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Materials Research Bulletin xxx (2011) xxx–xxx

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Materials Research Bulletin

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Short communication

Preparation and hydrothermal annealing of pure metastable b-MnS thin films

by chemical bath deposition (CBD) method
Yong Shi a,*, Fanghong Xue a, Chunyan Li b, Qidong Zhao a, Zhenping Qu a
a
Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University
of Technology, Dalian 116024, China
b
School of Materials, Dalian University of Technology, Dalian 116024, China

A R T I C L E I N F O A B S T R A C T

Article history: Pure metastable b-MnS thin films have been deposited by chemical bath deposition (CBD) method and
Received 26 July 2010 subsequently annealed in a Na2S solution (denoted as hydrothermal annealing). The effects of
Received in revised form 18 November 2010 preparative parameters and hydrothermal annealing on structure, morphology and optical property of
Accepted 6 December 2010
the films have been investigated. Experimental results indicate that the crystalline b-MnS thin films can
Available online xxx
be prepared at a low concentration of Mn and S ions without using any organic chelator. The as-
deposited b-MnS can be transformed to g-phase MnS after the hydrothermal treatment in an autoclave
Keywords:
at 200 8C for 1 h. The estimated Eg values are in the range of 3.15–3.18 eV.
A. Thin films
B. Chemical synthesis
Published by Elsevier Ltd.
C. X-ray diffraction
D. Phase transactions
D. Optical properties

1. Introduction as the low fabrication cost, the growth repeatability, and it is

Manganese sulfide (MnS) is a wide gap (Eg  3.1 eV) VIIB–VIA
dilute magnetic semiconductor (DMS) that has potential applica-
tions in short wavelength optoelectronic devices [1]. MnS occurs in
three polymorphic forms, the stable green a-MnS with rock-salt
type structure, and two pink metastable tetrahedral structures, b-
MnS (sphalerite type) and g-MnS (wurtzite type) [2]. The
thermodynamically stable a-phase forms at a relatively higher
temperature. Both the metastable phases b-MnS and g-MnS can
only exist in a low temperature range, and will be totally converted
into the stable a-form by heating in vacuum at 500 8C [3].
Nevertheless, it is well accepted that metastable materials may
possess unique chemical or physical properties that are of
particular interest for both basic and applied research [4,5].
Therefore, there is a need for developing a simple, inexpensive, and
efficient way to synthesize the metastable forms of MnS.
Various techniques for the formation of MnS in one or more of
the three polymorphic forms have been reported. These include
solvothermal synthesis [4–6] radio-frequency sputtering [3,7],
hydrothermal method [8,9], molecular beam epitaxy [10], chemi-
cal bath deposition (CBD), chemical vapor deposition [11], and
successive ionic layer adsorption and reaction (SILAR) [12]. CBD
has many advantages when compared to other technologies, such
* Corresponding author. Tel.: +86 411 8831 9496; fax: +86 411 8470 7733.
E-mail address: sys-99@163.com (Y. Shi).
readily scalable to large-area deposition [13]. Moreover, CBD
method is an efficient way for the synthesis of metastable
materials under a mild condition [14,15]. Pramanik et al. firstly
prepared amorphous MnS thin films onto glass substrate by CBD
method [16]. Then Lokhande et al. further obtained polycrystalline
film consisting of mixed (b and g) phases [17]. More recently, pure
g-phase MnS films have been successfully prepared using CBD
technique [18–20]. However, literature survey shows that pure b-
MnS thin films formed under such aqueous conditions have not
been reported.
In addition, poor adhesion and non-uniform films are common
problems when depositing CBD films onto smooth surface, such as
ordinary glass slides. Consequently, post-annealing treatments,
which were usually carried out in a vacuum system or in N2, Ar, or
H2 atmospheres, are normally required to stabilize and crystallize
the as-deposited CBD metal chalcogenide [21–23]. In order to
simplify the annealing process, we have developed a new and
simple hydrothermal method for the as-deposited MnS thin film.
The crystallization of the as-deposited MnS thin film was carried
out in a sealed Teflon-lined autoclave with Na2S solution at 200 8C.
Herein, we investigate the preparation of pure b-phase MnS by
varying the CBD deposition conditions: at a low concentration of
manganese acetate and thioacetamide without using organic
complexing agents. The samples were characterized with X-ray
diffraction (XRD), transmission electron microscopy (TEM) and
optical absorption spectrum. The effects of post-hydrothermal
annealing are discussed in detail.

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doi:10.1016/j.materresbull.2010.12.009

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2. Experimental Also, the CBD bath should contain Mn salt and a suitable
complexing agent to have soluble species of Mn2+ in the aqueous
2.1. Preparation of MnS thin films medium. In this study, NH3/NH4Cl was used as buffer to fix the
solution pH values and ammonia to control Mn2+ concentration,
Microscope glass slides of 26 mm  76 mm  1 mm dimension according to the following reaction:
were used as substrates. Before the deposition the substrates were
first etched with diluted hydrochloric acid (5%), then degreased MnðNH3 Þ4 2þ $ 4NH3 þ Mn2þ (2)
with ethanol, ultrasonically cleaned with purified deionized water
Finally, the initial concentration of Mn2+ and S2 ions in the
and finally dried in air.
mixed solution also plays an important role in the growth of MnS
The chemicals used for the preparation were AR grade. Pure
thin film. From previous studies, it should be noted that
b-MnS thin films was deposited using freshly prepared aqueous
triethanolamine (TEA) was usually used as a complexing agent
solutions of 10 mL of 0.25 mol/L Mn(CH3COO)2, 10 mL NH3/
to ensure the slow release of Mn2+ ions [17,20]. However, at a low
NH4Cl buffer solution (pH 10.5), 10 mL of 0.25 mol/L CH3CSNH2
initial concentration of Mn and/or S ions, the addition of TEA may
and 20 mL deionized water. The reactants mentioned above
result in a too low Mn2+ concentration in bath solution and cause a
were mixed well in 50 mL beakers with constant stirring. Then
non-uniform and discontinuous film formation, as reported by
the pre-treated substrates were introduced vertically into the
Lokhande et al. [17]. In this study, without the addition of TEA, b-
beakers when the solution temperature was appropriate. The
MnS was successfully obtained at the lower concentrations of Mn
deposition parameters such as temperature and growth time
and S ions (0.25 mol/L), which is only a quarter of the concentra-
have been optimized and the films prepared in this study were
tion for the synthesis of g-MnS in the previous report [20].
under the fixed synthesis conditions: bath temperature
The total formation of MnS film could be presented from the
(T) = 60 8C, and time (t) = 4 h.
formula (3):
The as-deposited b-MnS films were further hydrothermal
treated in a sealed Teflon-lined autoclave with 1 M Na2S solution at Mn2þ þ CH3 CSNH2 þ 2OH Ð MnS þ CH3 CSNH2 þ H2 O (3)
200 8C for 1 h to investigate the annealing effects.

2.2. Characterizations of MnS films 3.2. XRD analysis

The film thickness was measured from the scanning electron The XRD patterns of as-deposited and hydrothermal annealed
image (SEM) of the cross-section of the sample. The thickness of MnS thin film are shown in Fig. 1a and b, respectively. The (1 1 1)
the prepared MnS thin film is found to be about 0.6 mm. The and (2 2 0) peaks at 27.58 and 45.78 (Fig. 1a) exhibit the metastable
structure characterization of MnS films was carried out by a X-ray b-MnS (cubic phase) with lattice constant a = 0.5610 nm (JCPDS,
diffractometer (D/Max-2500, Rigaku Corp.) using Cu Ka radiations. no. 40-1288). The average crystallite size calculated by Scherer’s
The microstructure of the films was studied by transmission formula is 20.8 nm, indicating that the as-deposited b-MnS film is
electron microscopy (TEM) using a Philips TecnaiG2 F20 micro- made up of nanocrystal particles.
scope operating at 200 kV. Optical properties were determined by The hydrothermal annealed film showed several additional
using a JASCO V-570 UV–vis–NIR spectrometer. peaks at 25.68, 29.28 and 50.08 (Fig. 1b), which can be indexed to
(1 0 0), (1 0 1) and (1 0 3) planes of g-MnS (JCPDS, no. 40-1289).
The emergence of a new g-phase may be due to the fact that b-
3. Results and discussion
phase has the lowest free energy for the formation of the MnS
polytypes, followed closely by that of the g-phase [2]. Therefore, b-
3.1. Reaction mechanism
MnS is easily transformed to g-MnS when hydrothermally treated
at 200 8C in this study. Moreover, the intensity of the (1 1 1) plane
The morphology, particle size, optical properties and especial
the crystalline phase of MnS films are critically dependent on the
preparative conditions of CBD technique. The aqueous solution of
Mn(CH3COO)2 was used as Mn2+ source and thioacetamide as S2
source during the MnS deposition. The deposition of MnS occurs
when the ionic product of Mn2+ and S2 exceeds the solubility
product of MnS. The slow release of Mn2+ and S2 ions is the basis
for condense ion-by-ion CBD thin film. According to the early
reports [18–20], three aspects may play the main roles in obtaining
the crystalline CBD MnS thin films.
The first one involves the bath temperature and time. Initial
higher bath temperature favors the formation of crystalline thin
films. It was reported that the MnS film deposited at 30 8C for 3 h is
amorphous while the film deposited at 60 8C consists of phase-
pure g-MnS [20]. As mentioned above, in this study the optimized
bath temperature is 60 8C and bath time is 4 h.
The second one is related to the pH value, which is crucial to the
control of the concentration of S2 ions in the CBD synthesis. The
MnS film is commonly obtained from an aqueous alkaline bath, in
which thioacetamide is used to decompose to yield S2 ions. The
release rate of S2 ions is associated with pH values according to
the following formula:
Fig. 1. X-ray diffraction patterns of as-deposited and annealed (at 200 8C in Na2S
solution for 1 h) MnS thin films (a) as-deposited MnS thin film and (b) annealed
 2
CH3 CSNH2 þ 2OH Ð CH3 CONH2 þ S þ H2 O (1) MnS thin films.

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Fig. 3. Plot of optical absorption vs. wavelength of MnS thin films for (a) as
deposited and (b) annealed at 200 8C in Na2S solution for 1 h.

of b-MnS was drastically increased, showing that the crystallinity

of the films increased after annealing.

3.3. TEM study

For TEM studies of the prepared samples, the MnS thin film
deposited on glass substrate was scratched and placed onto a piece
of amorphous carbon coated copper grid. Fig. 2a shows the TEM
image of the as-deposited b-MnS thin film. The morphology of this
sample exhibits an irregular layer structure. The selected area
electron diffraction patterns shown in the inset of Fig. 2a, together
with high resolution TEM image (Fig. 2b), confirm that the lattice
spacing d is 0.32 nm, corresponding to the typical (1 1 1) plane of
b-MnS (JCPDS, no. 40-1288). This value is in good agreement with
the XRD results (see Fig. 1a). Fig. 2b shows the TEM images of b-
MnS thin films after the hydrothermal treatment. It can be seen
that the width of the layer structure increases and the boundaries
becomes more distinct and compact. These TEM observations,
together with XRD results, indicate that the post-deposition
hydrothermal annealing can effectively improve the crystallinity
of the as-deposited MnS thin films.

Fig. 2. TEM (a) and HRTEM (b) of as-deposited MnS thin films and TEM (c) of MnS
thin films annealed at 200 8C in Na2S solution for 1 h.

Fig. 4. Plot of (ahn)2 vs. ‘hn’ of MnS thin films for (a) as deposited (b) annealed at
200 8C in Na2S solution for 1 h.

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3.4. Optical properties study
UV–vis absorption spectra of the as-deposited b-MnS thin film
and annealed mixed phases (b and g) MnS thin film are shown in
Fig. 3. The absorption edge at around 345 nm for both MnS thin
films, is almost the same as the reported value of the metastable
form of MnS nanoparticles at 325/345 nm [24,25]. In addition, an
absorption band appears at 440 nm in Fig. 3, which may be
attributed to the electron transition between the sulfur ion and
manganese ion [26,27].
The optical absorption data was analyzed from Eq. (4) in order
to determine the bandgap value of direct bandgap semiconductors
[28]:
1=2
Aðhn  Eg Þ
a¼
hn
where a is the absorption coefficient, hn is the photon energy and
Eg is the optical band gap, A is a constant relative to the material.
The absorption coefficient a was evaluated from measurements of
optical absorbance (A) and film thickness (d) using the formula
[29]:
1 A
a¼
d log e
The curve of (ahn)2 vs. hn is plotted in Fig. 4, and the Eg value of
the product can be estimated by extrapolating the straight line
portion of the plot of (ahn) vs. hn = 0. The estimated Eg values of as-
deposited and annealed film are 3.18 eV and 3.15 eV, which fall
within the range of the bandgap energies reported for MnS thin
film [7,17,19].
Acknowledgements
This work is supported by the National Basic Research Program
of China (grant no. 2011CB936002), the doctoral scientific
research foundation of Liaoning Province of China (grant no.
20071088), the Fundamental Research Funds for Central Univer-
sities (grant no. DUT10LK22) and the Specialized Research Fund
for the Doctoral Program of Higher Education (grant no.
200801411065).
Please cite this article in press as: Y. Shi, et al., Mater. Res. Bull. (2010), doi:10.1016/j.materresbull.2010.12.009
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