Microelectronic Engineering 66 (2003) 46–52

www.elsevier.com / locate / mee

Synthesis of HgS and PbS nanocrystals in a polyol solvent by

microwave heating
Tao Ding, Jian-Rong Zhang, Su Long, Jun-Jie Zhu*
Laboratory of Mesoscopic Materials Science, Department of Chemistry, Nanjing University, Nanjing 210093, PR China

Abstract

A novel and quick method for the synthesis of PbS and HgS semiconductor nanoparticles using mercury
acetate and lead acetate as source materials and sulfur powder employed as chalcogenide source by microwave
heating in polyethylene glycol (PEG) solvent is presented in this paper. HgS and PbS nanoparticles were
obtained with average sizes from 20 to 30 nm in PEG, which acts as both solvent and reducing agent. The
products were characterized by powder X-ray analysis, transmission electron microscopy (TEM) and X-ray
photoelectron spectroscopy (XPS). The probable mechanism was presented.
 2003 Elsevier Science B.V. All rights reserved.

Keywords: Microwave heating; Polyol solvent; Semiconductors

1. Introduction

In recent years, sulfide semiconductors with nanometer size dimensions have been the focus of
many researchers due to the quantum size effect exhibited by these nanosized semiconductors [1–3].
Mercury sulfide is a useful material and it can be widely used in ultrasonic transducers [4,5],
electrostatic image materials [6] and photoelectric conversion devices [4–6]. Lead sulfide is also an
attractive semiconducting material because of its variety applications in potential photonic material [7]
and Pb 21 ion-selective sensor [8]. Nowadays, developments of techniques, such as the ‘Chemical
Scissors’ route [9], electrodeposition in acidic medium [10], the ion-exchange colloidal method [11],
and the ion beam method [12] have led to the preparation of lead and mercury sulfides. However,
finding fast and energy-efficient methods to produce metal sulfides are new challenges to synthetic
chemists and material scientists. The microwave-assisted route is yet another novel method to
synthesize lead and mercury sulfides [13,14], and is a very rapidly developing area of research. It is
well known that microwave is electromagnetic waves containing electric and magnetic field

* Corresponding author. Tel.: 186-25-359-4976; fax: 186-25-331-7761.

E-mail address: jjzhu@nju.edu.cn (J.-J. Zhu).

0167-9317 / 03 / $ – see front matter  2003 Elsevier Science B.V. All rights reserved.
doi:10.1016 / S0167-9317(03)00023-6
 T. Ding et al. / Microelectronic Engineering 66 (2003) 46–52 47

components. The electric field applies a force on charged particles as a result of which the charged
particles start to migrate or rotate. Due to the movement of charged particles, further polarization of
polar particles takes place. The concerted forces applied by the electric and magnetic components of
microwave are rapidly changing in direction, which creates friction and collisions of the molecules.
Claimed effects of microwave irradiation include thermal and non-thermal effects [15]. Compared
with conventional methods, microwave synthesis has the advantages of short reaction time, small
particle size, narrow particle size distribution and high purity. Thus, microwave irradiation as a
heating method has found a number of applications in chemistry.
In these years, there is a growing interest in the synthesis of nanosized semiconductors by
microwave irradiation in polyol solvent, such as in ethylene glycol and glycerol [16,17]. Polyethylene
glycol (PEG) as one of the polyols, combined with microwave irradiation, has also been widely
employed as a reducing agent and solvent in organic synthesis [18,19] and as a phase transfer catalyst
[20]. However, few studies have reported the preparation of inorganic nanomaterials by using PEG as
a solvent. Liu and co-workers prepared TiO 2 nanoparticles by using a sol–gel method with
inorganotitanates and polyethylene glycol (PEG) [21]. Zhu et al. prepared silver nanorods by an
electrochemical technique from an aqueous solution of AgNO 3 in the presence of PEG [22]. In those
studies discussed above, PEG was only used as a surface-modifying or capping agent. In this paper,
we present a novel way to prepare HgS and PbS semiconductor nanoparticles in PEG solvent by a
microwave-heating method, where PEG was employed as both a solvent and reducing agent. The
power of the microwave and reaction time affected the purity of the final products. The products were
characterized by powder X-ray analysis, transmission electron microscopy (TEM), X-ray photoelec-
tron spectroscopy (XPS). It was found to be a fast, convenient, mild, energy-efficient and
environmentally friendly route to produce HgS and PbS nanoparticles.

2. Experimental

2.1. Materials and synthesis

All the reagents used in the experiment were of analytical purity and were used without any
purification. In a typical procedure, | 1.6 g lead acetate (Pb(Ac 2 ) ? 3H 2 O) and | 1.5 g mercury acetate
(Hg(Ac) 2 ) were added to | 60 ml polyethylene glycol (PEG-200), respectively. Then | 0.2 g sulfur
powders were introduced into the two PEG solvents. The amount of the entire reagent was optimized.
The two mixtures were placed in the microwave-refluxed system and the reaction was performed
under ambient air for 20 min. The microwave oven followed a working cycle of 9 s on and 21 s off
(30% power). After the reaction finished, the black precipitates were centrifuged, washed with
distilled water and absolute acetone, and dried in air. The final products were collected for
characterization

2.2. Instrumentation

A microwave oven with 650 W power (Sanle General Electric Corp. Nanjing, China) was used in
this experiment. A refluxing system was connected with the microwave oven. The X-ray diffraction
(XRD) patterns were recorded on a Shimadzu XD-3A X-ray diffractometer (CuK a radiation,
48 T. Ding et al. / Microelectronic Engineering 66 (2003) 46–52

l 5 0.15418 nm). The transmission electron microscopy (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 an Escalab MKII instrument, using non-mono-
chromatized MgK a X-ray as the excitation source.

3. Results

3.1. XRD, TEM and XPS studies

The XRD patterns (Fig. 1) show that the products obtained are the cubic phase HgS and PbS. The
peaks are corresponding to khkll values of (111), (200), (220), (311) and (222), which match well
with literature patterns (JCPDF card No. 6-0261 and 5-0592). The average sizes of the PbS and HgS
nanoparticles are estimated by the Debye–Scherrer formula to be 20 nm and 30 nm, respectively.
The XPS was employed to investigate the composition and purity of the prepared PbS nanoparticles
(Fig. 2). The C1s peak lies at 294.55 eV, which should be correctly shifted to 284.6 eV. All the other
peaks are corrected accordingly. Fig. 3a and b show the high-resolution XPS spectra of Pb (4f) and S
(2p), respectively. The two strong peaks at 146.50 eV and 169.75 eV correspond to Pb (4f) and S (2p),
respectively. No peaks of impurities are detected, indicating the high purity of the products. The peak
areas of the Pb and S cores are measured and yield a ratio of Pb to S as 42:58, which shows that the
surface of the products is rich in sulfur. HgS nanoparticles were also investigated by XPS and the
ratio of Hg to S as 58:42 was given.
The TEM observation for the as-prepared PbS and HgS nanoparticles is shown in Fig. 3a and b. It
can be clearly seen that most particles are spherical. Although the majorities of the particles are in
aggregation, there are still some separated particles. The average sizes of HgS and PbS particles are in
the range of 30 | 35 nm and 15 | 20 nm, respectively. They are in good agreement with those
estimated by the Debye–Scherrer equation from the XRD patterns.

Fig. 1. The XRD patterns of the (A) PbS, (B) HgS nanoparticles prepared in PEG solvent.
 T. Ding et al. / Microelectronic Engineering 66 (2003) 46–52 49

Fig. 2. The high-resolution XPS spectra taken for the Pb and S region of PbS (a) Pb (4f); (b) S (2p).

4. Discussion

In the preparation of HgS and PbS, it was found the microwave power and the reaction time would
influence the formation of HgS and PbS. The reaction was carried out in different power and time. On
one hand, the reaction could not fully proceed with low power and short reaction time. On the other
hand, due to the insolubility of reactants in PEG, excessive high power could lead to the
agglomeration of the reactants, therefore, pure final products could hardly be obtained. Prolonging the
reaction time to 30 min did not change the morphology and size of the final products. The probable
reaction mechanism could be described as follows:
50 T. Ding et al. / Microelectronic Engineering 66 (2003) 46–52

Fig. 3. TEM images of the PbS and HgS nanoparticles prepared in PEG solvent: (a) PbS; (b) HgS.

PEG as reducing agent

Hg 21 , Pb 21 → Hg, Pb (1)
microwave irradiation

In PEG solvent
Hg or Pb 1 S → HgS or PbS (2)
microwave irradiation

In the first step, Hg 21 and Pb 21 were reduced to metal Hg and Pb as the intermediate of the whole
 T. Ding et al. / Microelectronic Engineering 66 (2003) 46–52 51

reaction. The process is known as the polyol process and temperature is a dominant factor in affecting
the reactivity [23]. There are two main modes of operation. The first occurring in the liquid phase is a
coupling between the oscillating electric field (2.45310 9 Hz) and the permanent dipole moment of the
molecule resulting in molecular rotations, which bring rapid volumetric heating of the liquid phase. In
the second mode, metallic particles produced in the polyol reaction are also good acceptors of
microwave irradiation and cause rapid heating of these particles. The two heating modes provide
enough high temperature to guarantee the reaction to be fully carried out. In addition to PEG, many
other polyols can also play reducing capacity at high temperatures [24]. In the second step, metal
particles were directly combined with S powder under microwave irradiation, leading to the formation
of the final product. With microwave irradiation in polar solvents, high and uniform heating could be
provided. Thus high temperature could be reached and temperature gradients could be avoided,
providing a uniform environment for the nucleation [25]. Then, uniform HgS and PbS nanosized
particles could be formed.

5. Conclusion

In summary, cubic HgS and PbS semiconductor nanoparticles were synthesized by a microwave
heating method in PEG solvent. It was found to be a quick and efficient route. Further studies may
extend the method for the preparation of the other semiconductor metal sulfides.

Acknowledgements

This work is supported by the National Natural Science Foundation of China (Nos. 50072006 and
90206037) and JiangSu New Technique Program of China (BG 2001093).

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