Materials Research Bulletin 42 (2007) 1565–1569

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Short communication
Preparation and characterization of amorphous manganese
sulfide thin films by SILAR method
H.M. Pathan a, S.S. Kale b, C.D. Lokhande c,
Sung-Hwan Han b,*, Oh-Shim Joo a,*
a
Eco-Nano Research Center, Korea Institute of Science and Technology, P.O. Box 131,
Cheongryang, Seoul 130-650, Republic of Korea
b
Department of Chemistry, Hanyang University, Sungdong-Ku, Haengdang-dong,
17, Seoul 133-791, Republic of Korea
c
Thin Film Physics Laboratory, Department of Physics, Shivaji University, Kolhapur 416004, India
Received 1 December 2005; received in revised form 28 October 2006; accepted 8 November 2006
Available online 18 December 2006

Abstract
Manganese sulfide thin films were deposited by a simple and inexpensive successive ionic layer adsorption and reaction
(SILAR) method using manganese acetate as a manganese and sodium sulfide as sulfide ion sources, respectively. Manganese
sulfide films were characterized for their structural, surface morphological and optical properties by means of X-ray diffraction,
scanning electron microscopy, energy dispersive X-ray analysis and optical absorption measurement techniques. The as-deposited
film on glass substrate was amorphous. The optical band gap of the film was found to be thickness dependent. As thickness increases
optical band gap was found to be increase. The water angle contact was found to be 348, suggesting hydrophilic nature of manganese
sulfide thin films. The presence of Mn and S in thin film was confirmed by energy dispersive X-ray analysis.
# 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Amorphous materials; A. Thin films; C. X-ray diffraction; D. Optical properties; D. Surface properties

1. Introduction

Manganese sulfide, MnS is a wide band gap (Eg = 3.1 eV) semiconductor with potential interest in short-
wavelength optoelectronic applications such as in solar selective coatings, solar cells, sensors, photoconductors,
optical mass memories and dilute magnetic semiconductor [1–4]. MnS occurs in three forms [5] 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). Preparation of MnS has been carried out by different methods such as radio frequency
sputtering [6,7], thermal evaporation [8–10], microwave irradiation [11] hydrothermal [12–14], molecular beam
epitaxy [15–18] and chemical bath deposition (CBD) [1,2,19–21]. The properties of thin films prepared by different
methods are critically dependents on the nature of preparation technique.
Recently, the soft chemical synthesis methods has opened route for the synthesis of advanced inorganic materials
that are difficult or impossible to obtain by high temperature solid-state reactions. The main advantage of such a soft

* Corresponding authors. Tel.: +82 2 958 5217; fax: +82 2 958 5219.
E-mail address: shhan@hanyang.ac.kr (S.-H. Han).

0025-5408/$ – see front matter # 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2006.11.017
1566 H.M. Pathan et al. / Materials Research Bulletin 42 (2007) 1565–1569

solution method is to induce the preparation of meta-stable phases and to reduce the considerably the reaction
temperature. In order to alleviate reaction conditions, environmental impact and decrease the economic cost, the
synthesis of this material through soft solution method would be prior if the properties of the material could be retained.
Successive ionic layer adsorption and reaction (SILAR) method is a relatively inexpensive, simple, and convenient soft
solution method for large area deposition [22]. Nicolau [23] has introduced the successive ionic layer adsorption and
reaction (SILAR) method to grow polycrystalline or epitaxial thin films of water insoluble ionic or ion covalent by
heterogeneous chemical reactions at the solid–solution interface between adsorbed cations and anions. The method
involves an alternative immersion of the substrate in a solution containing a soluble salt of the cation and anion of the
compounds to be grown. The substrate supporting the growing film is rinsed in distilled water after each immersion in
order to avoid homogeneous precipitation. The immersion and rinsing time periods can be experimentally determined.
In principle, SILAR is a deposition method in which thickness of the layer has determined by the number of deposition
cycles. The SILAR method has been employed for the deposition of CdS, ZnS, CdZnS, PbS, CuxS, CoS, etc. [22].
In this paper, we report for the first time, the deposition of manganese sulfide thin films by SILAR method at room
temperature. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX)
and optical absorption measurements were carried out to study the properties of manganese sulfide thin films.

2. Experimental

Analytical reagent manganese acetate (Mn(CH3COO)24H2O) and sodium sulfide (Na2SH2O) were used for the
deposition of manganese sulfide thin films. The cation precursor was 0.1 M manganese acetate solution (pH 6). The
source of sulfide ions was 0.1 M sodium sulfide (pH 13.5). Prepared solutions were taken into beakers and for rinsing
purpose ample quantity of distilled water (resistivity 18 MV/cm2) was used. After every five deposition cycles the
water for rinsing was replaced. The deposition was carried out near room temperature (27 8C) using unstirred reaction
solutions. By making several trials the time durations for adsorption, reaction and rinsing were optimized. Micro-slide
glass and ITO coated glass substrates were boiled in concentrated chromic acid (1 M) for 30 min and cleaned
ultrasonically for 10 min first in acetone and then in water:ethanol (1:1) solution and then rinsed with double distilled
water. The cleaned substrates were immersed in 0.1 M manganese acetate for 20 s. The Mn2+ ions were adsorbed to the
substrate. The substrates were rinsed with de-ionized distilled water for 60 s to remove the desorbed ions. Again, the
substrates were immersed in 0.1 M sodium sulfide solution for 20 s. Where the S2 ions were adsorbed and reacted
with Mn2+ ions on the substrates to form manganese sulfide thin films. The unreacted S2 ions were removed by
rinsing the substrates in distilled water for 60 s. By repeating such SILAR deposition cycles for 30 times, we have
obtained homogeneous, adherent, compact and specularly reflecting manganese sulfide thin films of thickness of about
200 nm on glass substrate. The colour of the film was found to be brownish. The darkness of brown colour increases
with increase in film thickness.
Thickness of the manganese sulfide thin film was determined by profilometer. X-ray diffraction patterns of
manganese sulfide films were obtained by using X-ray diffractometer (RINT/PMAX 2500, Rigaku, Japan) in the range
of scanning angle 10–90 (2u) with Cu Ka radiations. Microstructural studies were carried out with scanning electron
micrographs, with FE-SEM (SM-6340 F, Jeol, Japan). The optical absorption studies were carried out with UV–vis
spectrophotometer (Varian-Cary 100, Austria) in the wavelength range of 350–850 nm. The optical spectra were
recorded for the films deposited on glass substrates. The light beam was incident from the film side. The glass substrate
was the reference while recording the spectra. For the water contact angle measurement, sessile drop method was used.

3. Results and discussion

3.1. Reaction mechanism

Manganese acetate dissolves in a water and release Mn2+ as

MnðCH3 COOÞ2 ! Mn2þ þ 2ðCH3 COOÞ (1)
2
It is well known that in aqueous medium sodium sulfide dissolves and releases S as
Na2 S ! 2Naþ þ S2 (2)
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Fig. 1. X-ray diffraction pattern of manganese sulfide thin film onto amorphous glass substrate.

The formation of MnS occurs once the ions of Mn and S reacts with each other as
Mn2þ þ S2 ! MnS (3)
3.2. X-ray diffraction (XRD)

Fig. 1 shows the X-ray diffraction pattern of manganese sulfide thin film (thickness 170 nm) onto glass substrate.
Practically no difference was observed between XRD corresponding to glass and as-deposited manganese sulfide thin
films, which indicates very low crystallinity and amorphous characteristics. The XRD pattern presented here revealed
an amorphous nature of MnS films.

3.3. Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX)

Scanning electron micrographs of manganese sulfide thin film (thickness 170 nm) on ITO coated glass substrate
at 50,000 (: multiplier) is shown in Fig. 2. A well covering and rough manganese sulfide thin film surface can be
seen. A manganese sulfide film composed of unequal diameter grains structure is clearly visible. A compositional
analysis was carried out by energy dispersive X-ray analysis. Inclusion of Mn and S is confirmed from EDX
measurement.

Fig. 2. SEM image of manganese sulfide thin film on ITO coated glass substrate.
1568 H.M. Pathan et al. / Materials Research Bulletin 42 (2007) 1565–1569

Fig. 3. Plot of (absorbance)2 against hn for manganese sulfide thin films (inset: variation of optical absorption with wavelength).

3.4. Optical absorbance

The absorption spectra of MnS films for different thicknesses have been studied. The optical absorbance of thin film is
closely related to its morphology. Fig. 3 (inset) shows the variation of optical absorption with wavelength. The optical
absorption coefficient is of the order of 104 cm1 above the absorption edge. To determine the films have direct or indirect
band gap plot of (absorbance)2 against hn was drawn. Fig. 3 shows the plot of (absorbance)2 against hn for manganese
sulfide thin films for different thicknesses. Extrapolating the straight line portion to the energy axis gives the band gap
value. The estimated optical band gaps are 2.76, 2.82 and 3.00 eV for film thickness of 50, 120 and 170 nm, respectively.
The present value (3.00 eV) is comparable with the experimental values reported for CBD-MnS films [1,19–21].

3.5. Angle of contact measurement

An empirical diagnostic method for evaluation of thin film property is the measurement of water contact angle on
its surface. The presence of local inhomogenities, chemical composition and surface morphology in thin film is
directly related to the surface water contact angle. Fig. 4 shows a water contact angle measurement for amorphous
manganese sulfide films (thickness 170 nm). Here we recorded mean value of water contact angle after repeating
experiment at five different positions. For as-deposited amorphous manganese sulfide film, water contact angle of 348
was observed, confirming hydrophilic nature of the manganese sulfide surface.

Fig. 4. A water contact angle measurement on amorphous manganese sulfide thin film surface.
 H.M. Pathan et al. / Materials Research Bulletin 42 (2007) 1565–1569 1569

4. Conclusions

We have reported a soft solution, SILAR method for the preparation of amorphous manganese sulfide thin films
near room temperature. XRD study reveals that formed material is amorphous. From SEM micrograph, it is observed
that film showed good deposition coverage over the glass substrate. The inclusion of manganese sulfide in thin film
was confirmed by EDX analysis. The optical absorption studies showed that the manganese sulfide is of direct band
gap material with band gap energy increases from 2.72 to 3.00 eV with increase in film thickness from 50 to 170 nm.

Acknowledgement

This research was performed for the Hydrogen Energy R&D Centre, one of the 21st Century Frontier R&D
program, funded by the Ministry of Science and Technology of Korea.

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