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., 18. W. C. Jo h n so n and P. T. Panousis, IEEE Trans.
20, 27 (1977). Electron DevLces, ed-18, 965 (1971).
16. T. Am b ri d g e, J. L. Stevenson, and R. M. Redstall, 19. K. Hesse and H. Strack, Solid-State Electron., 15,
To be s u b m i tt e d to This Journal. 767 (1972).
17. D. L. Lile and D. A. Collins, Electron. Lett., 14, 457 20. C. P. Wu, C. W. Mueller, and E. C. Douglas, IEEE
(1978). 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 - as a seal. A sat u r at ed calomel electrode (SCE) con-
chemical oxygen e v o lu ti o n on TiO2, a substantial effort nected by a L u g g i n capillary was used as a r e f e r e n c e
has been m a d e to i m p r o v e on those e a r l y results. This electrode. The c o u n t e r e l e c t r o d e was a platinized pl a t -
w o r k has been the subject of several recent r e v i e w s i n u m electrode. Light to the TiO2 electrode e n t e r e d
(2-5). The w o r k r e p o r t e d here is p a r t of a continuing the ceil t h r o u g h a v~treous silica w i n d o w and passed
effort to u n d e r s t a n d the processes that occur on TiO2 t h r o u g h 1 cm of el ect r o l y t e before falling on the
during O2 evolution as a guide to the use of n a r r o w e r electrode. Th e light source was a 150W x e n o n l a m p
bandgap semiconductors for that purpose. with a Bausch and Lomb grating monochromator. The
In a previous r e p o r t (6) observation of a reduction 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
c u r r e n t peak produced by photoexcitation of a TiO2 potentiostat and a Model 175 u n i v e r s a l p r o g r a m m e r .
electrode was discussed briefly. In this p a p e r the e x - 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
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 recorder. Th e TiO2 electrodes w e r e p r e p a r e d using
m o r e detail and a model to describe the effect is methods p r e v i o u s l y described (7). The electrolytes
developed. Data are p r e s e n t e d to support the v i e w 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
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 - chemicals.
fer to a r e l a t i v e l y stable surface species that was Observations
produced by a reaction w i t h a hole in the valence
The n a t u r e of t h e observations to be described is
band of the TiO2 during illumination. A m o d e l for
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-
this process is presented. The possibility that this
teristics of a TiO2 electrode are shown w h e n the
stable surface species is an i n t e r m e d i a t e of the series
voltage is swept f r o m zero volts (SCE) at --200
of reactions leading to o x y g e n evolution is discussed.
m V / s e c in 1M K O H u n d er the following conditions:
It is f u r t h e r argued that this reduction by a conduc-
(i) in the dark w i t h no i l l u m i n a t i o n subsequent to
tion band electron is a r e v e r s a l of a previous oxidation
the previous n e g a t i v e voltage sweep; (it) i l l u m i n a t e d
by a valence band hole. The net results of these two
w i t h 350 n m light; (iii) in the d a r k af t er 30 sec
processes is an electron hole r e c o m b i n a t i o n and this
i l l u m i n a t i o n w i t h 350 nm light at 0 volts (SCE). As
r e c o m b i n a t i o n is the controlling factor in the onset
can be seen in cu r v e 3 of Fig. 1, additional cathodic
of p h o t o c u r r e n t with increasing positive voltage ap-
c u r r e n t occurs as a result of the short period of i l l u-
plied to the n - t y p e TiO2 electrodes.
m i n a t i o n at 0 volts. The principal features of this
Experimental Procedures reduction peak are observed to be i n d e p e n d e n t of
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 the crystal face of the TiO2 (they are also observed
4 m m diam opening to w h ic h a lar~er single crystal on SrTiO.~) and the doping density of the TiO2. Factors
TiO2 electrode was pressed using a thin silicone gasket 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
* Electrochemical Society Active Member. 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
Key words: photoelectrolysis, semiconductor, interfaces, photo-
electrochemistry. 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 AQUEOUS ELECTROLYTES 229

- 40 I n each case the electrode was i l l u m i n a t e d for 30 sec

/f
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
- 20 +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
-10 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 -
1 I
-0.4 -0.2 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
VSCE (VOLTS) 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
Fig. 1. Current-voltage curves of a TiO2 electrode in 1.0M KOH were after i l l u m i n a t i o n with 350 n m light at +0.8V
with - - 2 0 0 mV/sec scan from 0 volts (SCE). Curve 1, in dark; for 30 sec and then a 30 sec delay before i n i t i a t i n g
curve 2, with 350 nm light on; curve 3, in dark after 30 sec illu- the voltage sweep. Curves 2 were s u b s e q u e n t sweeps
mination with 350 nm light at 0 volts (SCE). 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
0 +08 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
(o) I I 1 I 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
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
sweep.

I
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
i/zo made in 1M KOH. The solid curves were initial m e a -
surements and the dashed curves after 0.1C of charge
VSCE (VOLTS) 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).
0 *0.8
(b) I 1 I I 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.
I
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
Fig. 2. Current-voltage curves of a TiO2 electrode in 0.SM H2SO4 c u r r e n t density growing more per u n i t of charge
with a - - 2 0 0 mV/sec scan from ~ 0 . 8 V (SCE) in dark (a) after passed at higher c u r r e n t density. While this extra
exposure to 350 nm light for curve 1, 0 sec; curve 2, 0.1 sec; curve 3, reduction peak is interesting, it will not be discussed
1.0 sec; curve 4, 5 sec; curve 5, 30 sec; curve 6, 180 sec with 5 in detail i n this report. As will be seen, it slowly dis-
sec delay before initiating voltage sweep; and (b) after exposure to appears in 0.5M H2SO4.
350 nm light far 30 sec and curve 1, 5 sec; curve 2, 30 sec; curve 3, A n o t h e r feature is a shift of the initial peak at
120 sec; curve 4, 6000 sec delay before initiating voltage sweep. --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
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
Vsc E (VOLTS)
N = No(1 -- e -t/y) [1]
0 +0.4 +0.8
where t is the time of exposure to light, N is the area t t I t I
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 [2]
// I SOL,O I/za
DASHED 0. IFa
/
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 Fig. 3. Current-voltage curves of a TiO2 electrode in 0.5M H2SO4
density. in dark after curves 1, 30 sec exposure to 350 nm light with 30 sec
The decay of the peak for different delay times delay before initiating voltage sweep at: solid curve 500 mV/sec;
before the sweep is initiated is shown in Fig. 2 ( b ) . dashed curve 50 mV/sec; curve 2, no exposure before sweep.
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 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 January 1980

(=l (b} VSCE ( VOLTS)

-I.0 VSCs (VOLTS) 0 -0.4 0 +0.8
I I .t.........~_ I I I I t i, i i I I

~ ~ L PEAK

/ I II,o

L PEAK
~'-EXTRA 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
(C VscE (VOLTS) 30 sec exposure or no exposure to 350 nm light with 5 sec delay
-04 0 +08
before scan. All measurements on the same electrode with a series
I i I l I i 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.

shift occurs i n the capacitance-voltage curve. The before the sweep. C u r v e 3 is after a n o t h e r 0.034C with
shift is reversible in the dark. This can be seen i n the same procedure. Curve 4 is a sweep with no
the position of curve 4 i n Fig. 2 (b). Again, this shift, i l l u m i n a t i o n after curve 3.
while interesting, will not be discussed f u r t h e r here. Again, several features can be noted in Fig. 4(c).
I n addition, it should be noted that this shift and the One is the absence of the second peak that developed
associated capacitance change come after long periods in Fig. 4(a) and was still evident in 4 ( b ) . The states
of photocurrent. There is no change i n capacitance at responsible for the peak are a p p a r e n t l y removed b y
0 volts as a result of the 30 sec i l l u m i n a t i o n responsible 0.5M H2SO4.
for the reduction peak. A second feature is the shift in peak position to
The existence, location, and size oE the initial peak more positive potentials similar to that seen in Fig.
are the features of interest here. These features will 4 ( a ) . It also is accompanied b y a corresponding shift
be considered f u r t h e r in the discussion section. i n the capacitance-voltage curve and is p r o b a b l y due
After more use i n KOH d u r i n g which the extra peak to a change in flatband voltage.
grew further, the electrode of Fig. 4(a) was m e a - A third feature is the variable b a c k g r o u n d c u r r e n t
sured in 0.5M H2SOa. The results are shown in Fig. from which the peak at +0.2V rises. This c u r r e n t is
4(b) and 4(c). The observations in Fig. 4(b) were a p p a r e n t l y the tail of some of the effects seen in Fig.
made shortly after the removal of KOH a n d the 4 (b) at more negative voltages.
addition of H2SO4. Note that a less sensitive c u r r e n t The features of interest i n this report are the size
scale is used in 4 ( b ) . Curve 1 is after 30 sec i l l u m i n a - and location of the peak itself. These will be dealt
tion with 350 n m light at +0.8V with no stirring of with q u a n t i t a t i v e l y i n the discussion section. There is
the electrolyte. Curve 2 is for the same conditions an obvious difference i n the size of this peak in H2SO4
b u t with the electrolyte stirred in the vicinity of and KOH. When the 0.SM H2SO4 was removed after
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 - curve 3 of Fig. 4(c) and was replaced by 1M KOH,
tion and voltage sweep. Curve 3 was with no i l l u m i n a - the peak was very similar to the initial peak shown
tion before the sweep. The c u r r e n t increase at more in Fig. 4 (a).
negative voltages in curve 3 is a function of the a m o u n t The behavior of the reduction peak described in
of dissolved oxygen in the electrolyte. Oxygen is this section has been reproduced on m a n y Tie2 elec-
u n a v o i d a b l e since it is produced d u r i n g the period of trodes with different p r e p a r a t i o n and different doping
illumination. Figure 4(b) is i n t e n d e d to illustrate densities. The peak, however, is not always as clean
the effect of stirring and the additional structure at and sharp as illustrated thus far. This is seen i n
--0.3V and to point out *.hat these features are not Fig. 5 where initial m e a s u r e m e n t s on a Tie2 electrode
those u n d e r consideration here. In addition, some of which had sat in the l a b o r a t o r y several weeks be-
the extra peak that grew in KOH can still be seen t w e e n the time it was prepared and the time it was
at +0.05V. first measured are shown i n the solid curves. No
F i g u r e 4(c) shows the behavior of the same elec- cleaning procedure was used prior to the m e a s u r e m e n t .
trode after sitting over a w e e k e n d in 0.5M H2SO4. The dashed curves are m e a s u r e m e n t s on the same
Curve 1 is an initial measurement. Curve 2 is after electrode after f u r t h e r use in 1M KOH, subsequent
0.018C passed through the electrode using 350 n m 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
i l l u m i n a t i o n at +0.8V, a subsequent sweep to --0.4V, in 1M KOH. S h a r p e n i n g of the reduction peak (curves
and then the usual 30 sec i l l u m i n a t i o n at +0.8V 3) is obvious. This s h a r p e n i n g developed gradually
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 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
= __. e 7cT exp [ -- e I~T ]
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 [9]
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- Thus, the shape of the reduction peak is fixed and its
ductors w h e n the electrolyte energy levels are in the size d e t e r m i n e d b y Ni and the voltage sweep rate.
range of the b a n d g a p of the semiconductor. A t u n n e l - Equation [8] can be r e a r r a n g e d to give
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 dV q [ q(Vp--Vfb) ]
-- - - exp [i0]
doping density dependence of the t u n n e l i n g analysis dt kTnbV kT
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 from which the cross section for electron capture can
published (9) does not seem to apply to the present be calculated from Vp if Vfb and nb can be determined.
case. I n Fig. 6 calculated j ( V -- Vp) curves are compared
A n u m b e r of investigators have used localized states with e x p e r i m e n t a l results taken from the shaded areas
at the interface in a qualitative way to explain this of Fig. 4(a) and 4(c). For the calculations the values
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 of Ni were d e t e r m i n e d from the areas u n d e r the
a n i n t e r a c t i o n cross section b e t w e e n semiconductor e x p e r i m e n t a l curves. These were 6.7 X 1013 and 1.9
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 10z3 per cm 2 respectively. The position of the peak
made for m a j o r i t y carriers (10, 11) and photoexcited i n the calculated curve was matched to the experi-
m i n o r i t y carriers (12) and the applicability of this 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
approach to a variety of interface states has been are broader than the calculated curves. This does not
suggested (6). It will be applied to the observations necessarily indicate that the model used to describe
reported here. the charge transfer process is not appropriate. The
Assume a surface density of e m p t y electron states, calculations assume a single value for ~, a u n i f o r m
N, at the surface of a n n - s e m i c o n d u c t o r with a bulk doping density, and a u n i f o r m flatband voltage across
electron density, rib. The density of electrons at the the surface of the electrode. A spread in the value
surface of the semiconductor, ns, is given b y 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
s "-- W'bexp [-- q (V -- Vfb)/kT] [3]
p r o b a b l y due to a spread in flatband voltage due to
w h e r e V is the v o l t a g e applied to the semiconductor surface contamination. Since this effect can be e l i m -
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 232 J. E l e c t r o c h e m . Soc.: SOLID-STATE SCIENCE AND TECHNOLOGY January I980

VSCE (VOLTS) coulombic attraction could make the cross section

m u c h larger t h a n geometric). A cross section smaller
(e) (b) 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.
-I0 -08 -06 0 +02 +04 The model developed here could be used to study

'2J v
I I I I [ l 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
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
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
Fig. 6. Comparison of experimental reduction peaks (solid curves) dN
corresponding to the shaded areas of (o) Fig. 4(a); and (b) Fig. = p s ( N s - - N ) ~ h v -- n s N a v - - N r [11]
dt
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 where r is the spontaneous hole emission constant, i.e.,
matching the peak position to the experimental curve. N r is the capture rate of electrons from the valence
b a n d (ns and ~ were defined at Eq. [3] and [4]).
inated b y proper surface p r e p a r a t i o n it will not be Neglecting hole emission and operating at a voltage
considered f u r t h e r here. well positive of the flatband voltage (in the s a t u r a t i o n
The model correctly describes the effect of voltage region of curve 2, Fig. 1) so that ns can be neglected
sweep rate illustrated i n Fig. 3. Equation [9] shows N = Ns[1 -- exp (--Ps~hVt) ] [12]
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 is readily obtained if Ps is assumed constant and t is
factor of 10 increase in sweep rate. Both of these effects the time the electrode is illuminated. I f the light is
are readily seen in Fig. 3. The background c u r r e n t stopped at time t and a negative voltage sweep is
on which the peak rides also increases with scan rate started the N of Eq. [12] becomes the :Ni of Eq. [9]
as expected since it is capacitive c u r r e n t due to a if spontaneous decay of N d u r i n g t h e initial period
changing voltage across the depletion region of the of the sweep is neglected. Neglecting hole emission
semiconductor. and assuming Ps constant in time are p r o b a b l y not
F r e q u e n c y dependent capacitance and n o n u n i f o r m precisely justified but are acceptable in this s e m i q u a n -
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- titative t r e a t m e n t i n t e n d e d to contrast different ap-
mination. The capacitance v s . voltage m e a s u r e m e n t s at proaches to describe the processes involved. It will
1000 Hz that were made in Conjunction with the e x - be noted that Eq. [12] and Eq. [1] are of the same
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 form. Furthermore, Ps is proportional to light i n t e n s i t y
show n o n u n i f o r m doping density with depth. Using (12) and consequently to j in the saturation region
capacitance-voltage m e a s u r e m e n t s it is possible, how- of the photocurrent for the c u r r e n t densities used here.
ever, to determine a difference in flatband potential This is consistent with Eq. [2].
of more than 1V for the electrode in 1M KOH and Another approach to describe the origin of the
0.5M H2SO4 corresponding to the two m e a s u r e m e n t s reduction peak is to treat it as due to a n intermediate
in Fig. 6. This differs from the 0.8V difference expected of the w a t e r splitting reaction
from the 0.059V/pH shift us~ually a t t r i b u t e d to TiOe. 2H20 + 4h + -~ 02 + 4 H + [13]
This discrepancy could be due to surface effects de-
t e r m i n e d by the sequence of measurements. It could where h+ is a hole in the valence b a n d of the semi-
affect the relative values for ~ b u t does not affect the conductor. If $I is a rate constant for the r a t e - l i m i t i n g
principal conclusions of this report. Using Vfb : step of a series of reactions in which a hole produces
--0.3V a n d Vp = ~0.21V in 0.5M H2SO4 and ~r = an i n t e r m e d i a t e with surface density, N, and % is the
--1.3V and "Vp m --0.85V in 1M KOH the values of cross section for a hole to react with this i n t e r m e d i a t e
a = 3.6 10-16 cm 2 and 3.6 10 -17 cm 2 respectively as a next step in 02 evolution the rate equation for
are obtained. [A value of n b : Nd = 7 X 1017 cm -3 this process is
was used. It can be shown that for n o n u n i f o r m doping dN
with depth the appropriate value for nb i n Eq. [3] = p s S I -- p s N ~ p v - - n s N ~ v -- N r [14]
is its value at the edge of the depletion region. This dt
value for b can be d e t e r m i n e d from the slope of where the other terms are as before. Using the same
A 2 / C 2 v s . V at the voltage corresponding to the peak assumptions as for Eq. [12], (r = 0; ns = 0)
(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 $1
N = [1 -- exp (--ps~pvt) ] [15]
with greater precision to see if there are sample to CrpV
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. is obtained. All the caveats applied to Eq. [12] should
A better u n d e r s t a n d i n g of the origin of the states be used for Eq. [15] also. The interesting comparison
responsible for the peak will provide the driving force is that the saturation value of N in Eq. [15] comes
for more precise measurements. The values for n a t u r a l l y as a result of the relative rates of a first
d e t e r m i n e d here are smaller than the geometric cross and second oxidation by photoexcited holes. The larger
section of a state localized on a single atom. This v a l u e for the reduction peak in KOH compared to
suggests that the state is not positively charged (the H~SO~ is readily explained as an increase in $1 due

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 Vol. 127, 17o. I AQUEOUS ELECTROLYTES 233

to some difference, e.g., the Helmholtz layer, b e t w e e n of a n eV above the valence b a n d with at least a t e n t h
KOH and H2SO4. Ns in Eq. [12] is p u r e l y ad hoc. of a volt distribution i n energy. Measurements on
I n most other respects the two approaches give other stable electrodes with valence bands higher i n
similar results. Both predict s a t u r a t i o n values of N energy could test this hypothesis.
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- The observed reduction peak produced b y these
p e n d e n t on light intensity. states d u r i n g a negative voltage sweep has been a n a -
The fact that the observed capacitance is i n d e p e n d e n t lyzed as a reaction with electrons in the conduction
of the states being filled or empty, however, suggests b a n d at the surface of the semiconductor. They i n t e r -
t h a t the states are n e u t r a l i n both cases. This favors act w i t h a cross section which can be d e t e r m i n e d b y
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 the position of the reduction peak. P r e l i m i n a r y m e a -
process such as H + l e a v i n g the surface after hole s u r e m e n t s indicate that the cross section is about
capture or O H - leaving the surface after electron 10 -16 cm 2, i.e., smaller t h a n the geometric cross sec-
capture could m a i n t a i n this neutrality. tion. This model describes all of the observed behavior
More precise analysis of the processes a n d / o r n e w and can be used to analyze other surface state i n t e r -
e x p e r i m e n t a l observations are necessary to distinguish actions with semiconductor electrons, e.g., attached
b e t w e e n the two approaches analyzed here. 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
Decay of peak.--The process by which the reduction cross section and a t t a c h m e n t process of the layer could
peak decreases d u r i n g the delay period b e t w e e n t u r n - be very useful.
ing the light off a n d i n i t i a t i n g the voltage sweep is The saturated density of these oxidized states was
p r o b a b l y hole emission to the valence band. Some explained as a n intrinsic density of surface states
a l t e r n a t i v e explanations can be eliminated, others or as the result of the relative rate of production and
seem too arbitrary. consumption of i n t e r m e d i a t e states of the O2 evolution
Electron capture from the conduction b a n d can be process. Kinetic considerations i n the growth in density
e l i m i n a t e d b y noting that the decay rate is the same of these oxidized states were discussed b u t a detailed
at ~0.6V a n d -{-0.8V in 0.JM H2SO4 as noted in the analysis was not developed.
observation section. The electron density at the surface Evidence supporting the view that the surface state
changes b y more t h a n three orders of m a g n i t u d e for is a n i n t e r m e d i a t e i n the O2 evolution process was
t h a t voltage change. discussed. The a r g u m e n t in favor of this view is n o t
Electron capture from an i m p u r i t y can be e l i m i n - conclusive at this point. M e a s u r e m e n t s i n other sol-
ated since the decay rate is i n d e p e n d e n t of stirring vents such as acetonitrile might be useful i n resolving
d u r i n g the delay. Other electrolyte levels are not this question.
able to donate an electron. F u r t h e r m o r e , the decay What is clear is that the surface state produced b y
rate is a p p r o x i m a t e l y the same in 1M KOH and 0.5M oxidation by a hole from the valence b a n d can also
be reduced b y a n electron from the conduction band.
H2SO4.
Electron capture from H20 in the electrolyte is a The net effect is an electron hole recombination. It is
possible e x p l a n a t i o n if a t h e r m a l activation to surface this recombination that controls the onset of photo-
states distributed i n e n e r g y is assumed to e x p l a i n c u r r e n t with voltage i n a m a n n e r previously de-
the long t e r m stability of some of the states. The scribed (12). If the state is a n i n t e r m e d i a t e of the 02
s u b s e q u e n t chemistry implied by this water oxidation evolution process it represents an i n h e r e n t l i m i t a t i o n
step makes this process seem untenable. i n attempts to use n a r r o w e r b a n d g a p semiconductors
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 if its cross sections and energy levels are the same
last term of both Eq. [11] and [14]. With the light for other semiconductors.
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 Acknowledgments
N ( E ) = No(E)e - r t [16] 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.
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 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
hole emission from a surface state of energy, E, above critical reading of the manuscript.
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 Manuscript submitted March 22, 1979; revised m a n u -
script received J u n e 5, 1979.
?" "-- Vo'e~v e - E / k w [17]
A n y discussion of this paper will appear i n a Dis-
where ~ ---- 1019 cm -3 is the estimated effective density cussion Section to be published in the December 1980
of states i n the valence b a n d and Ce is the cross section JOURNAL. All discussions for the December 1980 Dis-
for a valence b a n d electron to react with the surface cussion Section should be s u b m i t t e d by Aug. 1, 1980.
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 Publication costs oS this article were assisted by Gen-
be seen from Fig. 2(b) about 30% of the peak area is eral Electric Company.
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 REFERENCES
valence band. The n u m b e r s used for ~e and ~, are 1. A. F u j i s h i m a and K. Honda, Bull. Chem. Soc. Jpn.,
only estimates, however, the logarithmic dependence 44, 1148 (1971); Nature (London), 238, 37 (1972).
makes the value of E weakly d e p e n d e n t on these 2. L. A. Harris and R. H. Wilson, Annu. Rev. Mater.
parameters. This e x p l a n a t i o n is plausible and if the Sci., 8, 99 (1978).
states involved are intermediates of 02 evolution it 3. H. P. Maruska and A. K. Ghosh, Sol. Energy, 20,
suggests that they are 2-2.5 eV below the h y d r o g e n 443 (1978).
4. A. J. Nozik, Annu. Rev. Phys. Chem., ~9, 189
potential. (1978).
Summaryand Conclusions 5. M. Tomkiewicz a n d H. Fay, AppI. Phys., 18, 1
I n thi~ report e x p e r i m e n t a l results have been pre- (1979).
sented which indicate that oxidized states are pro- 6. R. H. Wilson, Abstract 415, p. 1038, The Electro-
duced on the surface of TiO2 electrodes in aqueous chemical Society Extended Abstracts, Seattle,
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- Washington, May 21-26, 1978.
7. R. H. Wilson, L. A. Harris. and M. E. Gerstner,
ditions which produce a p h o t o c u r r e n t in the cell. Most This Journal, 126, 844 (1979).
of these states are still there after several minutes. 8. R. M e m m i n g and F. Mollers, Ber. Bunsenges. Phys.
T h e y decrease at a rate consistent with t h e r m a l l y Chem., 76, 475 (1972).
activated hole emission from states several tenths 9. G. Beni, i n "Semiconductor L i q u i d - J u n c t i o n Solar
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 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 January 1980

Cells," A. Heller, Editor, p. 108, The E l e c t r o - 11. A. Many, CRC Crit. Rev. Solid State Sci., 4, 515
chemical Society Softbound Proceedings Series, (1974).
Princeton, N.J. (1977). 12. R. It. Wilson, J. Appl. Phys., 48, 4292 (1977).
10. T. F r e u n d and S. Roy Morrison, Surf. Sci., 9, 119 13. J. H i l i b r a n d and R. D. Gold, RCA Rev., 21, 245
(1968). (1960).

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 and S i F come from the reaction products of Si3N4 a n d
precise end p o i n t detection in p l a s m a etching (1-4) p o l y - S i w i t h CF4 in the plasma, respectively.
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 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
others such as mass spectroscopy (5), visual o b s e r v a - of the 674 n m line d u r i n g etching SigN4 films. The
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 emission intensity increased g r a d u a l l y w i t h increasing
(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 - 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
sure for the end point detection m e t h o d using an o p t i - w a r m e d up b y rf discharge, and then decreased r a p i d l y
cal emission and to e v a l u a t e the lower l i m i t of detec- as the surface a r e a of the r e m a i n i n g Si3N4 film d e -
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 creased, and finally leveled off a f t e r etching was com-
silicon n i t r i d e (Si3N4). pleted. The end point was c l e a r l y detected at the point
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 w h e r e the curve s u d d e n l y drops off in the figure.
and optical emission observation s y s t e m w h i c h has 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
been used in the e x p e r i m e n t . P l a s m a etching was car- 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
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 film.
(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- 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
p o r a t i o n ) . Wafers w e r e placed in a quartz w a f e r boat l o w e r limit of detection of the end point. The m e a s u r e
inside a quartz chamber. CF4 + 02 (4%) was used as is defined as the ratio of the change in emission in-
an etching gas. Typical etching condition was 100W tensity at the end point (B) to the m a x i m u m emis-
rf p o w e r and 0.5 Torr (66.5 P a ) . P o l y - S i and SisN4 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
films w e r e p r e p a r e d using the reaction of chemical 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
v a p o r deposition on t h e r m a l l y oxidized silicon s u b - and SigN4, the relations b e t w e e n B / A and the a r e a
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 END-POINT RF POWER IOOW
at one end of the chamber. No optical lens was used. CF4 +02(4%) 0,5 Tort
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 m'} (66.5 Pa)
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.
~F-OiF " B"
Z 'E-
REACTION CNAMSER

UJ

I~ ~'ETC..As
0 I 2 4
T I M E (rain

Fig. 1. Block dlagram of the etcMng apparatus and optical Fig. 2. Typical emission intensity of 674 nm .qs a function of
emission observation system. time.
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