Chinese Journal of Chemistry, 2007, 25, 1584—1587 Note

Molten-salt Synthesis and Properties of ZnS with Hexagonal

Prism Morphology

LIU, Jin-Song(刘劲松) JI, Guang-Bin(姬广斌) LI, Zi-Quan(李子全)

CAO, Jie-Ming*(曹洁明) ZHENG, Ming-Bo(郑明波) KE, Xing-Fei(柯行飞)
Nanomaterials Research Institute, College of Materials Science and Technology, Nanjing University of Aeronautics
and Astronautics, Nanjing, Jiangsu 210016, China

ZnS with hexagonal prism morphology has been synthesized successfully by molten-salt method with ZnS
nanoparticles as precursors, and the ZnS nanoparticles were prepared by one-step solid-state reaction of
Zn(CH3COO)2•2H2O with Na2S•9H2O at ambient temperature. Crystal structure and morphology of the product
were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and
HRTEM. Ultraviolet-visible optical absorption spectrum of the ZnS hexagonal prism shows a distinct red shift from
that of bulk ZnS crystals and photoluminescence spectrum exhibits strong emissions at 380 and 500 nm, respec-
tively. Further experiments were designed and the formation mechanism of the ZnS hexagonal prism has been also
discussed in brief.

Keywords molten-salt method, ZnS hexagonal prism, formation mechanism

Introduction nanoparticle precursors is as follows. In a typical syn-

Among the II—VI semiconductor nanocrystals, ZnS
is one of the important materials.1 Over the past few
years, a great deal of attention has been focused on syn-
thesis of ZnS nanostructural materials owing to its ex-
cellent properties, and different morphologies of ZnS
(for example: nanorods, nanowires, nanospheres, nano-
sheets, nanobelts, mesopores, nanotubes, and so on)
have been also obtained by various kinds of methods.2-9
However, it is still a challenge to obtain other different
morphologies or properties of ZnS.
Molten-salt synthesis (MSS) is one of the simplest
techniques for preparing nanomaterials with different
morphologies, which needs no expensive synthesis
equipments or complex experiment conditions.10-13 In
this paper, we reported on preparation of ZnS hexagonal
prism by an easy method. The reaction was accom-
plished by heat-treating a precursor, which has been
synthesized by one-step solid-state reaction between
Zn(CH3COO)2•2H2O and Na2S•9H2O at ambient tem-
perature, in NaCl flux. We chose NaCl as the solvents
because it could protect the product from being oxided,
provide a favorable growth environment and be easily
removed from the final products. This method is easy to
operate and very efficient for crystal growth.
Experimental
Synthesis of ZnS nanoparticle precursors
The procedure employed by us for preparing ZnS
thesis, 0.02 mol of Zn(CH3COO)2•2H2O was ground for
5 min before it was mixed with 4 mL of polyethylene-
glycol-400 (PEG400), and then 0.02 mol of Na2S•9H2O
was added to the mixture. After 30 min of grinding, the
product was washed with distilled water and absolute
alcohol and dried in an oven at 80 ℃ for 3 h.
Synthesis of ZnS hexagonal prism
The above-prepared ZnS precursor (0.40 g) was
mixed with 2.00 g of NaCl powder in an agate mortar,
and then the mixture was ground for 5 min. The mixed
sample was heated in a muffle furnace at 800 ℃ for 2
h in air, and then cooled gradually to room temperature.
The product was washed several times with distilled
water, filtered, and then dried in an oven at 100 ℃ for
3 h. The resulting product was collected for charact-
erization.
Characterization and apparatus
X-ray diffraction (XRD) patterns were obtained on a
Bruker D8 Advance X-ray diffractometer with Cu Kα
radiation (λ＝0.154178 nm) at a scanning rate of 0.02
－
(°)•s 1. Scanning electron microscopy (SEM) images
were taken with an LEO1530VP field emission scan-
ning electron microscope. Transmission electron mi-
croscopy (TEM) micrographs and selected area electron
diffraction (SAED) pattern were taken using an FEI
Tecnai-20 transmission electron microscope. Ultra-
violet-visible (UV-Vis) optical absorption spectrum was

* E-mail: jmcao@nuaa.edu.cn; Tel.: 0086-025-84893633; Fax: 0086-025-84895871

Received January 10, 2007; revised May 14, 2007; accepted June 15, 2007.
Project supported by the Doctor Innovation Funds of Nanjing University of Aeronautics and Astronautics (No. BCXJ05-07) and the National Natural
Science Foundation of China (No. 50502020).

© 2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Molten-salt method Chin. J. Chem., 2007 Vol. 25 No. 10 1585

recorded on an Hp-6010 spectrophotometer. Photol-

uminescence (PL) spectrum was recorded on a Fluor-
escence spectrophotometer using an Xe lamp with an
excitation wavelength of 335 nm at room temperature.

Results and discussion

Figure 1(a) shows XRD pattern of the ZnS nanop-
article precursors. The three pronounced peaks with
2θ＝28.7°, 47.9° and 56.8° correspond to three crystal
planes of (111), (220) and (311) of cubic phase ZnS
(JCPDS file 05-0566), respectively. The broadening of
X-ray diffraction peaks indicates that the particle sizes
are in the nanometer range. According to the Scherrer
equation, the particle size calculated from the data of the
peak (111) is about 3.5 nm. The XRD pattern of ZnS
with hexagonal prism morphology is shown in Figure
1(b). All the diffraction peaks could be also indexed to
standard cubic ZnS within experimental errors. The
main diffraction peaks at 28.7°, 34°, 47.9°, 56.4°, 59°,
69.5°, 76.8° and 79° correspond to the crystal planes of
(111), (220), (311), (222), (400), (331) and (420), re-
spectively. Compared with the XRD pattern of the ZnS
nanoparticle precursors, it shows that the ZnS with
hexagonal prism morphology is crystallized well in the
process of heat-treatment with NaCl powder.
Figure 2 SEM images of ZnS nanoparticles (a) and ZnS hex-
agonal prism (b), (c) and TEM micrograph and SAED pattern of
ZnS hexagonal prism (d).
sample has hexagonal prism morphology and the typical
hexagonal prism has side length of about 50 nm. Thus,
SAED pattern confirmed that the sample took a single
crystalline structure.
Figure 3 reveals HRTEM image of the ZnS hexa-
gonal prism. The highly crystal structure in the HRTEM
image further proves that the ZnS hexagonal prism is
single-crystal. A layer separation of about 0.31 nm can
be observed, corresponding to the separation between
(111) planes of ZnS, which indicates that the growing
plane of hexagonal prism is plane (111), as marked in
Figure 3.

Figure 1 XRD patterns of the products: ZnS nanoparticle pre-

cursors (a) and ZnS hexagonal prism (b).

SEM image of the ZnS nanoparticles is shown in

Figure 2(a). The image indicates that the typical mor-
phology for the precursor is small spheres with diame-
ters of 3—9 nm, which is in agreement with the XRD
result. The agglomeration of particles may arise from
the small dimensions and high surface energy. Figure
2(b) and 2(c) show SEM images of the product synthe-
sized by the molten-salt method. In the images, the
products display hexagonal prism morphology with
50—100 nm of side length and height in the range of
50—200 nm. From the figure, we can also find that the
hexagonal prisms are relatively regular and the surfaces
are also smooth. TEM micrograph of the product is
shown in Figure 2(d), from which it can be seen that the
Figure 3 HRTEM image of ZnS hexagonal prism.
Figure 4(a) shows the UV-Vis optical absorption
spectrum of the ZnS hexagonal prism. We can estimate
that a UV-Vis optical absorption peak of the sample is
at ca. 380 nm. The corresponding band gap energy of
absorption maximum for the sample has been estimated
to be ca. 3.27 eV, and it shows a distinct red shift from
that of bulk ZnS crystals (345 nm, 3.6 eV).14 The PL
spectrum of the ZnS hexagonal prism is shown in Fig-
ure 4(b). It can be seen that the ZnS hexagonal prism
has two intense peaks at about 380 and 500 nm, respec-
tively. The peak at 380 nm peak was attributed to zinc
vacancies and the 500 nm PL peak occurred as the

© 2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1586 Chin. J. Chem., 2007, Vol. 25, No. 10
Figure 4 UV-Vis absorbance spectrum (a) and PL spectrum (b)
of ZnS hexagonal prism.
electrons transited from the energy level of sulfur va-
cancies to the energy level of zinc vacancies.15,16 In ad-
dition, two weak peaks at 420 and 460 nm can be also
observed from the figure. The 420 nm PL peak was at-
tributed to sulfur vacancies and the 460 nm PL peak was
caused by sulfur bonds dangling at the interface of zinc
sulfide grains.17
Several experiments have been designed to explore
the growth mechanism of the ZnS hexagonal prism:
(1) ZnS products failed to be obtained when the
precursor was heated at 800 ℃ in the absence of NaCl,
and the XRD pattern and SEM image [Figure 5(a) and
(b)] show that only ZnO nanoparticles were obtained
instead of the ZnS hexagonal prism.
(2) The ZnS hexagonal prism failed to form if ZnCl2
was used instead of Zn(CH3COO)2•2H2O. SEM image
shows that the product sample contained nanosheets
[shown in Figure 5(c)].
(3) It was found that the precursor could not be ob-
tained if thioacetamide (TAA) was used instead of
Na2S•9H2O.
(4) It was found that ZnS nanoblocks were synthe-
sized when LiCl was used as solvents instead of NaCl
[shown in Figure 5(d)].
From the results of the experiments, it was shown
that ZnS could be oxidized into ZnO in the absence of
NaCl, so it was thought that NaCl played an important
role in the formation of the ZnS hexagonal prism. First,
it keeps oxygen in air away from ZnS nanoparticles and
© 2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
LIU et al.
Figure 5 XRD pattern and SEM images of the products ob-
tained in different conditions: in the absence of NaCl (a), (b) and
using ZnCl2 instead of Zn(CH3COO)2•2H2O (c) and using LiCl
instead of NaCl (d).
accordingly, ZnS nanoparticles are hardly oxidized into
ZnO. On the other hand, NaCl can significantly de-
crease the viscosity of the melt, leading to the easier
mobility of components in the flux.12 Thus, addition of
NaCl can provide a favorable environment for form-
ation of the hexagonal prism. In general, the growth
habit of ZnS crystal is tetrahedron.18 In the zinc blende
structure, the sulfur atoms are arranged in the cubically
closest packing, in which one half of the tetrahedral
sites are filled with zinc atoms and the orientation of
tetrahedron ZnS64− is the same. The whole structure is
of tetrahedron symmetry.19 When the precursor was
heated in NaCl flux, the molten salt provided a fluent
liquid phase for tiny ZnS particles and was ionized into
＋ －
Na , and Cl . These ions had a strong electrostatic in-
teraction with the closely-packed plane of ZnS. So they
absorbed onto certain plane of ZnS crystal selectively
and changed the surface energies, and decreased the
growth rate, resulting in the formation of ZnS hexagonal
prism. While LiCl was used instead of NaCl, only ZnS
nanoblocks were obtained, which may be attributed to
the different electrostatic interaction. In addition, ex-
perimental results also show that the character of the
starting reactants and surfactants also had some impor-
tant effects on the formation of ZnS with different mor-
phologies: we obtained ZnS with nanosheet morphology
when using ZnCl2 instead of Zn(CH3COO)2•2H2O and
no precursor was synthesized when TAA was used in-
stead of Na2S•9H2O. The surfactant PEG400 may be
very important for the formation of the ZnS hexagonal
prism, and it has been reported that ZnS nanorods could
be obtained when using nonylphenyl ether (NP-9) in-
stead of PEG400.20 From the above experiments, we
concluded that the starting reactants, surfactants and
NaCl all played crucial roles in the formation of the
hexagonal prism. The more detailed study of the forma-
Molten-salt method Chin. J. Chem., 2007 Vol. 25 No. 10 1587

tion mechanism of various morphologies will be de-
scribed in progress.
Conclusion
In summary, ZnS hexagonal prism has been synthe-
sized by heating ZnS nanoparticles with NaCl powder at
800 ℃. ZnS nanoparticle precursors with the diameter
of about 3.5 nm were obtained by a one-step solid-state
reaction. Side length and height of the ZnS hexagonal
prism is in the range of 50—100 nm and 50—200 nm,
respectively. UV-Vis absorbance spectrum of the ZnS
hexagonal prism shows a distinct red shift from that of
the bulk ZnS crystal and the PL spectrum exhibits
strong emissions at 380 and 500 nm, respectively. Fur-
ther experiments were designed and the results show
that the starting reactants, surfactants and NaCl all
played important roles in formation of the ZnS hexago-
nal prism.
References
1 Nicolau, Y. F.; Dupuy, M.; Bruuel, M. J. Electrochem. Soc.
1990, 137, 2915.
2 Zhang, Y. C.; Wang, G. Y.; Hu, X. Y.; Chen, W. W. Mater.
Res. Bull. 2006, 41, 1817.
3 Cheng, C. W.; Xu, G. Y.; Zhang, H. Q.; Cao, J. M.; Jiao, P.
P.; Wang, X. X. Mater. Lett. 2006, 60, 3561.
4 Jiang, C. L.; Zhang, W. Q.; Zou, G. F.; Yu, W. C.; Qian, Y.
T. Mater. Chem. Phys. 2007, 103, 24.
5 Fang, X. S.; Ye, C. H.; Peng, X. S.; Wang, Y. H.; Wu, Y. C.;
Zhang, L. D. J. Cryst. Growth 2004, 263, 263.
6 Ding, Y.; Wang, X. D.; Wang, Z. L. Chem. Phys. Lett. 2004,
398, 32.
7 Li, J.; Zhao, X. P.; Yan, C. M. Mater. Lett. 2006, 60, 2896.
8 Zhai, T. Y.; Gu, Z. J.; Ma, Y.; Yang, W. S.; Zhao, L. Y.;
Yao, J. N. Mater. Chem. Phys. 2006, 100, 281.
9 Wu, Q. S.; Zheng, N. W.; Ding, Y. P.; Li, Y. D. Inorg.
Chem. Commun. 2002, 5, 671.
10 Wang, Y.; Lee, J. Y. J. Phys. Chem. B 2004, 108, 17832.
11 Jiang, Z. Y.; Xu, T.; Xie, Z. X.; Lin, Z. W.; Zhou, X.; Xu,
X.; Huang, R. B.; Zheng, L. S. J. Phys. Chem. B 2005, 109,
23269.
12 Wang, W. Z.; Xu, C. K.; Wang, G. H.; Liu, Y. K.; Zheng, C.
L. Adv. Mater. 2002, 14(11), 837.
13 Wang, X.; Zhuang, J.; Li, Y. D. Eur. J. Inorg. Chem. 2004,
946.
14 Dhas, N. A.; Zaban, A.; Gedanken, A. Chem. Mater. 1999,
11, 806.
15 Hebalkar, N.; Lobo, A.; Sainkar, S. R.; Vogel, W.; Kulkarni,
S. K. J. Mater. Sci. 2001, 36, 4377.
16 Dimitrova, V.; Tate, J. Thin Solid Films 2000, 365, 134.
17 Li, Y.; Li, X.; Yang, C.; Li, Y. J. Phys. Chem. B 2004, 108,
16002.
18 Wang, Z. R.; Cheng, W. Mineralogy, Shanghai Scientific
and Technical Publishers, Shanghai, 1965, 181 (in Chinese).
19 Li, W. J.; Shi, E. W.; Chen, Z. Z.; Yin, Z. W. Chin. Sci. Bull.
2000, 45, 1662.
20 Lan, C.; Hong, K. Q.; Wang, W. Z.; Wang, G. H. Solid
State Commun. 2003, 125, 455.

(E0701101 CHENG, B.; DONG, H. Z.)

© 2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim