J. Photochem Photobiol.

A: Chem, 79 (1994) 189-195

Photochemistry of semiconductor
I. Optical properties of ZnS sols
189
particles
Ling Zang, Chun-Yan Liu and Xin-Min Rent
Insti&te of Photogmphic Chemisby, Academia Sinicu, Be&g 100101 (Peoples Republic of China)
(Received October 15, 1993; accepted November 30, 1993)
Abstract
A ZnS sol stabilized by polyphosphate was prepared. The particle size is smaller than 3 nm. During the aging
and illuminating processes, the change in particle size was followed by the absorption and fluorescence measurement.
The mean size of ZnS particles in the solution has a limited value which did not decrease further owing to the
large surface tension. A more reasonable description of the optical processes in ZnS sols has been given. This
explains well the disappearance of discernibility of the exciton peak, as well as the band shift of fluorescence
which was caused by the surface modification. The effects of such parameters as aging, temperature, illumination
and surface condition on the fluorescence intensity of ZnS sols were studied. The luminescence efficiency could
be increased by a factor of 5 under the most favorable conditions.
1. Introduction
In recent years, numerous investigations have
been conducted on the photophysical and pho-
tochemical properties of semiconductor sols [l-5],
such as TiOz, CdS or ZnO, while only a few studies
have been done on the ZnS sol. This may be due
to its high electrical resistance and large band gap
which prevents electrochemical and photochemical
studies on it.
The luminescence of ZnS has been extensively
studied because ZnS crystals have a high emission
efficiency [6, 71. Since the first report on the
luminescence of colloidal ZnS was made by Becker
and Bard [8], a few significant studies have been
done by some workers [g-11]. The luminescence
properties can serve as a probe of not only the
interfacial electron-hole process but also the size
change in colloidal particles. Such a change was
observed by Henglein and coworkers in their earlier
work [9, lo], in which a continuous decrease in
size was found for ZnS colloids under illumination.
It is in contrast with the results obtained in our
and some other workers experiments [ll, 121. A
more reasonable explanation of the size change
of ZnS colloids under various experimental con-
ditions (such as aging and illumination) was pro-
posed in this study.
Author to whom correspondence should be addressed.
lOlO-6030/94/$07.00 Q 1994 Elsevier Sequoia. All rights reserved
SSDI 1010-6030(93)03760-E
A generally accepted view of the absorption
process in semiconductor colloids is that the initial
step involves the excitation of an electron into the
conduction band or the exciton level (slightly below
the conduction band) of the semiconductor by
ultraband gap radiation. If so, the absorption
spectra of semiconductor sols should be such that
the exciton peak falls slightly below the absorption
edge. However, the absorption edge often lies far
above the exciton peak. A more plausible de-
scription of the absorption process is indispensable
although a description of such process, with specific
reference to that in CdS, using a quantum-me-
chanical model has been developed by Chestnoy
et al. [13]. In this study, we tried to give a more
reasonable depiction of the optical processes in
ZnS sols, which has not, to our knowledge, been
reported in previous work.
2. Experimental details
2.1. Materials
Zn(NO,),, Na,S, NaOH and polyphosphate (PP)
were of analytical grades. They were all used
without further purification. Doubly distilled water
was used in all experiments.
2.2. Preparation of ZnS sols
The ZnS sol was prepared by a simple rapid
injection technique: 0.8 ml of 0.1 M Na,S solution
was added ragidly under vigorous stirring to 199.2
ml of 4 X 10- M Zn(NO& aqueous solution with
190 L. Zmg et al. I Photochemistry of semiconductor particles I
2 x 10m4 M PP, the concentration of which is given
by referring to the formula Na,P,O10 (formula
weight, 367.86). ZnS sols were aged in the re-
frigerator at about 10 C. The absorption and
fluorescence measurement were followed during
aging.
2.3. I lumination
Two kinds of ZnS sol (fresh and aged for 3
days) were used in the illumination experiments.
The illumination was carried out with a 500 W
high pressure Hg lamp (distance, about 15 cm;
without a fllter), and the solution was saturated
with air during the process. Absorption and fluor-
escence spectra were measured at given time in-
tervals during the illumination experiments.
2.4. Apparatus
Absorption spectra were recorded on a Hew-
lett-Packard diode array 8451A spectrophotometer
and the fluorescence spectra were recorded on a
Perkin-Elmer IS-05 fluorometer equipped with a
computer for data acquisition, storage and ma-
nipulation. Fluorescence quantum yields were de-
termined by comparison with rhodamine B in
ethanol, which is known to fluoresce with a quan-
tum yield of 0.69 [14].
3. Results
3.1. Effect of aging on the optical propetiies
The absorption spectra of ZnS sols aged for
different lengths of time are shown in Fig. 1. The
particle size of these sols cannot be larger than
3 nm since the absorption edge (about 315 nm)
is lower than 335 nm, which corresponds to the
size range of 2-3 nm [9]. Some changes in the
absorption spectra of ZnSsol occurred upon aging.
Wovelength (d
Wavelength hml
Pi. 1. Absorption spectra of ZnS sol at various aging times
(ZnS (diatomic) concentration, 4x lo- M, stabilizer, 2~10~
M PP). The sol was used in all the subsequent experiments.
Fig. 2. Fluorescence spectra of ZnS sol at various aging times.
The inset shows the dependence of fluorescence intensity cm the
aging time.
The absorbance reduced by about 10% in 9 days
(Fig. 1). This was believed to be a result of the
slow air oxidation
ZnS+202- Zn2++S0,2-
(1)
The Zn+ ions in the sol thus were in excess. The
exciton peak became pronounced and shifted
slightly to a longer wavelength, whereas hardly
any shift in the absorption edge was found.
Figure 2 shows the fluorescence spectra of ZnS
sols aged for different lengths of time. The quantum
efficiency for the fresh sol is about 1.7% and
reaches a highest level of about 5.5% for the sol
aged for 6 days. This efficiency is much higher
than that reported in the work of Dunstan et al.
[ll], in which the ZnS sols luminesced with a
quantum yield of 2X10-. In addition to the
increase in intensity with increasing aging time,
the maximum fluorescence shifted slightly to a
longer wavelength within the first 3 days. This
implies that the particle size increases slightly. No
band gap emission was observed for the ZnS ~01s.
3.2. Effect of illumination on the optical
properties
The ZnS sol is very sensitive to illumination
with a photon energy higher than its band gap.
The absorption spectrum changed drastically with
illumination time, as shown in Fig. 3. First, the
shoulder (the exciton peak) at about 282 nm
became slightly pronounced. On increasing the
illumination time, it became increasingly vague
and almost disappeared after about 60 min. In
the meantime, the absorption edge shifted to a
longer wavelength. This was quite different from
the results obtained by Henglein and Gutierrez
[9], in which the onset of light absorption shifted
continuously to a shorter wavelength and the ex-
L. Zang et al. / Photochemdy of semiconductor panicles I 191
Wavelength (nm)
Fig. 3. Absorption spectra of the ZnS sol aged for 3 days at
various times of illumination in the presence of air. The fresh
sol showed a similar behavior.
.V
fresh sol 40 60 I
60
z
:
60
c
2
.g 40
5
20
0
330 400 450 500
loo
3-day-aped Sol
- 1
28 60
Fig. 4. Fluorescence spectra of the two ZnS sols at various times
Of ihninatiDn in the presence Of air. The flUOreXence hItenSit&
were manipulated to be at the same kvel for the observation
Of band shift.
citon peak became more and more pronounced
during the whole illumination process. The ab-
sorbance of ZnS sol decreases very quickly upon
illumination, as can be seen in Fig. 3.
The fluorescence spectra of ZnS sols illuminated
for different times are shown in Fig. 4. It can be
seen that the fluorescence spectra of the two sols
escence maximum of the fresh sol shifted contin-
uously to a longer wavelength in the whole illu-
mination period. In fact, the shift in the initial
period is a consequence of the decrease in fluor-
escence at a shorter wavelength. The width of the
fluorescence band became narrower and narrower
at the same time. For the sol aged for 3 days,
the fluorescence maximum shifted to a shorter
wavelength in the first 4 min and then shifted to
a longer wavelength as in the case of the fresh
sol.
It was also found that the intensity of fluor-
escence of the two sols underwent different changes
during the illumination process (Fig. 5). Consid-
ering the great change in absorbance during the
illumination, the specific intensity (the ratio of the
fluorescence intensity to the absorbance at 282
nm) was used to compare the fluorescence in-
tensities of sols in different illumination times.
With the exception of the slight decrease in the
first 4 min, the fluorescence intensity of the sol
aged for 3 days increases steadily with illumination.
However, for the fresh sol, the fluorescence in-
tensity increased sharply in the first 20 min of
illumination and then decreased quickly with fur-
ther illumination.
3.3. Effect of temperature on fluorescence
It is known that the fluorescence intensity de-
pends strongly upon temperature [lo, 151. In the
Arrhenius plot (Fig. 6), In l/I is plotted vs. the
reciprocal temperature as is usually done for fluor-
escence processes with competing thermal deac-
tivation, where I is the fluorescence intensity. With
increasing temperature for 0 C to about 50 C,
-B-fresh sol
--+--3-doy-oqsd sol
01
I I I
0 20 40 60
J
Illumination time, t (min.1
Fig. 5. Fluorescence intensity of the two ZnS sols as a function
changed differently upon illumination. The fluor- of the illumination time (from the data in Fig. 4).
192 L. Zang et al. / Photochemirny of semiconductor parricks I
I .6
1.2
z
C
5
e 0.0
D
w
.
5
0.4
0
-4-day-aged sol
--+--14-day-aged sol
I/T (I lO+K-)
Fig. 6. Plot of In(W) VS. the reciprocal temperature for the hvo
zas sols.
the fluorescence intensity decreased to about 25%
of its value at 0 C. The fluorescence intensity of
the two ZnS sols changed similarly with temper-
ature. In other words, the degree of dependence
does not change with the surface condition, which
may be quite different for various aging times.
The activation energy for the competing process
can be calculated from the slope of line in Fig.
6, to be about 19 kJ mol-l.
3.4. Efict of surface condition on fluorescence
In our experiments, various ions, such as Cu+,
Ag+,Cd2+,Zn2+, m+,.S-,OH-,I- andSCN-,
were used to modify the surface of ZnS colloids.
Some of the ions were found to be very effective
in changing the optical properties of the ZnS ~01s;
this will be described in the next paper of this
series. Figure 7 showed the change in the fluor-
escence spectrum of the ZnS sol aged for 9 days
with the addition of OH- and Zn+ ions. The
fluorescence intensity increased on addition of
OH- ions up to 5 X 10e4 M, and no increase was
found on further addition (inset in Fig. 7). The
fluorescence spectra became wider owing to the
addition of OH- ions. The intensity increased
were markedly at longer wavelengths than at
shorter wavelengths. If 2.5X 10e8 M Zn2+ was
added to the ZnS sol with a prior addition of
5~10~~ M OH-, the fluorescence intensity de-
creased and the shape of the spectra did not
change. The same effect was also shown in spectrum
d in Fig. 7 which was obtained by adding 2 X low4
M Zn2+ to the ZnS sol aged for 9 days without
any prior addition. The fluorescence intensity de-
420 460
Wavelength Lnml
Fig. 7. Fluorescence spectra of the ZnS sol aged for 9 days upon
addition of OH- and Zn2+ ions: curve a, no addition; curve b,
addition of 5 X lo- M OH-; curve c, addition of 2.5 X 10ms M
Zn2* to sample for curve b; curve d, addition of 2x10- M
zn2+.
creased about 60%. A clear red shift of fluorescence
maximum was observed, as shown in Fig. 7.
4. Discussion
4.1. Sire of ZnS colloids
It is well known that the colloids are thermo-
dynamically unstable with respect to the bulk phase.
The surface tension favors a small surface area.
This means that the colloidal particles have a
natural tendency to aggregate. The smaller the
particles, the more dramatic is the increase in the
specific surface area, and hence the stronger is
the tendency to particle aggregation. Such tendency
was found in the initial aging period of ZnS sols
(Fig. 2). The smaller particles in the fresh sol
tend to dissolve and the larger particles grow
through Ostwald ripening.
Considering the size dependence of the tendency
to particle aggregation, the average size of ZnS
particles under the condition of our experiments
should have a limited value, which does not de-
crease further even under photodegradation. The
results shown in Fig. 4 can be regarded as an
indication of the change in particle size in view
of the size quantization effect, which has been
reported elsewhere [lo, 16, 171. The blue shift
and red shift of the fluorescence maximum suggest
a decrease and an increase respectively in particle
size. This is similar to the results obtained by
Dunstan et al. [ll] and Rossetti et al. [12], but
quite contrary to the results obtained by Henglein
and Gutierrez [9], in which a continuous decrease
in particle size of the ZnS sol was found during
illumination. The contraditory results may be
caused by the different stabilizers used in the
experiments.
L. Zang et a.! I Photochemishy of semiconduct0r parti cl es I 193
4.2. Absorption process in ZnS sols
In our studies, the exciton peak (absorption
involved between the valence band and the exciton
level) of ZnS sols is not so pronounced as that
obtained in methanol by Rossetti et nl. [12]. Even
in their results, the ZnS sol prepared in aqueous
solution shows a much less pronounced exciton
peak compared with that prepared in methanol
solution. A similar phenomenon was also observed
for CdS sols prepared in water and propanol-2
solution [18]. Obviously, the solvent is the most
effective factor that affects the characteristics of
the exciton peak. In the work of Rossetti er al.,
this solvent effect was referred to as a prevention
of the colloid particles from aggregation, which
was believed to be the origin of the difference
between the exciton peaks. The ZnS sol obtained
in our experiments, which was stabilized by PP,
was very stable and no obvious aggregation can
be found after a long aging time (e.g. 14 days).
This can be seen from the fact that the onset of
the absorption spectra did not shift significantly
to a longer wavelength, while the exciton peak
became a little more pronounced upon aging. This
is also in contrast with the results of Rossetti et
al. [12].
The disappearance of the discernibility of the
exciton peak can be attributed to either a broad-
ening or a decrease in this peak. This may be due
to trapping of the excitons by an impurity center
at the surface. This may happen as follows: the
impurity center first traps an electron (or hole)
and, once this has happened, the impurity center
(now charged) can attract a hole (or electron)
through the coulombic force. The level of such a
trapped exciton is lower than that of an untrapped
exciton by the interaction energy of the exciton
with the impurity center. Thus the exciton peak
is broadened to a longer wavelength where the
absorption associated with the trapped exciton
level occurs. The intensity of the original exciton
peak weakens owing to the decrease in the number
of untrapped excitons. Roth Zn and S2- ions
on the surface can trap photogenerated excitons
in ZnS colloids. The increase in the discernibility
of the exciton peak during aging (in the process
the Zn* ions were in excess) indicates that S2-
(hole trap) is more efficient than Zn*+ (electron
trap) in trapping excitons. This is understandable
considering the different electrode potentials of
the two ionpairs,E(S-S), -0.51 V;E(Zn+-Zn),
-0.76 V.
The trapping of excitons is affected by the
dielectric properties of the environment of the
ZnS particle, which in turn is determined to a
great extent by the properties of the solvent. A
solvent with a higher polarity is always favorable
for the creation of a gradient of electrostatic
potential around the ZnS particle and hence is
conducive to the movement of photogenerated
charge carriers (hole and electron) from the in-
terior to the surface. Tbe difference in the polarities
of the solvents used in the experiments of Rossetti
et al. [12] and in our experiments can therefore
be reasonably regarded as an origin of the dif-
ference in the discemibilities of the exciton peaks.
In addition to the absorption processes asso-
ciated with band gap and exciton excitation, the
absorption processes involving impurities (acceptor
and donor) in semiconductor colloids may also
occur. This is shown in Fig. 8, where a and b
represent the processes in which an electron is
excited from the valence band to a donor or from
an acceptor to the conduction band, and c illus-
trates an absorption process involving transition
from an acceptor to a donor. Such processes lead
to absorption with a photon energy lower than
the band gap if the donor or acceptor exists in
a relatively deep site.
For small particles, the number of molecules
on the surface is comparable with that in the
interior. Even a minute amount of impurities ad-
sorbed on the surface lattice can cause a striking
increase in the concentration of defects in one
particle. Zn2+ or S*- ions strongly adsorbed at
the surface lattice can be regarded as the deep
traps contributing to absorption lower than the
band gap.
It can be seen from the above discussion that
the absorption edge of the semiconductor sol is
not equivalent exactly to the band gap but is lower
than the latter in energy. In fact, the exciton peak
(if it is sufficiently pronounced) is more precise
than the absorption edge as an indicator for the
change in particle size.
CB
D
A
VE
Fig. 8. Various absorption processes invoting impurities (see
text for details): CB, conduction band; VB, valence band; A,
acceptor; D, donor.
194 L. Zang et al. I Photochemirhy of semiconductor particles I
4.3. Fluorescence
4.3.1. I ntensity
It is commonly accepted that the S2- vacancy
(in the surface layer) is the fluorescence center
for the sols of CdS [I%213 or ZnS [lo] in the
cubic zinc-blende structure. That is to say, the
S2- ion can quench the fluorescence more effi-
ciently than the cations Cd+ or ZP. Removal
of S2- ions on the surface is always favorable to
the enhancement of fluorescence. The removal
can be achieved either by illumination (photo-
oxidation) or by aging (air oxidation). Owing to
oxidation the Zn ions on the surface were in
excess. A sufficiently high concentration of ZrP
ions can also effectively quench the fluorescence.
This is because the high concentration of Zn+
favors the electron-trapping reaction
Zn2+ +2e---, Zn
(2)
which hardly occurs in the condition of a low
concentration of Zn+ ions.
Of particular interest is .the sharp decrease in
the fluorescence intensity of the ZnS sol. This can
be attributed to the high concentration of defects
generated in the colloidal particles. The size dis-
tribution of the fresh ZnS particles is not narrow.
Under illumination, larger particles in a poor crystal
structure were formed through Ostwald ripening,
which proceeded much faster under illumination
than under aging [X3]. In contrast, few of these
poor crystalline particles can be formed in the
ZnS sol aged for 3 days owing to its narrow size
distribution.
As reported by the previous workers [19, 221,
the fluorescence intensity also depends to some
extent on the pH of the solution. The OH- ion
is effective for blocking the defect on the surface
of colloid. Such a defect is believed to be the
center for the radiationless recombination of the
photogenerated charge carriers. The increase in
the fluorescence intensity caused by OH- has not
been clearly explained to date, although Henglein
et al. [17] postulated a possible explanation for
the CdS ~01s: the removal of SH- groups and the
accumulation of Cd* on the surface in the form
of S2-. . .Cd2*.. .OH- seem to destroy the sites
where radiationless recombination of the charge
carriers occurs. This is hard to accept because the
excess Cd+ ions in the case of a high pH should
precipitate to form Cd(OH)2 and they could not
be in the postulated form. The binding of OH-
with the excess cations Cd2 or Zn2+ at the surface
lattice seems to be the main reason for the fluor-
escence enhancement because the binding can
weaken the ability of the cation+ for trapping the
photogenerated electron (eqn. (2)). This was ver-
ified by the results shown in Fig. 7. The addition
of OH- to the ZnS sol aged for 9 days (with
excess Zn2 + ions) resulted in an enhancement in
fluorescence. The subsequent addition of Zn2+ (in
the form of Zn(OH),, n 22) [24], however, de-
creased the intensity. This led us to conclude that
the excess Zn(OH), which covered the surface
acted as new centers for the radiationless recom-
bination of the photogenerated charge carriers.
Temperature has another significant effect on
the intensity of fluorescence. The photogenerated
charge carriers decay in two competitive ways,
namely radiation and radiationless recombination.
radiationles
ZnSh ZnS (e--h*)
rJ
heat + ZnS
photodecomposition products
\
(Zn+ , S, SOJz- etc.)
radiation
hv + ZnS
The radiationless process is temperature depen-
dent with an exp( -E/RT) law, where E is the
activation energy. The higher the temperature, the
faster is the radiationless process, and hence the
lower is the fluorescence intensity. The dependence
of the radiationless process on temperature was
little affected by the surface condition (Fig. 6).
Thii implies that the radiationless recombination
of the charge carriers possibly happens in the inner
part of ZnS colloids.
4.3.2. Wavelength
In addition to the size change, the shift in the
fluorescence maximum can also be caused by sur-
face modification with adsorbed ions. The adsorbed
ions often act as shallow traps of photogenerated
charge carriers in the luminescence process. As
a result, the fluorescence maximum shifts to a
longer wavelength. The excess OH- ions (possibly
%ppose that the binding form of M(OH)2, the standard
potential of the reaction M(OH),+2e- =M+20H-(aq) can be
obtained as
&(M(OH),OH-, M)==E(ti+-M)+ g In rz,
where M represents the element Cd or Zn and K,_ is the solubility
product of &OH)% Using the standard potent& and solubili6
oroducts EKd2-Cd~ = - 0.40 V, EfZn2+-ZnI = -0.76 V.
jC,(Cd(OH)& 2.5 X lo-l4 and Kz(kn(Ok)z)= 1.2~ lo-l7 froi
ref. 23, one can ohtain the standard potential EO(M(OH)+H-,
M) as follows: E(OH--Cd(OH)2, Cd)= -0.80 V,
E(OH--ZII(OH)~, Zn)= -1.26 V. So the negative potential
makes it hard for Cd(OH)2 and Zn(OH), to trap the photo-
generated electrons.
L. Zang et al. I Photochemiptry of semiconductor particles I 195
in the form of Zn(OH),, n B 2) at the surface of It should be emphasized here that the optical
ZnS particles can be regarded as shallow traps process in semiconductor sols is very complicated
which caused a red shift in the fluorescence spectra and cannot be thoroughly discussed in this article.
(Fig. 7). Some further studies are necessary in this regard.
The absence of band gap emission (Fig. 2)
indicates that electrons in the conduction band
or exciton level cannot recombine directly with
holes in the valence band. As postulated by Weller
[25], at least one of the charge carriers is trapped
in the luminescence process. In this paper, the
trapped charge carrier is further described in the
form of trapped exciton as described above. Prior
to luminescence, the trapped exciton relaxes
through interaction with other charge carriers or
defects in the surface layer where the trapping is
believed to take place. This relaxation causes a
decrease in energy of the trapped exciton which
now luminesces with a longer wavelength. One
can see that the decrease in energy of the trapped
exciton depends upon the concentration of defects
in the surface layer of the particle. For zinc sulfide,
it is hard to obtain colloidal particles with a perfect
crystal structure by&situ generation. Some defects
always exist in the generated particles (especially
in the surface layers) owing to the peculiar prop-
erties of the Zn+ ion in alkaline solutions [24].
During the rapid precipitation, such ions as
Zn(OH),- and Zn(OH)42- can be formed as
interstitials in the particle. On the contrary, band
Acknowledgments
Thanks are due to the National Natural Science
Foundation of China and Eastman Kodak Com-
pany for their financial support for this work.
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5. Conclusions
For a stable semiconductor sol, a limiting low
value of the particle size exists because the large
surface tension of small particles favors aggre-
gation. The decrease in absorbance of ZnS sols
under illumination is caused by the reduction in
the number of particles and not by the decrease
in particle size.
Owing to the small size of the colloidal particles
and thus the large surface-to-bulk ratio, the nature
of the surface is responsible for the physi-
cal-chemical properties of the particle. Therefore
surface effects should be taken into account when
studying optical processes in semiconductor ~01s.
As the particle size decreases, not only quantization
effects but also surface effects become significant.
The changes in optical properties are caused si-
multaneously by the two kinds of effect instead
of by just one of them.
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