Materials Science and Engineering B100 (2003) 307
/313

www.elsevier.com/locate/mseb

Microwave heating synthesis of HgS and PbS nanocrystals in ethanol

solvent
Tao Ding, Jun-Jie Zhu *
Laboratory of Mesoscopic Materials Science, Department of Chemistry, Nanjing University, Nanjing 210093, China

Received 29 November 2002; received in revised form 22 March 2003; accepted 7 April 2003

Abstract

A novel route was developed to prepare PbS and HgS nanocrystals in ethanol solvent in the presence of sodium hydroxide by
microwave heating method. PbS and HgS nanocrystals were obtained with an average size of approximately 10 and 6 nm,
respectively. In the reaction, mercury acetate and lead acetate were used as mercury and lead source; sulfur powder was employed as
chalcogenide source. The products were characterized by X-ray powder analysis (XRD), transmission electron microscopy (TEM),
X-ray photoelectron spectroscopy (XPS) and UV
/Vis absorption spectroscopy. The probable mechanism was presented.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Microwave; Ethanol; PbS and HgS, nanocrystals

1. Introduction mercury sulfides, [17,18] and is a very rapidly developing

area of research. It is well known that microwave is
Over the past decades, sulfide semiconductors with electromagnetic waves containing electric and magnetic
nanometer size dimensions had attracted so much field components. The electric field applies a force on
interest of many researchers because of the quantum charged particles as a result of which the charged
size effect exhibited by these nanosized semiconductors particles start to migrate or rotate. Due to the movement
[1
/3]. Mercury sulfide is a useful material and it could of charged particles, further polarization of polar
be widely used in ultrasonic transducers [4,5], electro- particles takes place. The concerted forces applied by
static image materials [6] and photoelectric conversion the electric and magnetic components of microwave
devices [4
/6]. Lead sulfide is also an attractive semi- rapidly change in direction, which creates friction and
conducting material due to its multipurpose in potential collisions of the molecules. Claimed effects of microwave
photonic material [7] and Pb2 ion-selective sensor [8]. irradiation include thermal and non-thermal effects [19].
Nowadays, various techniques, such as single molecule Compared with conventional method, microwave synth-
precursors approach [9], gas phase method [10], gamma- esis has the advantages of short reaction time, small
irradiation method [11], electrodepositions in acidic particle size, narrow particle size distribution and high
medium [12], ion exchange colloidal method [13], Ion purity. Thus, microwave irradiation as a heating method
beam method [14], ‘‘Chemical Scissors’’ route [15] and has found numerous applications in synthetic chemistry.
sonochemical method [16] have been employed in the In recent years, organic solvents, including formalde-
preparation of lead and mercury sulfides. However, hyde [18], benzene, tetrahydrofuran, triethylene tetra-
finding fast and energy-efficient method to produce amine [20], ethylenediamine [21,22], etc., have been
metal sulfides are new challenges to synthetic chemists introduced into the preparation of lead and mercury
and material scientists. The microwave-assisted route is sulfides. Owing to the different viscosity, polarity,
softness of different organic solvents, various synthetic
yet another novel method to synthesize lead and
environments could be presented, which would affect
the solubility and transport behavior of the precursors
* Corresponding author. Fax: /86-25-331-7761. and as a result, influence the morphology and size of the
E-mail address: [email protected] (J.-J. Zhu). final products [23]. Up to now, only a few literatures
0921-5107/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-5107(03)00125-9
308 T. Ding, J.-J. Zhu / Materials Science and Engineering B100 (2003) 307
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have reported the synthesis of HgS and PbS nanocrys- and the reaction was performed under ambient air for 20
tals in ethanol solvent. Zeng and his co-workers min. The microwave oven followed a working cycle of 6
prepared HgS nanocrystals in ethanol by a solvothermal s on and 24 s off (20% power). In the process of
method. The reaction was conducted in an autoclave for conventional heating method, the same amount of
12 h and the size of the as-prepared HgS nanocrystals reagents and solvent was placed in a round-bottom
was about 40 nm in diameter [20]. Qiao et al. reported flask and the reaction was conducted with constant stir
the preparation of nanocrystalline PbS in ethanol by at approximately 60 8C for about 1 h. After the reaction
employing gamma-radiation method [24]. finished, the black precipitates were centrifuged, washed
Herein, we present a quick, convenient and safe way with absolute ethanol and acetone, and dried in the air.
to synthesize HgS and PbS nanoparticles in ethanol The final products were collected for further character-
solvent in the presence of sodium hydroxide. The izations.
reaction could be preformed in short time. The average
size of as-prepared HgS and PbS was only approxi-
mately 6 and 10 nm. To the best of our knowledge, HgS 3. Results and discussion
and PbS nanocrystals were synthesized in alkali ethanol
by microwave method for the first time. The products 3.1. XRD, XPS and TEM studies
were characterized by X-ray powder analysis (XRD),
transmission electron microscopy (TEM), X-ray photo- The XRD and XPS were used to investigate the
electron spectroscopy (XPS) and UV
/Vis absorption composition and purity of as-prepared HgS and PbS
spectroscopy. The probable mechanism was presented. nanoparticles. The XRD patterns of as-prepared PbS
and HgS nanoparticles by conventional heating and
microwave heating method are shown in Fig. 1. The
2. Experimental sections diffraction peaks correspond to the (111), (200), (220),
(311), and (222) planes, which can be indexed to the pure
2.1. Materials and instruments cubic phase for PbS and HgS. No peak of any other
phase is detected. The intensities and positions of the
All the reagents used in the experiment were of the peaks are in agreement with the literature pattern
analytical purity and were used without further purifica- (JCPDF card No. 6-0261 and 5-0592). The average
tion. Mercury acetate, lead acetate and sodium hydrox- size of the PbS (Fig. 1a) and HgS (Fig. 1c) nanoparticles
ide were purchased from Shanghai Second Chemical synthesized by conventional heating method is calcu-
Regent Factory (China). Sulfur powder was purchased lated to be approximately 35 and 10 nm, respectively,
from Shandong Chemical Research Institute (China). according to Debye
/Scherrer formula. In contrast, the
Distilled water was used in the experiments. average size of PbS (Fig. 1b) and HgS (Fig. 1d)
Experiments were carried out in a commercial micro- nanoparticles prepared by microwave heating method
wave oven (Sanle General Electric Corp., Nanjing, is approximately 10 and 6 nm accordingly. The XPS was
China). The instrument consisted of a 150 ml reactor employed to investigate the composition and purity of
immersed into the resonant cavity, and equipped with as-prepared HgS nanoparticles prepared by microwave
refluxing condenser pipe [25]. The X-ray diffraction
(XRD) patterns were recorded on a Shimadzu XD-3A
X-ray diffractometer (Cu Ka radiation, l /0.15418
nm). The TEM images were obtained by employing a
JEOL JEM-200CX instrument, working at 200 kV
accelerating voltage. The X-ray photoelectron spectra
(XPS) measurements were performed on ESCALAB
MKII instrument, using non-monochromatized Mg Ka
X-ray as the excitation source. Shimadzu UV-2401
spectrophotometer was used to record the UV
/Vis
absorption spectra of the as-prepared particles.

2.2. Synthesis

Typically, /1.6 g Pb(AC)2 ×/3H2O and /1.5 g

Hg(AC)2 were added in /60 ml ethanol, respectively.
About 0.2 g sulfur powders and 0.5 g sodium hydroxide Fig. 1. XRD patterns: (a), (c) the PbS and HgS prepared by
were introduced into the ethanol solvent. The two conventional heating method; (b), (d) the PbS and HgS prepared by
mixtures were placed in the microwave-refluxed system microwave heating method.
 T. Ding, J.-J. Zhu / Materials Science and Engineering B100 (2003) 307
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heating method. In the wide XPS spectrum of as-

prepared HgS (Fig. 3), it can be observed that the C
(1s) peak coming from contaminated carbon lies at
285.35 eV, which should be correctly shifted to 284.6 eV.
All the other peaks are corrected accordingly. No peaks
of impurities are detected, indicating the high purity of
the products. Fig. 2a and b show the high-resolution
XPS spectra of Hg (4f) and S (2p). The two strong peaks
at 100.55 eV and 161.95 eV correspond to Hg (4f) and S
(2p), respectively. The peak areas of the Hg and S cores
are measured and yield a ratio of Hg to S as 53:47,
which shows that the surface of the products are a little
rich in mercury. The morphology of the prepared
nanoparticles was studied by TEM. Fig. 4a and b
show the typical images for HgS nanoparticles prepared
by microwave and conventional heating method, respec-
Fig. 3. The wide XPS spectrum of the HgS prepared by microwave
tively. Because HgS particles are very small as we
heating method.
observed in XRD pattern, it can be aggregated easily.
But we still observe some very small HgS particles in the heating method. In the Fig. 4c and d, we find that size
image and the shape of the products are close to of PbS nanoparticles is in great difference by employing
spherical shape. In the images, it is clearly seen that different heating method. In conventional method, the
the size of HgS nanoparticles prepared by conventional shape of the PbS nanoparticles synthesized is irregular,
heating method is about 7
/15 nm in diameter and a but some are of cubic shape (Fig. 4d) and the size is in
little larger than the ones produced by microwave the range 20
/60 nm. By comparison, the size of PbS
nanoparticles prepared by microwave heating method is
smaller and the shape is spherical. The particle size
distributions of HgS and PbS produced by microwave
heating method, which are measured directly from TEM
images, are shown as histogram in Fig. 5.

3.2. Optical measurement

The UV
/Vis absorption spectrum of HgS nanopar-

ticles is shown in Fig. 6a. The solution used in UV
/Vis
experiment was obtained by dispersing 10.70 mg HgS in
100 ml ethanol. A broad absorption peak at approxi-
mately 360 nm is observed in the spectrum. Probable
optical band-gap could be calculated by utilizing the
following equation:
a(n) A(hn=2Eg )m=2
where a is the absorption coefficient and m /1 for a
direct transition. The energy intercept of a plot of
(aEphot)2 versus Ephot yields Eg for a direct transition
(Fig. 6b) [26]. The band gap of this sample is calculated
to be 2.60 eV from the UV
/Vis absorption spectrum,
which is larger than the reported value for bulk HgS (Eg
2.0 eV) [27], indicating the size quantization effects [28].

3.3. Discussion

To fully understand the role of the ethanol solvent in

the formation of HgS and PbS, several control experi-
Fig. 2. The high-resolution XPS spectra taken for the Hg and S region ments were carried out. Firstly, the reactions were
of HgS prepared by microwave heating method: (a) Hg (4f) (b) S (2p). performed in the absence of sodium hydroxide, no
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Fig. 4. The TEM images of as-prepared HgS and PbS nanoparticles: (a), (c) the HgS and PbS nanoparticles prepared by microwave method; (b), (d)
the HgS and PbS prepared by conventional heating method.

expected HgS and PbS nanoparticles were generated, contrast, in ethyl ether, black HgS and PbS could be
which indicated that sodium hydroxide played an obtained, but most of the reactants, such as sulfur
important part in the synthesis. Secondly, in the powder, still remained in products. It is well known that
experiments, we tried to use other solvents, such as the behavior of solvent under microwave irradiation has
water, ethyl ether and toluene, to replace ethanol. It was a close relationship with its polarity; the increasing
found when water and toluene was acted as solvent, no polarity resulted in the increasing absorptive ability of
expected HgS and PbS was obtained. The final color of microwave energy [29]. Dielectric constants could be
solution was nacarat and milky white in the preparation used as criterion to judge the absorptive ability of
of HgS and PbS by using water as solvent, which is microwave energy. The dielectric constants of water,
indicative of the formation of HgO and Pb(OH)2, while ethanol, ethyl ether and toluene at 25 8C are 78.5, 24.3,
in toluene, the reaction did not proceed at all. In 4.3 and 2.4 correspondingly. Although the dielectric
 T. Ding, J.-J. Zhu / Materials Science and Engineering B100 (2003) 307
/313 311

Fig. 4 (Continued)

constants of water is much more larger than that of We proposed that the temperature played an important
ethanol, the formation of HgO and Pb(OH)2 make it role in accelerating the reaction. Berlan [30] demon-
hard to convert them to final products. strated that due to the delicate balance between dis-
In our experiments, conventional heating method was sipated energy and heat losses, there was an over-heated
used as a control experiment. It was found that pure PbS phenomenon in ethanol solvent by using microwave-
and HgS nanoparticles were also obtained by conven- heating method, while the same phenomenon was not
tional heating method, but the average size of HgS and observed in conventional heating method. It would be
PbS was large and the reaction time was apparently long one of the reasons that microwave-assisted heating
in comparison with microwave heating method. The method could greatly improve the rate of the reaction.
reaction was also conducted by constant stir without With microwave irradiation in polar solvents, high and
heating, but no expected products could be synthesized. uniform heating could be provided and temperature
312 T. Ding, J.-J. Zhu / Materials Science and Engineering B100 (2003) 307
/313

Fig. 5. The particle size distribution picture of HgS and PbS prepared
by microwave heating method: (a) HgS (b) PbS.

gradients could be avoided, providing a uniform envir-

onment for the nucleation [26]. In this way, uniform and Fig. 6. (a) The UV
/Vis absorbance spectrum of HgS nanocrystal
small HgS and PbS nanosized particles could be formed. prepared by microwave method in ethanol. (b) Plots of (aEphot)2/a.u.
vs. Ephot for direct transition.
We speculated that the reactions take place as follows:
microwave heating
4S6NaOH 0 2Na2 SNa2 S2 O3 3H2 O Acknowledgements
ethanol solvent

This work is supported by JiangSu New Technique

(1) Program of China (BG 2001093), the National Natural
Na2 SHg2 0 HgS2Na Science Foundation of China (No. 90206037) and
Na2 SPb2 0 PbS2Na (2) Analytical foundation of Nanjing University. The
authors also thank Ms Xiaoshu Wang and Mr Jianming
In the first reaction, ethanol solvent was heated to a Hong, Modern Analytic Center of Nanjing University,
certain temperature by the absorption of microwave for extending their facilities to us.
irradiation and sulfur powder reacted with sodium
hydroxide to generate S2. Then S2 combined with
Hg2 or Pb2 to form the final HgS or PbS nanopar-
ticles (Fig. 6).
References

[1] S. Gorer, G. Hodes, J. Phys. Chem. 98 (20) (1994) 5338.

[2] S.A. Empedocles, J. Phys. Chem. B 103 (11) (1999) 1826.
4. Conclusions [3] B. Ludolph, M.A. Malik, P.O. Brien, N. Revaprasadu, Chem.
Commun. 17 (1998) 1849.
In summary, HgS and PbS nanocrystals have been [4] N. Tokyo, Jpn. Kokai Pat. 75130378 (C1. H01L. C01B) 1975.
successfully prepared in alkaline ethanol solvent by [5] N. Tokyo, K. Azkio, Jpn. Kokai Pat. 7855478 (C1. C23C15/00)
1978.
microwave-assisted heating method. This method is
[6] N. Tokyo, J. Appl. Phys. 46 (1975) 4857.
proved to be simple and efficient. It may also be [7] Y. Wang, Acc. Chem. Res. 24 (5) (1991) 133.
extended to the preparation of some other sulfide [8] P. Gademne, Y. Yagil, G. Deutscher, J. Appl. Phys. 66 (1989)
nanocrystals. 3019.
 T. Ding, J.-J. Zhu / Materials Science and Engineering B100 (2003) 307
/313 313

[9] T. Trindade, P. O’Brien, X.M. Zhang, M. Motevalli, J. Mater. [20] J. Zeng, J. Yang, Y.T. Qian, Mater. Res. Bull. 36 (2001) 343.
Chem. 7 (6) (1997) 1011. [21] Y.D. Li, Y. Ding, H.W. Liao, Y.T. Qian, J. Phys. Chem. Solids 60
[10] F.E. Kruis, K. Nielsch, H. Fissan, B. Rellinghaus, E.F. Wasser- (7) (1999) 965.
mann, Appl. Phys. Lett. 73 (4) (1998) 547. [22] J.J. Zhu, S.W. Liu, O. Palchik, Y. Koltypin, A. Gedanken, J.
[11] Z.P. Qiao, Y. Xie, Y.J. Zhu, Y.T. Qian, Mater. Sci. Eng. B 77 (2) Solid State Chem. 153 (2) (2000) 342.
(2000) 144
/146. [23] W.S. Sheldrick, M. Wachhold, Angew. Chem. Int. Ed. Engl. 36
[12] S. Maheshwar, K.S. Ramaiah, K. Mukul, M. Neumann-Spallart, (1997) 206.
C. Levy-Clement, J. Electroanal. Chem. 436 (1-2) (1997) 49. [24] Z.P. Qiao, Y. Xie, J.G. Xu, Y.J. Zhu, Y.T. Qian, J. Colloid Interf.
[13] H.S. Zhou, I. Honma, H.H. Komiyama, W. Joseph, Mesosc. Sci. 214 (2) (1999) 459.
Mater. Clusters (1999) 187. [25] A.A. Jose, A.M. Peiro, S. Lahcen, V. Elena, D. Xavier, P. Jose, J.
[14] C.W. White, J.D. Budai, A.L. Meldrum, S.P. Withrow, R.A. Mater. Chem. 10 (2000) 1911.
Zuhr, E. Sonder, A. Purezky, D.B. Geohegan, J.G. Zhu, D.O. [26] S. Tsunekawa, T. Fukuda, A. Kasuya, J. Appl. Phys. 87 (2000)
Henderson, Mater. Res. Soc. Symp. Proc. 504 (1999) 399. 1319.
[15] Y. Xie, P. Yang, Y.T. Qian, Chem. Lett. 7 (1999) 655. [27] S.S. Kale, C.D. Lokhande, Mater. Chem. Phys. 59 (1999)
[16] J.J. Zhu, S.W. Liu, O. Palchik, Y. Koltypin, A. Gedanken, J. 242.
Solid State Chem. 153 (2) (2000) 342. [28] J.P. Yang, F.C. Meldrum, J.H. Fendler, J. Phys. Chem. 99 (1995)
[17] H. Wang, J.R. Zhang, J.J. Zhu, J. Crystal Growth 233 (2001) 829. 550.
[18] X.H. Liao, J.J. Zhu, H.Y. Chen, Mater. Sci. Eng. B B85 (2001) 85. [29] D.R. Baghursl, J. Chem. Soc. Commun. 9 (1992) 674.
[19] A.G. Saskia, Chem. Soc. Rev. 26 (1997) 233. [30] J. Berlan, Radiat. Phys. Chem. 45 (4) (1995) 581
/589.