i n d e p e n d e n t of V. The c u r r e n t density, j, of electrons
reacting with the surface states is given by
j = qnsN~v [4]

-I0 -0.8/
/////Vsc.s
I-0.6
(VOLTS)
--0.4
where v is the t h e r m a l velocity of the electrons (about
107 cm/sec) and r is the cross section for i n t e r a c t i o n
b e t w e e n the electrons and the surface states. If it is
f u r t h e r assumed that each state that is filled by this
electron c u r r e n t is not reemptied t h e n
dN dN dV j
- - _ [5]
dt = dV dt q
i//I'- k.~/ I~o If the initial voltage is large enough so that ns is

I very small a n d the voltage is swept negative at a

constant dV/dt, Eq. [3], [4], and [5] can be combined
and a p p r o x i m a t e l y integrated as
q(V--Vtb)

_ e kT dV [6]
Fig. 5. Current-voltage curves of a TiO2 electrode in 1.0M KOH i N dV
with --200 mV/sec scan from 0 volts (SCE), curve 1, in dark, no
light exposure; curve 2, with 350 nm light on; curve 3, in dark dt
after 30 sec illumination with 350 nm light and 5 sec delay before to get
voltage scan: solid curves--initial measurement on electrode with N=Niexp{ v~nbkTexp[--q(V--Vfb)/kT]/q d-~t }
no cleaning before use; dashed curves--after 0.02C photocurrent in
KOH and 0.01C photocurrent in H2SO4.
[7]
as more p h o t o c u r r e n t was passed in both 1M KOH C o m b i n i n g Eq. [3], [4], and [7] a n expression for
and 0.5M H2SO4. The p h o t o c u r r e n t - v o l t a g e curves j (V) can be determined.
(curves 2) shown in Fig. 5 show corresponding changes The voltage, Vp, for the m a x i m u m in the j ( V )
as do the b a c k g r o u n d dark c u r r e n t curves (curves 1) expression can readily be obtained as
on which the reduction peak rides. S i m i l a r changes
were produced b y cleaning the electrode in concen- kT ( nb~vkT )
Vp -- Vfb = - - I n [8]
trated H2SO4 at t e m p e r a t u r e s above 50~ No attempt q qdV/dt
was made to analyze the surface to establish the
cause of this behavior. It is described here to e m p h a - Using Eq. [8], the current density can be written as
size the i m p o r t a n c e of surface cleaning and to point a function of (V -- Vp).
out the correspondence b e t w e e n the reduction peak q(V--Vp) q(V--Vp)
a n d the p h o t o c u r r e n t - v o l t a g e curves.

Discussion
Peak size and position.--Few q u a n t i t a t i v e t r e a t m e n t s
h a v e b e e n published of charge transfer processes be-
t w e e n electrolyte species and the bands of semicon-
ductors w h e n the electrolyte energy levels are in the
range of the b a n d g a p of the semiconductor. A t u n n e l -
ing analysis (8) has been applied to explore the
d i s t r i b u t i o n of electrolyte energy levels. The strong
doping density dependence of the t u n n e l i n g analysis
precludes that as a n e x p l a n a t i o n of the observations
presented here. The brief, small polaron t r e a t m e n t
published (9) does not seem to apply to the present
case.
A n u m b e r of investigators have used localized states
at the interface in a qualitative way to explain this
charge transfer process. Q u a n t i t a t i v e t r e a t m e n t s using
a n i n t e r a c t i o n cross section b e t w e e n semiconductor
carriers a n d i n t e r f a c e / e l e c t r o l y t e states have been
made for m a j o r i t y carriers (10, 11) and photoexcited
m i n o r i t y carriers (12) and the applicability of this
approach to a variety of interface states has been
suggested (6). It will be applied to the observations
reported here.
Assume a surface density of e m p t y electron states,
N, at the surface of a n n - s e m i c o n d u c t o r with a bulk
electron density, rib. The density of electrons at the
surface of the semiconductor, ns, is given b y
s "-- W'bexp [-- q (V -- Vfb)/kT]
w h e r e V is the v o l t a g e applied to the semiconductor
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= __. e 7cT exp [ -- e I~T ]
[9]
Thus, the shape of the reduction peak is fixed and its
size d e t e r m i n e d b y Ni and the voltage sweep rate.
Equation [8] can be r e a r r a n g e d to give
dV q [ q(Vp--Vfb) ]
-- - - exp [i0]
dt kTnbV kT
from which the cross section for electron capture can
be calculated from Vp if Vfb and nb can be determined.
I n Fig. 6 calculated j ( V -- Vp) curves are compared
with e x p e r i m e n t a l results taken from the shaded areas
of Fig. 4(a) and 4(c). For the calculations the values
of Ni were d e t e r m i n e d from the areas u n d e r the
e x p e r i m e n t a l curves. These were 6.7 X 1013 and 1.9
10z3 per cm 2 respectively. The position of the peak
i n the calculated curve was matched to the experi-
m e n t a l peak. As can be seen the e x p e r i m e n t a l c u r v e s
are broader than the calculated curves. This does not
necessarily indicate that the model used to describe
the charge transfer process is not appropriate. The
calculations assume a single value for ~, a u n i f o r m
doping density, and a u n i f o r m flatband voltage across
the surface of the electrode. A spread in the value
for a n y of these could explain the width of the ex-
p e r i m e n t a l peaks: The v e r y broad peak in Fig. 5 is
[3]
p r o b a b l y due to a spread in flatband voltage due to
surface contamination. Since this effect can be e l i m -
 232 J. E l e c t r o c h e m . Soc.: SOLID-STATE SCIENCE AND TECHNOLOGY
VSCE (VOLTS)
(e) (b)
-I0 -08 -06 0 +02 +04
'2J v
I I I I [ l
I these states are assumed to be filled with electrons.
I W h e n the i l l u m i n a t i o n is started the density of holes
I at the surface increases b y Ps. These holes' move with
I a t h e r m a l velocity, v (assuming t h e same effective
I mass as electrons gives v = 107 cm/sec f o r both holes
Fig. 6. Comparison of experimental reduction peaks (solid curves)
corresponding to the shaded areas of (o) Fig. 4(a); and (b) Fig.
4(c) with curves calculated (dashed curves) from Eq. [9] using
Ni = 6.7 1013 cm - 2 and 1.9 1013 cm - 2 respectively and
matching the peak position to the experimental curve.
inated b y proper surface p r e p a r a t i o n it will not be
considered f u r t h e r here.
The model correctly describes the effect of voltage
sweep rate illustrated i n Fig. 3. Equation [9] shows
the c u r r e n t proportional to the s w e e p rate. Equation
[8] shows the peak position decreasing 0.06V for a
factor of 10 increase in sweep rate. Both of these effects
are readily seen in Fig. 3. The background c u r r e n t
on which the peak rides also increases with scan rate
as expected since it is capacitive c u r r e n t due to a
changing voltage across the depletion region of the
semiconductor.
F r e q u e n c y dependent capacitance and n o n u n i f o r m
doping density p r e v e n t p r e c i ~ e f l a t b a n d voltage deter-
mination. The capacitance v s . voltage m e a s u r e m e n t s at
1000 Hz that were made in Conjunction with the e x -
p e r i m e n t a l reduction peak m e a s u r e m e n t s in Fig. 6
show n o n u n i f o r m doping density with depth. Using
capacitance-voltage m e a s u r e m e n t s it is possible, how-
ever, to determine a difference in flatband potential
of more than 1V for the electrode in 1M KOH and
0.5M H2SO4 corresponding to the two m e a s u r e m e n t s
in Fig. 6. This differs from the 0.8V difference expected
from the 0.059V/pH shift us~ually a t t r i b u t e d to TiOe.
This discrepancy could be due to surface effects de-
t e r m i n e d by the sequence of measurements. It could
affect the relative values for ~ b u t does not affect the
principal conclusions of this report. Using Vfb :
--0.3V a n d Vp = ~0.21V in 0.5M H2SO4 and ~r =
--1.3V and "Vp m --0.85V in 1M KOH the values of
a = 3.6 10-16 cm 2 and 3.6 10 -17 cm 2 respectively
are obtained. [A value of n b : Nd = 7 X 1017 cm -3
was used. It can be shown that for n o n u n i f o r m doping
with depth the appropriate value for nb i n Eq. [3]
is its value at the edge of the depletion region. This
value for b can be d e t e r m i n e d from the slope of
A 2 / C 2 v s . V at the voltage corresponding to the peak
(13).]
No a t t e m p t has b e e n made to d e t e r m i n e values of
with greater precision to see if there are sample to
sample and electrolyte to electrolyte variations or
if ~ is a p p r o x i m a t e l y the same u n d e r all conditions.
A better u n d e r s t a n d i n g of the origin of the states
responsible for the peak will provide the driving force
for more precise measurements. The values for
d e t e r m i n e d here are smaller than the geometric cross
section of a state localized on a single atom. This
suggests that the state is not positively charged (the
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January I980
coulombic attraction could make the cross section
m u c h larger t h a n geometric). A cross section smaller
t h a n geometric could be due to poor electronic or pho-
n o n coupling b e t w e e n the state and the semiconductor.
The model developed here could be used to study
factors that affect this coupling i n the e x p e r i m e n t a l
situation described here or i n other e x p e r i m e n t a l
circumstances i n v o l v i n g charge transfer between sur-
face coatings and semiconductors.
Growth of peak.--Two possible circumstances will
be analyzed to describe the observed growth of the
reduction peak. One of these assumes a fixed density,
Ns, of electron s t a t e s on the surface of the electrode.
After a negative voltage sweep and before i l l u m i n a t i o n
a n d electrons), a n d i n t e r a c t with the filled states with
a cross section, qh. The density of e m p t y states, N,
grows according to
dN
= p s ( N s - - N ) ~ h v -- n s N a v - - N r [11]
dt
where r is the spontaneous hole emission constant, i.e.,
N r is the capture rate of electrons from the valence
b a n d (ns and ~ were defined at Eq. [3] and [4]).
Neglecting hole emission and operating at a voltage
well positive of the flatband voltage (in the s a t u r a t i o n
region of curve 2, Fig. 1) so that ns can be neglected
N = Ns[1 -- exp (--Ps~hVt) ] [12]
is readily obtained if Ps is assumed constant and t is
the time the electrode is illuminated. I f the light is
stopped at time t and a negative voltage sweep is
started the N of Eq. [12] becomes the :Ni of Eq. [9]
if spontaneous decay of N d u r i n g t h e initial period
of the sweep is neglected. Neglecting hole emission
and assuming Ps constant in time are p r o b a b l y not
precisely justified but are acceptable in this s e m i q u a n -
titative t r e a t m e n t i n t e n d e d to contrast different ap-
proaches to describe the processes involved. It will
be noted that Eq. [12] and Eq. [1] are of the same
form. Furthermore, Ps is proportional to light i n t e n s i t y
(12) and consequently to j in the saturation region
of the photocurrent for the c u r r e n t densities used here.
This is consistent with Eq. [2].
Another approach to describe the origin of the
reduction peak is to treat it as due to a n intermediate
of the w a t e r splitting reaction
2H20 + 4h + -~ 02 + 4 H + [13]
where h+ is a hole in the valence b a n d of the semi-
conductor. If $I is a rate constant for the r a t e - l i m i t i n g
step of a series of reactions in which a hole produces
an i n t e r m e d i a t e with surface density, N, and % is the
cross section for a hole to react with this i n t e r m e d i a t e
as a next step in 02 evolution the rate equation for
this process is
dN
= p s S I -- p s N ~ p v - - n s N ~ v -- N r [14]
dt
where the other terms are as before. Using the same
assumptions as for Eq. [12], (r = 0; ns = 0)
$1
N = [1 -- exp (--ps~pvt) ] [15]
CrpV
is obtained. All the caveats applied to Eq. [12] should
be used for Eq. [15] also. The interesting comparison
is that the saturation value of N in Eq. [15] comes
n a t u r a l l y as a result of the relative rates of a first
and second oxidation by photoexcited holes. The larger
v a l u e for the reduction peak in KOH compared to
H~SO~ is readily explained as an increase in $1 due
 Vol. 127, 17o. I AQUEOUS ELECTROLYTES
to some difference, e.g., the Helmholtz layer, b e t w e e n
KOH and H2SO4. Ns in Eq. [12] is p u r e l y ad hoc.
I n most other respects the two approaches give
similar results. Both predict s a t u r a t i o n values of N
i n d e p e n d e n t of light i n t e n s i t y b u t growth rates de-
p e n d e n t on light intensity.
The fact that the observed capacitance is i n d e p e n d e n t
of the states being filled or empty, however, suggests
t h a t the states are n e u t r a l i n both cases. This favors
the r e a c t i o n - i n t e r m e d i a t e model i n which a chemical
process such as H + l e a v i n g the surface after hole
capture or O H - leaving the surface after electron
capture could m a i n t a i n this neutrality.
More precise analysis of the processes a n d / o r n e w
e x p e r i m e n t a l observations are necessary to distinguish
b e t w e e n the two approaches analyzed here.
Decay of peak.--The process by which the reduction
peak decreases d u r i n g the delay period b e t w e e n t u r n -
ing the light off a n d i n i t i a t i n g the voltage sweep is
p r o b a b l y hole emission to the valence band. Some
a l t e r n a t i v e explanations can be eliminated, others
seem too arbitrary.
Electron capture from the conduction b a n d can be
e l i m i n a t e d b y noting that the decay rate is the same
at ~0.6V a n d -{-0.8V in 0.JM H2SO4 as noted in the
observation section. The electron density at the surface
changes b y more t h a n three orders of m a g n i t u d e for
t h a t voltage change.
Electron capture from an i m p u r i t y can be e l i m i n -
ated since the decay rate is i n d e p e n d e n t of stirring
d u r i n g the delay. Other electrolyte levels are not
able to donate an electron. F u r t h e r m o r e , the decay
rate is a p p r o x i m a t e l y the same in 1M KOH and 0.5M
H2SO4.
Electron capture from H20 in the electrolyte is a
possible e x p l a n a t i o n if a t h e r m a l activation to surface
states distributed i n e n e r g y is assumed to e x p l a i n
the long t e r m stability of some of the states. The
s u b s e q u e n t chemistry implied by this water oxidation
step makes this process seem untenable.
A s t r a i g h t f o r w a r d e x p l a n a t i o n is contained in the
last term of both Eq. [11] and [14]. With the light
off and at high voltages both Ps and ns are negligible
a n d the equation can be i n t e g r a t e d to
N ( E ) = No(E)e - r t [16]
w h e r e a d i s t r i b u t i o n i n e n e r g y is emphasized. Since
hole emission from a surface state of energy, E, above
the valence b a n d is an endoenergetic process, t h e r m a l
activation is r e q u i r e d and r can be w r i t t e n in the form
?" "-- Vo'e~v e - E / k w [17]
where ~ ---- 1019 cm -3 is the estimated effective density
of states i n the valence b a n d and Ce is the cross section
for a valence b a n d electron to react with the surface
state. Using a decay constant 9 ---- 100 sec and ~e :
10 -16 cm ~ a v a l u e of E _-- 0.7 eV is obtained. As can
be seen from Fig. 2(b) about 30% of the peak area is
lost i n 120 sec. U n d e r the above assumptions 70%
of the states would be more t h a n 0.7 eV above the
valence band. The n u m b e r s used for ~e and ~, are
only estimates, however, the logarithmic dependence
makes the value of E weakly d e p e n d e n t on these
parameters. This e x p l a n a t i o n is plausible and if the
states involved are intermediates of 02 evolution it
suggests that they are 2-2.5 eV below the h y d r o g e n
potential.
Summaryand Conclusions
I n thi~ report e x p e r i m e n t a l results have been pre-
sented which indicate that oxidized states are pro-
duced on the surface of TiO2 electrodes in aqueous
electrolytes w h e n the TiO2 is i l l u m i n a t e d u n d e r con-
ditions which produce a p h o t o c u r r e n t in the cell. Most
of these states are still there after several minutes.
T h e y decrease at a rate consistent with t h e r m a l l y
activated hole emission from states several tenths
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233
of a n eV above the valence b a n d with at least a t e n t h
of a volt distribution i n energy. Measurements on
other stable electrodes with valence bands higher i n
energy could test this hypothesis.
The observed reduction peak produced b y these
states d u r i n g a negative voltage sweep has been a n a -
lyzed as a reaction with electrons in the conduction
b a n d at the surface of the semiconductor. They i n t e r -
act w i t h a cross section which can be d e t e r m i n e d b y
the position of the reduction peak. P r e l i m i n a r y m e a -
s u r e m e n t s indicate that the cross section is about
10 -16 cm 2, i.e., smaller t h a n the geometric cross sec-
tion. This model describes all of the observed behavior
and can be used to analyze other surface state i n t e r -
actions with semiconductor electrons, e.g., attached
surface layers. A correlation b e t w e e n e l e c t r o n - c a p t u r e
cross section and a t t a c h m e n t process of the layer could
be very useful.
The saturated density of these oxidized states was
explained as a n intrinsic density of surface states
or as the result of the relative rate of production and
consumption of i n t e r m e d i a t e states of the O2 evolution
process. Kinetic considerations i n the growth in density
of these oxidized states were discussed b u t a detailed
analysis was not developed.
Evidence supporting the view that the surface state
is a n i n t e r m e d i a t e i n the O2 evolution process was
discussed. The a r g u m e n t in favor of this view is n o t
conclusive at this point. M e a s u r e m e n t s i n other sol-
vents such as acetonitrile might be useful i n resolving
this question.
What is clear is that the surface state produced b y
oxidation by a hole from the valence b a n d can also
be reduced b y a n electron from the conduction band.
The net effect is an electron hole recombination. It is
this recombination that controls the onset of photo-
c u r r e n t with voltage i n a m a n n e r previously de-
scribed (12). If the state is a n i n t e r m e d i a t e of the 02
evolution process it represents an i n h e r e n t l i m i t a t i o n
i n attempts to use n a r r o w e r b a n d g a p semiconductors
if its cross sections and energy levels are the same
for other semiconductors.
Acknowledgments
This work was supported in part b y the Office of
Basic E n e r g y Sciences of the D e p a r t m e n t of Energy.
I a m i n d e b t e d to L. A. Harris a n d R. S c h u m a c h e r for
critical reading of the manuscript.
Manuscript submitted March 22, 1979; revised m a n u -
script received J u n e 5, 1979.
A n y discussion of this paper will appear i n a Dis-
cussion Section to be published in the December 1980
JOURNAL. All discussions for the December 1980 Dis-
cussion Section should be s u b m i t t e d by Aug. 1, 1980.
Publication costs oS this article were assisted by Gen-
eral Electric Company.
REFERENCES
1. A. F u j i s h i m a and K. Honda, Bull. Chem. Soc. Jpn.,
44, 1148 (1971); Nature (London), 238, 37 (1972).
2. L. A. Harris and R. H. Wilson, Annu. Rev. Mater.
Sci., 8, 99 (1978).
3. H. P. Maruska and A. K. Ghosh, Sol. Energy, 20,
443 (1978).
4. A. J. Nozik, Annu. Rev. Phys. Chem., ~9, 189
(1978).
5. M. Tomkiewicz a n d H. Fay, AppI. Phys., 18, 1
(1979).
6. R. H. Wilson, Abstract 415, p. 1038, The Electro-
chemical Society Extended Abstracts, Seattle,
Washington, May 21-26, 1978.
7. R. H. Wilson, L. A. Harris. and M. E. Gerstner,
This Journal, 126, 844 (1979).
8. R. M e m m i n g and F. Mollers, Ber. Bunsenges. Phys.
Chem., 76, 475 (1972).
9. G. Beni, i n "Semiconductor L i q u i d - J u n c t i o n Solar
 234 J. Electrochem. S oc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y
Cells," A. Heller, Editor, p. 108, The E l e c t r o -
chemical Society Softbound Proceedings Series,
Princeton, N.J. (1977).
10. T. F r e u n d and S. Roy Morrison, Surf. Sci., 9, 119
(1968).
End Point Detection in Plasma Etching
by Optical Emission Spectroscopy
Kadou Hirobe and Takashi Tsuchimoto*
Computer Development Laboratories Limited, Kodaira, Tokyo 187, Japan
Optical emission spectroscopy has been a p p l i e d to
precise end p o i n t detection in p l a s m a etching (1-4)
a n d the m e t h o d has m a n y a d v a n t a g e s s u p e r i o r to the
others such as mass spectroscopy (5), visual o b s e r v a -
tion of change in i n t e r f e r e n c e colors, and e l l i p s o m e t r y
(6). The p u r p o s e of this p a p e r is to i n t r o d u c e a m e a -
sure for the end point detection m e t h o d using an o p t i -
cal emission and to e v a l u a t e the lower l i m i t of detec-
tion for etching p o l y c r y s t a l l i n e silicon ( p o l y - S i ) and
silicon n i t r i d e (Si3N4).
F i g u r e 1 shows a block d i a g r a m of etching a p p a r a t u s
and optical emission observation s y s t e m w h i c h has
been used in the e x p e r i m e n t . P l a s m a etching was car-
ried out in a volume loading, b a r r e l t y p e a p p a r a t u s
(Model 2005-1813 SC from I n t e r n a t i o n a l P l a s m a Cor-
p o r a t i o n ) . Wafers w e r e placed in a quartz w a f e r boat
inside a quartz chamber. CF4 + 02 (4%) was used as
an etching gas. Typical etching condition was 100W
rf p o w e r and 0.5 Torr (66.5 P a ) . P o l y - S i and SisN4
films w e r e p r e p a r e d using the reaction of chemical
v a p o r deposition on t h e r m a l l y oxidized silicon s u b -
strates. The optical emission observation system was
composed of a s p e c t r o m e t e r (Model 139 from Hitachi,
L i m i t e d ) , a photomultiplier, an amplifier, and a r e -
corder. The resolution of the system was 0.5 nm. The
emission was v i e w e d t h r o u g h the thick q u a r t z w i n d o w
at one end of the chamber. No optical lens was used.
In the e x p e r i m e n t a l m e a s u r e m e n t , the w a v e l e n g t h s of
674 and 777 n m w e r e selected for those spectra w h i c h
w e r e most useful for Si3N4 and p o l y - S i etching, r e s p e c -
tively. It is considered that the 674 n m line is f r o m N2
molecule a n d the 777 nm is from S i F molecule, a n d N2
* Electrochemical Society Active Member.
Key words: rf discharge, barrel type etching apparatus, poly-
crystalline silicon, mass spectroscopy, carbon tetrafluoride.
REACTION CNAMSER
I~ ~'ETC..As
Fig. 1. Block dlagram of the etcMng apparatus and optical
emission observation system.
Downloaded on 2015-03-09 to IP 132.174.255.116 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
January 1980
11. A. Many, CRC Crit. Rev. Solid State Sci., 4, 515
(1974).
12. R. It. Wilson, J. Appl. Phys., 48, 4292 (1977).
13. J. H i l i b r a n d and R. D. Gold, RCA Rev., 21, 245
(1960).
and S i F come from the reaction products of Si3N4 a n d
p o l y - S i w i t h CF4 in the plasma, respectively.
F i g u r e 2 shows a t y p i c a l change in emission i n t e n s i t y
of the 674 n m line d u r i n g etching SigN4 films. The
emission intensity increased g r a d u a l l y w i t h increasing
t e m p e r a t u r e of the c h a m b e r and of wafers which w e r e
w a r m e d up b y rf discharge, and then decreased r a p i d l y
as the surface a r e a of the r e m a i n i n g Si3N4 film d e -
creased, and finally leveled off a f t e r etching was com-
pleted. The end point was c l e a r l y detected at the point
w h e r e the curve s u d d e n l y drops off in the figure.
S i m i l a r c h a r a c t e r i s t i c changes in the i n t e n s i t y of t h e
777 n m line emission w e r e o b t a i n e d for etching p o l y - S i
film.
A n e w m e a s u r e is i n t r o d u c e d for expressing the
l o w e r limit of detection of the end point. The m e a s u r e
is defined as the ratio of the change in emission in-
tensity at the end point (B) to the m a x i m u m emis-
sion i n t e n s i t y ( A ) , n a m e l y B/A. In o r d e r to e v a l u a t e
the l o w e r l i m i t of detection of the m e t h o d for p o l y - S i
and SigN4, the relations b e t w e e n B / A and the a r e a
END-POINT RF POWER IOOW
CF4 +02(4%) 0,5 Tort
m'} (66.5 Pa)
.=_
~F-OiF " B"
Z 'E-
UJ
0 I 2 4
T I M E (rain
Fig. 2. Typical emission intensity of 674 nm .qs a function of
time.