Chemical Conversion Synthesis and Optical Properties of Metal Sulde

Hollow Microspheres
Y. F. Zhu, D. H. Fan, and W. Z. Shen*
Laboratory of Condensed Matter Spectroscopy and Opto-Electronic Physics, Department of Physics,
Shanghai Jiao Tong UniVersity, 1954 Hua Shan Road, Shanghai 200030, Peoples Republic of China
ReceiVed May 18, 2008. ReVised Manuscript ReceiVed July 5, 2008
A facile chemical conversion method has been demonstrated to prepare various metal sulde hollow microspheres.
The present strategy utilizes the large difference in solubility between ZnS and other metal suldes (Ag
2
S, PbS, CuS,
Cu
2
S, Bi
2
S
3
, and Sb
2
S
3
) for the effective transformation and shows mild growth conditions and good reproducibility.
The morphology, structure, and composition of the yielded hollownanostructures have been conrmed by transmission
electron microscopy, energy-dispersive X-ray analysis, and X-ray diffraction measurements. The optical properties
of the metal sulde hollow microspheres have been systematically investigated by absorption, micro-Raman, and
photoluminescence spectroscopy. The results demonstrate that these metal sulde hollow microspheres possess good
optical quality with tunable band gaps and luminescence properties, which indicate their broad potential applications.
This simple chemical conversion technique can be further extended to the synthesis of other semiconductors with
various morphologies.
I. Introduction
Well-dened hollow micro- and nanospheres have recently
attracted much attention in physics, chemistry, and material
science communities because of their unique properties including
low density, high specic surface area, and distinct optical
properties.
1-8
Until now, hollow spheres made of various
materials such as metals, semiconductors, and organic materials
have been extensively investigated.
1-19
Among the above-
mentioned hollow spheres, the study of semiconductor metal
sulde hollow spheres is of particular interest for the potential
applications of such materials in the elds of optics, electronics,
and optoelectronics.
9-13
Templates, including bacteria, poly-
styrene, blockcopolymers, siliconspheres, polymer latexspheres,
andemulsiondroplets/micelles, have beensuccessfullyemployed
to synthesize metal sulde hollow spheres.
14-19
However, the reported template methods always require
extremely complicated synthetic procedures and are usually
suitable only for a certain specic material.
20
The development
of a facile, versatile synthetic pathway to prepare various metal
sulde hollowmicrospheres is veryimportant andquite necessary.
In particular, it is highly desirable for such a method that can
convert the chemical compositions of hollow microspheres
without destroying the original morphology. Recently, cation
exchange has been demonstrated as an effective way to convert
the chemical compositions of nanostructures without destroying
the original morphology.
21
Nevertheless, little has been devoted
to the conversion of one kind of metal sulde hollow micro-
spheres to others to realize diversication of the yielded hollow
microsphere compositions to broaden their potential applications.
Moreover, in spite of earlier efforts on the synthesis of metal
sulde hollow micro- and nanospheres, the optical properties of
the yielded products are rarely systematically reported.
14-19
A
detailed exploratory study of their room-temperature optical
properties canbe muchinterestingas a result of their technological
importance and fundamental interests.
In this article, we present the successful realization of various
metal sulde hollowmicrospheres (Ag
2
S, PbS, CuS, Cu
2
S, Bi
2
S
3
,
and Sb
2
S
3
) transformed from the ZnS hollow microspheres. The
key point of the method is to utilize the large difference in
solubility between ZnS and the other metal suldes for the
effective transformation. Systematic optical investigation dem-
onstrates that the yielded hollow microspheres possess good
optical quality with tunable band gaps and luminescence
properties. The prepared metal sulde hollowmicrospheres may
nd potential applications in photocatalysts, photovoltaic cells,
nanoscale chemical reactors, energy-storage media, drug-delivery
carriers, and articial cells because of their unique hollow
geometrical shapes and optical properties.
9-14,22
Although the
current work focuses on the synthesis and optical properties of
metal sulde hollow spherical structures, other semiconductors
* Correspondingauthor. Fax:+86-21-54747552. E-mail:wzshen@sjtu.edu.cn.
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11131 Langmuir 2008, 24, 11131-11136
10.1021/la801523h CCC: $40.75 2008 American Chemical Society
Published on Web 08/23/2008
with various shapes and different properties are expected to be
synthesized under similar chemical conversion approaches.
II. Experimental Details
Synthesis of ZnSHollowMicrospheres. The preparation details
for ZnO spherical structures can be found in our recently published
papers.
23
As a typical synthesis process, silicon or quartz substrates
were put into a glass bottle containing 40 mL of a mixed solution
of 25 mM Zn(NO
3
)
2
6H
2
O, 25 mM C
6
H
12
N
4
, and 6.8 mM
C
6
H
5
Na
3
O
7
2H
2
O. The sealed bottle was then heated to 90 C for
about 50 min in a conventional laboratory oven. After the product
is washed, dried, and annealed at 400 C under an air atmosphere
for 120 min, the synthesis of ZnOmicrospheres can be realized. The
obtained ZnO microspheres on substrates (silicon or quartz slides)
were transferred to a glass bottle containing 40 mL 0.2 M
thioacetamide (TAA). The sealed bottle was then heated to 90 C
for 2-9 h in a conventional laboratory oven to synthesize ZnO/ZnS
core/shell structures. Subsequently, the as-prepared ZnO/ZnS mi-
crospheres were transferred into a bottle containing a dilute sulfuric
acid solution (0.05 M) for 90 min. This dilute acid solution can react
with ZnO to dissolve it gradually without destroying ZnS. The nal
products on the substrates were washed repeatedly with deionized
water several times and then dried at 60 C before being used for
the next step in the reaction and further characterization.
Synthesis of Other Metal Sulde Hollow Microspheres. The
synthesis of other metal sulde hollow microspheres was realized
by transferring the silicon or quartz substrates with ZnS hollow
microspheres on them to a glass bottle containing 40 mL of an
aqueous solution. As for Ag
2
S, PbS, CuS, Cu
2
S, Bi
2
S
3
, and Sb
2
S
3
,
the aqueous solutions used are 50 mM AgNO
3
, 50 mM Pb(NO
3
)
2
,
100 mM Cu(NO
3
)
2
, 20 mM CuCl, 100 mM Bi(NO
3
)
3
, and 150 mM
C
8
H
4
K
2
O
12
Sb
2
, respectively. Because Cu
+
, Bi
3+
, and Sb
3+
are apt
to hydrolyze in water, a small amount of tartaric acid (70 mM) was
added to the latter three solutions. In the case of an aqueous Bi(NO
3
)
3
solution, 2 mLof triethanolamine was also added. During the reaction
process, the solutiontemperature was kept at 90C. The nal products
on the substrates were washed with deionized water repeatedly and
then dried at 60 C. For better crystal quality, some of the as-prepared
metal sulde hollow microspheres were annealed in an argon
atmosphere.
Characterizationof the Samples. The morphology and structure
of the samples were characterized using a eld-emission scanning
electron microscope (FE-SEM, Philips XL30FEG) with an ac-
celerating voltage of 5 kVand a high-resolution transmission electron
microscope (HRTEM, JEOL JEM-2100F). Selected-area electron
diffraction(SAED) andenergy-dispersive X-ray(EDX) microanalysis
were also performed during the TEM and SEM observations. X-ray
diffraction (XRD) was carried out on a diffractometer (Bruker/D8
Discover with GADDS) equipped with a Cu KR source ( )1.5406
). The UV-visible absorption spectra of the obtained metal suldes
were recorded using a Nicolet Evolution 300 spectrophotometer
(Thermo Electron Corporation) with a bare quartz slide substrate as
a background reference. Raman and photoluminescence (PL) spectra
were measured at room temperature on a Jobin Yvon LabRAM HR
800UV micro-Raman/PL system. Raman spectra were recorded at
the backscattering conguration under the excitation of a HeCd
laser (325.0 nm) for ZnS and Ag
2
S hollowmicrospheres and an Ar
+
laser (514.5 nm) for the other metal suldes. PL spectra of ZnS- and
PbS-modied ZnS hollow microspheres were taken under HeCd
laser excitation.
III. Results and Discussion
Structural and Compositional Characterization of ZnS
Hollow Microspheres. To convert ZnO microspheres to ZnO/
ZnS core/shell microspheres, we transfer the ZnO microspheres
intoa solutioncontaining0.2MTAA. The TAAsolutionprovides
sulde ions to react with zinc ions dissolved from the ZnO
microspheres to form ZnO/ZnS core/shell structures. After the
ZnO cores dissolve in dilute sulfuric acid solution, the synthesis
of ZnShollowmicrospheres canbe realized. Figure 1a-c presents
the FE-SEM images of three samples obtained at different
suldation times (2, 6, and 9 h). If the suldation time is very
short (2 h), then the obtained ZnS hollow spheres are seriously
deformed as shown in Figure 1a, probably because the shells of
the hollow microsphere are too thin to support themselves. As
the suldation time is increased to 6 h, the shells are robust
enough, and as depicted in Figure 1b, the yielded hollowspheres
are whole with smooth surfaces. With the further increase in the
suldation time to 9 h, the thickness of microsphere shells is
obviouslyincreased, andthe surface becomes roughwithnanodots
grown on the shells (Figure 1c). The formation of nanodots on
the hollowmicrosphere shells is probably due to the fact that the
zinc ions dissolved from ZnO react with sulde ions and then
growon the shells. In the following text, we will employ the ZnS
microspheres with thicker shells (as demonstrated in Figure 1c)
to synthesize various other metal sulde hollow microspheres
(i.e., all of the samples that were used to make other metal sulde
microspheres were left in the TAA solution for 9 h).
As already shown in Figure 1b,c, one can see that some of the
shells have a partially opened mouth on them, clearly demon-
strating the hollow nature of the prepared microspheres. The
openedmouths onthe shells of the hollowspheres canbe attributed
to the fact that ZnS is eroded by dilute sulfuric acids during the
process of dissolvingZnOfromthe ZnO/ZnScore/shell structures.
Althoughsome of the microspheres are closed, further evidence
for the hollowstructure can be found fromthe TEMobservation.
Figure 1d,e presents TEM images of the obtained ZnS hollow
microspheres corresponding to the SEM images in Figure 1b,c,
respectively. The strong contrast difference in the microspheres
with a light inner center and a relative dark edge further conrms
that the yielded ZnS microspheres are all hollow. From these
two TEM images, one can also conclude that the thicknesses of
microsphere shells obviously increase with suldation time.
HRTEM observation can give further insight into the structural
features of these obtained hollowmicrospheres. Figure 1f shows
(23) (a) Zhu, Y. F.; Fan, D. H.; Shen, W. Z. J. Phys. Chem. C 2007, 111,
18629. (b) Zhu, Y. F.; Fan, D. H.; Shen, W. Z. J. Phys. Chem. C2008, 112, 10402.
Figure 1. FE-SEM images of the ZnS hollow microspheres obtained
at different suldation times: (a) 2, (b) 6, and (c) 9 h. (d, e) TEM images
of the obtained ZnS hollowmicrospheres corresponding to SEMimages
in panels b and c, respectively. (f) HRTEM image of a ZnS hollow
microsphere shell.
11132 Langmuir, Vol. 24, No. 19, 2008 Zhu et al.
a HRTEM image of a typical hollow microsphere shell, which
clearly exhibits that the shell is composed of ZnSnanocrystalline
grains with a polycrystalline nature. The composition of the ZnS
hollow microspheres can be easily identied by the EDX and
XRD spectra in Figure 2.
Compositional and Structural Characterization of Ag
2
S
Hollow Microspheres. The main attempt in the present work
is to synthesize various metal sulde hollow microspheres and
to investigate the optical properties. Here, we describe the
transformation from ZnS hollow microspheres to Ag
2
S ones in
detail and then extend this method to the synthesis of other metal
sulde hollow microspheres in the next section. To make the
conversion of ZnShollowmicrospheres to Ag
2
Sones, we transfer
the substrates with ZnS hollow microspheres on them into 40
mL of a 50 mM aqueous silver nitrate solution for 7 h. A rapid
color change (from white to black) is observed right after
immersingthe ZnShollowmicrospheres intothe above-mentioned
solution, indicating the formation of new products.
To conrm the chemical composition of the newly formed
materials, we have employed EDX spectroscopy to analyze the
yielded products. Curves a and b in Figure 2a are the EDX
spectra of the hollowmicrospheres before and after the chemical
reaction, respectively. Curve a indicates that the hollow micro-
spheres before the chemical reaction are composed of Zn and
S elements. The signal of Cu originates from the copper grid,
whereas the C peak comes from the carbon lm on the Cu grid.
After the chemical reaction is nished, the absence of Zn and
the appearance of Ag peaks clearly conrm the total transforma-
tion from ZnS to Ag
2
S. XRD measurements have also been
performed to identify the microstructural transformation. The
results are shown in Figure 2b, from which it can be clearly
observed that only diffraction peaks originating frommonoclinic
Ag
2
S(Joint Committee for Powder DiffractionStandards (JCPDS)
no. 14-0072) are detected after the chemical reaction, further
conrming that the ZnS (JCPDS no. 05-0566) hollow micro-
spheres have been completely converted into Ag
2
S ones.
FE-SEM and TEM measurements have also been carried out
to demonstrate the fact that the yielded products are morphologi-
cally retained after the chemical reaction. Figure 3a,b shows
the FE-SEM and TEM images of the prepared Ag
2
S hollow
microspheres. Compared with morphology of the ZnS micro-
spheres in Figure 1c, no signicant changes were observed,
conrmingthe successful realizationof morphologytransfer from
one material to another. The HRTEM image shown in Figure 3c
indicates that the hollow microsphere shells are polycrystalline
with a single-crystalline local area. The enlarged HRTEMimage
of Figure 3d further conrms that the local area of the hollow
microsphere shell is single-crystalline. The lattice fringe spacing
is measured to be 0.27 nm, which is consistent with the unique
0.2664 nm separation between two (120) planes in bulk Ag
2
S
crystallites.
24
The corresponding SAED pattern displayed in the
inset of Figure 3d suggests the crystallinity of the local area.
There are some additional diffraction spots, which may be due
to the large diameter of the electron beamand the small diameter
of the local single-crystalline area.
According to the experimental observation described above,
the whole process can be described as follows. After the ZnS
hollowmicrospheres were transferred into silver nitrate solution,
cation exchange began at the interfaces between the hollow
microspheres and solution. With the increase in the reaction
time, the ZnS hollow microspheres completely changed into
Ag
2
S ones. The driving force for the cation exchange is provided
by the large difference in solubility between ZnS and Ag
2
S
(solubility product constant (K
sp
) of ZnSis 2.93 10
-25
, whereas
K
sp
of Ag
2
Sis 6.69 10
-50
).
25
The above conversion mechanism
suggests that the ZnS hollow microspheres can act as both
reactants and templates during the cation-exchange process (i.e.,
we can extend this chemical conversion approach to the synthesis
of other metal sulde hollow microspheres under the condition
that those yielded metal suldes have lower K
sp
values than do
those of ZnS. In fact, it is because of the large K
sp
in ZnS that
we choose ZnShollowmicrospheres as the reactants andtemplates
to synthesize various metal sulde hollow microspheres.
Extension to the Synthesis of Other Metal Sulde Hollow
Microspheres. To conrm the validity of the above proposal,
we have extended this easy and effective method to prepare
other metal sulde hollow microspheres. Several other metal
sulde hollowmicrospheres (PbS, Cu
2
S, CuS, Bi
2
S
3
, and Sb
2
S
3
)
have beensuccessfullysynthesizedbytransferringthe ZnShollow
microspheres into solutions containing the corresponding metal
cations. Figure 4a-e presents the FE-SEMimages of these yielded
metal sulde hollow microspheres. It is obvious that the
morphologies of the ZnS hollow microspheres are all preserved
during the cation exchange process. The hollow nature of the
microspheres is clearly evidenced by the holes in the surfaces
of the obtained microspheres. XRD measurements have been
carried out to identify the composition of the products and to
analyze the crystalline properties of the prepared samples. It is
found that all diffraction peaks are consistent with the corre-
sponding metal suldes (Figure 4f). EDX measurements have
also been performed to check the compositions of the yielded
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Chem. B 2006, 110, 10534.
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Press: Boca Raton, FL, 1988-1989.
Figure 2. (a) EDX spectra and (b) XRD patterns of the obtained ZnS
hollow microspheres (curve a) and Ag
2
S hollow microspheres (curve
b).
Figure 3. (a) FE-SEMand (b) TEMimages of the prepared Ag
2
S hollow
microspheres. (c, d) HRTEM images of a Ag
2
S hollow microsphere
shell. The inset in panel d shows the SAED pattern corresponding to
the local single-crystalline area.
Synthesis and Properties of Hollow Microspheres Langmuir, Vol. 24, No. 19, 2008 11133
metal sulde hollow microspheres (Figure 4g). No impurities
are detected in any of these samples, indicating the successful
transformations fromZnShollowmicrospheres to the other metal
sulde hollow structures. Therefore, a facile, versatile method
has been demonstrated to synthesize metal sulde hollow
microspheres.
Furthermore, because ZnS hollow microspheres are solid and
insoluble in the solutions we used, cation exchange takes place
rst at the interfaces between the hollow microspheres and
solutions. As a result, the synthesis of surface-modied ZnS
hollow microspheres can be possible if one stops the chemical
reaction before the entire cation exchange. PbS modied ZnS
hollowmicrospheres have been successfully realized along with
this proposal by transferring the ZnS hollow microspheres into
aqueous solutions containing Pb(NO
3
)
2
(50 mM, 40 mL) for
60 s. Figure 5a presents the FE-SEM image of the PbS/ZnS
hybrid hollow microspheres whereas the corresponding EDX
spectrum shown in Figure 5b clearly demonstrates the obtained
hollow microspheres composed of Zn, Pb, and S (with the
molecular proportion between PbS and ZnS being about 1:3).
The Si signal originates from the silicon substrate, whereas the
Au peaks should come from the thin gold lm sputtered on the
surface for the SEM observation. As we know, surface
modication is also a current research interest because of the fact
that surface-modied nanostructures usually exhibit attractive
physical and chemical properties that are different fromthe those
of the constituent components.
26-29
We will show below the
interesting luminescence property fromthe yielded PbS-modied
ZnS hollow microspheres.
Optical Properties of the Yielded Metal Sulde Hollow
Microspheres. To examine the optical properties of these yielded
metal sulde hollow microspheres, we rst perform room-
temperature UV-visible absorption measurements. From the
absorption spectra of the ZnS and Ag
2
S hollow microspheres in
Figure 6a, it is clear that the absorption edge of the Ag
2
S hollow
microspheres shows an obvious red shift compared to that of
ZnS ones. As we know, the optical band gap E
g
of ZnS (Ag
2
S)
andthe correspondingabsorptioncoefcient Rnear the absorption
edge obey the relationship
Rh )C

(h -E
g
)
where C is a constant and h is the photon energy. Hence, the
optical band gaps of the yielded products can be obtained by
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Figure 4. FE-SEM images of (a) PbS, (b) Cu
2
S, (c) CuS, (d) Bi
2
S
3
, and (e) Sb
2
S
3
hollow microspheres. (f) XRD patterns of (a) PbS, (b) Cu
2
S, (c)
CuS, (d) Bi
2
S
3
, and (e) Sb
2
S
3
hollow microspheres. (g) EDX spectra of (a) PbS, (b) Cu
2
S, (c) CuS, (d) Bi
2
S
3
, and (e) Sb
2
S
3
hollow microspheres.
Figure 5. (a) FE-SEMimage of PbSmodied ZnShollowmicrospheres.
(b) EDX spectrum of the corresponding hollow microspheres.
11134 Langmuir, Vol. 24, No. 19, 2008 Zhu et al.
extrapolating the linear portion of the plots of (Rh)
2
h, as
shown in the inset of Figure 6a. The estimated values for the
band gap energy of these ZnS and Ag
2
S hollow microspheres
are 3.9 and 1.1 eV, respectively. Those results are very similar
to the reported data of other ZnS and Ag
2
S nanostructures,
30,31
indicating that we have successfully realized the synthesis of
hollow microspheres with the same morphology but different
optical properties.
Figure 6a has also presented the typical absorption spectra
taken from the other metal sulde hollow microspheres. It is
obvious that the absorption edges of the obtained hollow
microspheres are different fromeach other and are all red-shifted
compared with those of ZnS, providing the possibility to broaden
the potential applications of metal sulde hollow microspheres.
Because ZnS is abundant, stable, and environmentally benign,
many kinds of ZnS nanostructures, such as nanowires, nanorods,
nanotubes, andhierarchical nanostructures, have beensuccessfully
fabricated by a variety of methods for potential optoelectronic
device application.
32
Unfortunately, the ZnS band gap (3.72 eV)
is too large to use in efcient photovoltaic devices.
33
The above
experiments demonstrate that the absorption edges of the hollow
microspheres can be effectively modulated without destroying
the original morphology of ZnS and some of the obtained metal
sulde hollowmicrosphere band gaps are near the optimal value
of photovoltaic conversion, indicating that they may be used in
solar energy and photoelectronic applications.
22
Raman spectroscopy can provide valuable structural informa-
tion on semiconductor nanostructures. However, until now, there
has been little work reported on the Raman characterization of
metal sulde hollow microspheres. Figure 6b shows the room-
temperature Raman spectra of the yielded metal sulde hollow
microspheres. The Raman frequencies of the main bands due to
the lattice modes in all of the studied metal sulde hollow
microspheres are similar to the previously reported results for
metal sulde nanostructures with other shaps.
34-37
It should be
noted that strong resonant Raman scattering with high-order
longitudinal optical (LO) modes can be obtained in the case of
ZnS hollow microspheres. The Raman peaks located at 350,
699, and 1045 cm
-1
correspond well to the rst-, second-, and
third-order LO phonon modes in ZnS, respectively.
38
The
observation of multiple resonant Raman peaks indicates that the
yielded ZnShollowmicrospheres possess good optical quality.
39
In addition, there is no peak corresponding to the surface optical
phonon mode in the Raman spectrum, indicating few defects on
the surface of the ZnS hollow microspheres.
35
Finally, we present the luminescence characteristics of the
yielded hollow microspheres. Figure 7 shows the room-
temperature PLspectrumof the ZnShollowmicrospheres (curve
a). Inmost cases, the PLspectra of ZnSnanostructures synthesized
by wet chemical routes usually display two emission bands.
40,41
One broad peak at around 400 nm originates from the
recombination of free charge carriers at the surface defect sites.
40
Another peak at around 510 nm is usually attributed to the self-
activated defect centers formed by the zinc vacancies inside the
lattice.
41
It is clear that the PL spectrum has only a strong broad
PL peak at around 510 nm. The absence of a blue emission band
at around 400 nm indicates that the yielded ZnS hollow
microspheres have small number of defects on their surfaces,
which is in good agreement with the observation from Raman
spectroscopy.
As mentioned above, the surface-modied nanostructures
usually exhibit physical and chemical properties that are different
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1525.
Figure 6. (a) UV-visible absorption spectra of metal sulde hollow
microspheres. The inset shows the plots of (Rh)
2
h for ZnS and
Ag
2
S hollow microspheres. (b) Raman spectra of metal sulde hollow
microspheres.
Figure 7. Room-temperature PL spectra of (a) pure ZnS hollow
microspheres and (b) PbS-modied ZnS hollow microspheres with two
Gaussian peak ts for the spectrum.
Synthesis and Properties of Hollow Microspheres Langmuir, Vol. 24, No. 19, 2008 11135
from those of the constituent components. The PL spectrum of
the PbS-modied ZnS hollow microspheres is also shown in
Figure 7 (curve b), which is different from that of the pure ZnS
hollowmicrospheres (curve a). The spectrumof the PbS-modied
ZnS hollowmicrospheres displays a broad visible emission with
a slightly redshift compared with that of pure ZnS hollow
microspheres. To our knowledge, this is the rst report on the
luminescence investigation of the PbS-modied ZnS nanostruc-
tures. To identify the origin of the PLchanges, we have employed
the Gaussian t for the spectrum of PbS-modied ZnS hollow
microspheres. As demonstrated in Figure 7, the luminescence
spectrum can be well tted by two Gaussian peaks centered at
about 510 and 600 nm. In comparison with the pure ZnS hollow
microsphere case, the spectrum of PbS-modied ZnS hollow
microspheres shows quenched green emission (around 510 nm)
and a new broad visible emission (around 600 nm). This new
broad visible band is similar to that of previously reported Pb-
doped ZnS nanostructures.
42,43
Therefore, we believe that the
present observation can be explained as follows. After immersing
the pure ZnS hollow microspheres into a Pb(NO
3
)
2
aqueous
solution for a very short time (tens of seconds), the Pb atoms will
ll up the zinc vacancies on and near the surface of the ZnS
hollowmicrospheres. Because the Pb atoms have occupied some
of the zinc vacancies, the green emission (around 510 nm) due
to the self-activated defect centers formed by the zinc vacancies
will be quenched. At the same time, a broad visible emission
corresponding to the Pb-doped ZnS appears.
42,43
Although the
detailed luminescence mechanism for the PbS modied ZnS
hollow microspheres is worthy of further study, the above
experimental results indicate that the surface-modicationprocess
has a great impact on the luminescence properties of ZnS hollow
microspheres. As a result, the PL properties of the ZnS hollow
microspheres can be tuned by controlling the chemical reaction
for further broadening their potential optoelectronic applications.
Perspective. Although the current work focuses on the
synthesis of metal sulde hollow microspheres, other pure and
hybrid metal sulde nanostructures are expected to be realized
by using ZnS nanostructures with other shapes (e.g., previously
reported nanowires, nanorods, nanotubes, hierarchical nano-
structures, etc.
32
) as reactants and templates during the chemical
conversion process. Furthermore, in addition to ZnS, other
semiconductor micro- and nanostructures with large K
sp
values
can also be employed as reactants and templates. Because the
properties of materials are related to their compositions, sizes,
and morphologies, the yielded micro- and nanostructures may
nd broad applications in optoelectronics, photocatalyts, pho-
tovoltaics, and so on. Hence, the present chemical conversion
process is a facile, economic, and versatile way to synthesize
semiconductor micro- and nanostructures with different com-
positions and geometries and novel and unique properties.
IV. Conclusions
In summary, the successful chemical conversion of ZnShollow
microspheres into various metal sulde hollow microspheres,
such as Ag
2
S, PbS, CuS, Cu
2
S, Bi
2
S
3
, and Sb
2
S
3
, was achieved.
The morphological and structural characterization showed that
the morphology of ZnS hollow microspheres is perfectly
maintained after the conversion, whereas the compositional
conversion was veried by EDXand XRD. The optical properties
of the obtained metal sulde hollow microspheres were sys-
tematically investigated by absorption, micro-Raman, and PL
spectroscopy. The absorption spectra revealed that some of the
band gaps of these hollow microspheres are near the optimal
value of photovoltaic conversion, indicating that the products
may be applicable in solar cells and photoelectronics. The micro-
Raman results demonstrated that the yielded hollowmicrospheres
possess good optical quality. The PL studies found that the
luminescence properties of the ZnS hollow microspheres can be
tuned by modifying them with PbS, further broadening their
potential applications. We have further expected that the facile
method of material synthesis described in this article can be used
in a broad range of applications to fabricate innovative
semiconductor micro- and nanostructures with different com-
positions and shapes having unique properties.
Acknowledgment. This work was supported by the Natural
Science Foundation of China under contracts 10734020 and
10674094, the National Major Basic Research Project of
2006CB921507, the National Minister of Education Program of
IRT0524, andthe Shanghai Municipal KeyProjects of 06JC14039
and 08XD14022.
LA801523H
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2001, 336, 76.
(43) Borse, P. H.; Vogel, W.; Kulkarni, S. K. J. Colloid Interface Sci. 2006,
293, 437.
11136 Langmuir, Vol. 24, No. 19, 2008 Zhu et al.