JOURNAL OF APPLIED PHYSICS VOLUME 84, NUMBER 5 1 SEPTEMBER 1998

Luminescence studies of localized gap states in colloidal ZnS nanocrystals

D. Denzler, M. Olschewski, and K. Sattlera)
Department of Physics and Astronomy, University of Hawaii at Manoa, 2505 Correa Road,
Honolulu, Hawaii 96822
~Received 23 March 1998; accepted for publication 4 June 1998!
ZnS nanoparticles were prepared by chemical precipitation of Zn21 with sulfur ions in aqueous
solution. The ultraviolet-excited samples reveal detailed structure in the luminescence spectra. A
doublet pattern observed in the long wavelength region is attributed to the coexistence of the two
crystalline forms in ZnS particles. The visible luminescent radiation at 590.1 nm is due to Mn
impurities. The dominant emission band at short wavelengths exhibits a quadruple fine structure
with peaks located at 416.1, 423.9, 430.1, and 437.8 nm which are identified with optical transitions
arising from vacancy and interstitial sites for both Zn and S atoms. © 1998 American Institute of
Physics. @S0021-8979~98!07717-2#

I. INTRODUCTION The reported luminescence spectra show a broad ultraviolet

Colloidal semiconductor nanocrystallites have been
studied intensively,1 and as there is a potential of application
in nonlinear optical devices,2 focus has been on their optical
properties. Such materials are promising for the production
of optical sensitizers and photocatalysts.3–5 Further, they can
be used for light converting electrodes,6 electroluminescent
applications7–9 and quantum devices.10,11 The optical proper-
ties can be tuned due to quantum-size effects which effec-
tively lead to a size-dependent variation of the band gap
energy. Differently colored powders can be produced just by
variation of the grain sizes. The preferred characterization
methods for such size-dependent behavior are optical absorp-
tion and luminescence.
If discrete energy levels are present in the band gap of
the crystallites, these may dominate the optical spectrum.
Luminescence measurements then yield information about
the energetic positions of the electronic states in the gap.
Such localized states can be due to various types of imper-
fections like vacancies, interstitial atoms, and atoms at sur-
faces and grain boundaries. It is often difficult to determine
the exact energy positions of these states, because they may
be very close in energy and cannot be resolved in the lumi-
nescence bands.
Luminescence in bulk solids with wide band gaps has
been investigated for a long time.12,13 However, nanocrystals
of such materials became of interest just recently. Among the
most studied particles in colloidal form are the II-VI semi-
conductor compounds CdS and ZnS.14 ZnS has a band gap of
3.6 eV at 300 K. This corresponds to ultraviolet ~UV! radia-
tion for optical interband transition, with a wavelength of
340 nm. Wide-band gap semiconductors are ideal materials
for studies of discrete states in the gap. Visible luminescence
can only originate from transitions involving these localized
states.
Previous studies of luminescence and absorption in col-
loidal ZnS have been performed for pure ZnS samples.15–17
a!
Electronic mail: Sattler@hawaii.edu
peak at around 420 nm. ZnS can be doped with Mn very
easily, where few Mn atoms substitute for Zn atoms.18 This
doping causes a visible orange luminescence at about 590
nm. Both the ultraviolet and the orange peak have been re-
ported to shift by a few nm upon prolonged irradiation to UV
light or aging of the colloid.19
The crystallography of ZnS is complicated by its propen-
sity to crystallize in a variety of polymorphic modifications.
The principal structure types are cubic zinc blende ~sphaler-
ite! and hexagonal wurtzite in which the atoms are tetrahe-
drally bound in network arrangements related to those of the
group IV semiconductors. In addition, there are related poly-
types, with sustantially deviative structures of zinc blende
and wurtzite. Crystals encountered in practice are usually
nonideal and contain defects and imperfections. Because of
the extensive polytypism, particularly in the case of ZnS,
defect structures associated with intergrowths of several
crystal forms are commonly encountered. Therefore, the
peaks in luminescence spectra are often broad and individual
lines characteristic for the different polytypes are not re-
solved.
II. EXPERIMENT
For sample preparation, zinc sulfate and sodium sulfide
were used as supplied. An 831025 molar solution of ZnSO4
and a 431023 molar solution of Na2S were prepared in de-
ionized water and stirred for about 1 h. Then 1 ml of the
Na2S solution was injected into 50 ml of the rapidly stirred
ZnSO4 solution. The colloidal sample was then stirred for
another 10 min.
Chemical precipitation is widely used for the preparation
of colloidal nanoparticles.20,21 In the method described
above, we used the following exchange/replacement reac-
tion:
ZnSO4↔Zn211SO22
4 , ~1!
N~Zn211Na2S!↔~ZnS!N12N~Na1!. ~2!

0021-8979/98/84(5)/2841/5/$15.00 2841 © 1998 American Institute of Physics

2842 J. Appl. Phys., Vol. 84, No. 5, 1 September 1998
FIG. 1. Schematic sketch of the experimental setup used for luminescence
measurements of colloids. Photoexcitation radiation is emitted by a 254 nm
UV lamp.
Due to the high solvatation energy in water, the equilibrium
of Eq. ~1! lies far on the right side. The driving force for
reaction ~2! is the formation of strong ZnS bonds. This tech-
nique is known to produce fairly monodispersed crystalline
particles with diameters of 1–5 nm.15
Auger and x-ray photoemission spectroscopy were used
to characterize the chemical composition of the reaction
products. A drop of the colloid was placed on a gold sub-
strate and studied after evaporation of the solvent. The analy-
sis of the spectra shows the expected peaks at the character-
istic ZnS electron energies. This confirms that Zn and S were
forming a chemical compound.
The setup for the luminescence measurements is shown
in Fig. 1. A 254 nm UV lamp was the exciting light source.
Wavelengths below 400 nm were cut off by a filter. The 254
nm wavelength corresponds to a photon energy of 4.9 eV.
ZnS has an energy gap of E g 53.7 eV. For excitation ener-
gies above E g , electrons of the valence band are excited into
the conduction band and electron-hole pairs are created.
Their recombination can occur at various lattice or interstitial
sites, leading to light emission with distinct and site-specific
luminescence peaks. The luminescence spectra were re-
corded using a EG&G Princeton Applied Research model
1420R HQ 1024-channel photomultiplier array. The applied
UV source did not give any structure to the luminescence
spectrum. We checked this very carefully. Using a cutoff
filter the exciting radiation was restricted to the far UV. The
measured sample spectra were normalized with a reference
spectrum of pure water.
III. RESULTS AND DISCUSSION
Luminescence spectra for three ZnS samples in the range
400–800 nm are shown in Fig. 2. The spectra can be divided
into three regions: ~A! a nonvisible UV emission band from
400 to 450 nm, ~B! a visible emission band from 450 to 650
nm, and ~C! a nonvisible infrared ~IR! region above 650 nm.
In the UV and IR regions, different samples exhibit the same
spectral features. However, they differ significantly in the
visible region, even though the three samples were prepared
in the same way.
A. IR region
The emission in the IR region ~Fig. 3! can be divided
further into two bands. The band between 675 and 715 nm
Denzler, Olschewski, and Sattler
FIG. 2. Survey of luminescence spectra for three different colloidal ZnS
samples. Three regions ~UV, visible, and IR! are specified for separate dis-
cussion.
consists of four peaks which form two identical doublets,
shifted by 18 nm. In each doublet there is a narrow and a
broad peak, separated by 7 nm. The other band, ranging from
725 to 800 nm, consists of 10 major peaks. Again we can
identify several doublets, split by 7 nm. The relatively small
intensity of the peaks in the IR indicates that the transitions
have small oscillator strengths. This is the case for transi-
tions between distinct localized states in the gap which arise
from impurities and imperfections.
In order to understand the observed doublets we may
look closer at the atomic structure of ZnS. There is a close
relation between the wurtzite and zinc blende structures. The
atomic arrangements are very similar out to the second-
nearest neighbors. The only difference in coordination is the
substitution of a trigonal prism in wurtzite for an antiprism in
zinc blende. It is necessary to go to third-nearest neighbors to
find significant differences between the structures. Both zinc
blende and wurtzite modifications of ZnS are found in natu-
ral deposits of ZnS.
The structural interrelations are conveniently treated by
using a hexagonal description for cubic zinc blende. Then,
wurtzite and zinc blende structures can be viewed as the
stacking of interleaved close-packed double layers of zinc
FIG. 3. IR luminescence for three different samples. The five doublets
present in this region are marked for easy identification.
J. Appl. Phys., Vol. 84, No. 5, 1 September 1998
and sulfur. Regarded as such close-packed sequences, wurtz-
ite repeats after two double layers, zinc blende after three.
The observation of the five doublets, all showing the
same 7 nm splitting, is a puzzling result. The observed peaks
in the IR are closer than 25 meV ~the thermal broadening at
room temperature! which clearly shows that the peaks are
not from transitions at the same site but rather from different
sites in different crystalline environments. We propose that it
is due to zinc blende- and wurtzite-type domains present in
the same particle. While bulk crystals of ZnS encountered in
practice may contain complex mixtures of polytypes, the dif-
ferent phases rather seem to separate in small particles. The
electronic transitions at an ionic site are known to depend on
the local crystal field produced by its neighbors. Different
crystalline environments lead to small differences in the elec-
tronic state distribution which may show up as a splitting of
levels in optical spectra. It would be nice to verify the an-
ticipated coexistence of the two crystal structures. However,
this is a difficult task in the case of small particles.
The essential difference between the potential that an
electron experiences in an ideal wurtzite lattice and that in a
zinc blende lattice is the relatively small difference in ‘‘crys-
tal field’’ due to sites beyond the next nearest neighbors.
Therefore, if two types of lattices coexist side by side in one
particle, the energies of localized states in different domains
assume slightly different values. This results in doublet
structures for the transitions between these states.
B. Visible region
In the visible region the spectra in Fig. 1 show a broad
and intense emission band around 590 nm. It is this orange
luminescence which is observed with the human eye. This is
in correspondence with earlier results for Mn-doped bulk22
and colloidal ZnS.19 Therefore the visible emission observed
in our experiments is attributed to states arising from Mn
impurities. The emission is due to the 4 T 1 (G)→ 6 A 1 (S) tran-
sition within the 3d shell of Mn21. The manganese occupies
substitutionally the Zn lattice sites. Recombination of
electron-hole pairs and energy transfer to the Mn21 centers
cause this emission. In fact, films of zinc sulfide doped with
manganese are the active layers of both ac and dc addressed
thin film electroluminescent devices. In our studies, the Mn
ions are trace amounts in the chemicals used for sample
preparation. Consistent with this explanation is our observa-
tion that different samples exhibit this peak at the same
wavelength but with different intensities. Also, we deliber-
ately doped ZnS with Mn, and always found the expected
orange emission band. For absolutely pure ZnS nanoparticles
no visible luminescence would be observed.
In contrast to the distinct narrow peaks in the infrared
region, the intensity distribution in the orange band is
smooth. This smoothness is in correspondence with the pro-
posed origin of the visible luminescence for Mn-doped
samples. Both, the broad band and its smoothness are attrib-
uted to the large number of optical transitions associated
with the 3d 5 states of Mn. As the Mn atoms substitute Zn in
the crystal lattice, the energy states of the 3d electrons are
split in the tetragonal crystal field. The superposition of tran-
Denzler, Olschewski, and Sattler 2843
FIG. 4. Luminescence in the UV region for several samples. A quadruple
fine structure is observed for all spectra.
sitions from this wide energetic distribution then yields the
observed broad and smooth peak.
C. UV region
The emission band in the UV region shows a quadruple
fine structure ~Fig. 4!. All prepared samples of colloidal ZnS
revealed this structure. Each spectrum was fitted with four
Gaussians in order to determine the exact peak positions.
The result of a fit for one sample is given in Fig. 5~a!. From
five analyzed samples, the following peak positions with
their standard deviations were obtained: 416.160.6, 423.9
60.9, 430.161.0, and 437.860.3 nm. The full width at half
maximum for these four peaks ranges from 6.0 to 8.7 nm.
In previous studies of ZnS colloids only one UV peak at
428 nm was observed15 and was assigned to transitions due
to sulfur vacancies. After irradiation treatment, the peak had
shifted to 418 nm and was attributed to transitions involving
interstitial zinc or sulfur atoms. In both samples, the freshly
prepared and the photodegradated, only a single emission
peak in the UV was found. This peak had a width of about
80 nm and no fine structure.
It has been reported in previous work on colloidal ZnS
that vacancy states lie deeper in the gap than states arising
from interstitial atoms.15 Therefore we conclude that the two
long ~430.1 and 437.8 nm! and the two short ~416.1 and
423.9 nm! wavelength peaks @Fig. 5~a!# are due to transitions
involving vacancy states and interstitial states, respectively.
Figure 5~b! shows a schematic energy level diagram
with the four types of point defects which can be present in
pure ZnS particles. Vacancies of sulfur and zinc are equiva-
lent to localized donor and acceptor states, respectively. In
the case of interstitials, zinc atoms lead to donor states and
sulfur atoms to acceptor states. Involving these four levels in
the energy gap, four optical transitions in the observed UV
range can occur. These are transitions either from or into
extended states of the conduction and valence bands. Com-
pared to the transitions between only localized states ~as ob-
served in the IR!, the participation of band states yields the
intense luminescence in the UV.
It remains to be discussed which one of the transitions
involves states of Zn or S. A clue is provided by considering
2844 J. Appl. Phys., Vol. 84, No. 5, 1 September 1998 Denzler, Olschewski, and Sattler

TABLE I. Wavelengths and photon energies for the observed luminescence

peaks with their full widths at half maximum ~FWHM!.

Wavelength FWHM Photon energy FWHM

~nm! ~nm! ~eV! ~meV!

UV region 416.1 8.75 2.980 62.7

423.9 6.36 2.925 43.9
430.1 5.97 2.883 40.0
437.8 6.35 2.832 41.1

Visible region 590.1 42.14 2.101 150.2

IR region 684 5.40 1.813 14.3

691 2.56 1.794 6.6

702 6.48 1.766 16.3

709 2.76 1.749 6.8

744 8.98 1.666 20.1

751 2.89 1.651 6.4

757 6.22 1.638 13.5

764 1.45 1.623 3.1

774 2.38 1.602 4.9

789 3.85 1.571 7.7

796 2.52 1.558 4.9

FIG. 5. ~a! One of the spectra of Fig. 4 fitted by four Gaussian curves to
determine the exact peak positions. ~b! Schematic energy level diagram for
the point defects in pristine ZnS: I S5interstitial sulfur, I Zn5interstitial zinc, the electron levels due to surface and interface states should
V S5sulfur vacancy, and V Zn5zinc vacancy. The levels are drawn corre-
sponding to the peaks in the luminescence spectrum of ~a!. theoretically be determined for ZnS nanocrystals.

the defective incorporation of Zn or S into the crystal. In the
case of interstitials, extra ions are located at sites not occu-
pied in the perfect crystal. When an atom is placed into such
a site, a rearrangement of the nearest neighbors takes place.
The extent of deformation depends on the size of the incor-
porated atom. As the sulfur ions are larger than the zinc ions,
interstitial sulfur induces more strain to the lattice. Electron
levels originating from this site will have smaller binding
energies due to such strain. Therefore, interstitial sulfur
states should be located closer to the valence band edge than
interstitial zinc states to the conduction band edge. Conse-
quently, we attribute 416.1 nm peak to interstitial sulfur and
the 423.9 nm peak to interstitial zinc. Similar considerations
can be applied for the vacancies. Therefore we attribute the
430.1 nm peak to sulfur vacancies and the 437.8 nm peak to
zinc vacancies.
While the positions of the quadruplet peaks are the same
for all samples, the heights of the two vacancy-related peaks
fluctuate for different samples. A different ratio of zinc va-
cancies to sulfur vacancies induced by slightly varying
preparation conditions may be responsible for this effect.
Table I shows wavelengths and photon energies for the
observed photoluminescence peaks, with their widths at half
maximum ~FWHM!. In order to assign the transitions quan-
titatively to the involved gap states, a detailed theoretical
study of the point defects in ZnS nanocrystals is required. It
needs to consider the different polymorphs of ZnS and their
separation in different domains in the small particles. Also,
IV. SUMMARY
Luminescence spectra of colloidal ZnS have been re-
corded between 400 and 800 nm. In the IR region ~650–800
nm!, the low intensity doublet structure is attributed to inter-
impurity transitions. The small doublet splitting of 7 nm is
interpreted by a coexistence of wurtzite and zinc blende do-
mains in one particle. The well known visible orange emis-
sion band is related to Mn traces. In the UV region ~400–450
nm!, a quadruple fine structure is observed. It is explained by
optical transitions involving the localized states which arise
from the point defects of pure ZnS.
ACKNOWLEDGMENTS
The authors would like to thank John Akutagawa, Bjo-
ern Marsen, William Pong and Paul Scheier for their help
and for useful discussions.
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