Optical Materials 29 (2007) 1183–1187

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Optical and structural properties of manganese sulfide thin films

C. Gümüsß *, C. Ulutasß, Y. Ufuktepe
Physics Department, University of Cukurova, 01330 Adana, Turkey

Received 27 March 2006; accepted 25 April 2006

Available online 24 July 2006

Abstract

Highly transparent crystalline manganese sulfide (c-MnS) thin films were prepared on glass substrate by chemical bath deposition
(CBD) method at room temperature (27 °C). The refractive index n(k), extinction coefficient k(k) and film thickness t are evaluated from
spectrophotometric transmittance spectrum by using envelope method. The optical band gap of the film was estimated to be 3.88 eV.
XRD measurements show that the MnS films are crystallized in the wurtzite phase and present a preferential orientation along the
c-axis. The effect of trisodium citrate on crystalline films has been determined. The grain size of the film is estimated to be 29.8 nm using
by the Scherrer’s formula.
Ó 2006 Elsevier B.V. All rights reserved.

PACS: 78.66.Hf; 78.20.e; 73.61.r; 75.50.Pp; 71.55.Gs

Keywords: MnS; Optical properties; Thin films

1. Introduction niques it crystallizes into the zinc-blende (b-MnS) or wurtz-

The investigation of diluted magnetic semiconductors
(DMS) has received a great deal of renewed attention in
the last few years due to their important semiconducting
as well as magnetic properties [1–4]. In DMS, the band
electrons and holes strongly interact with the localized
magnetic moments and cause a variety of interesting phe-
nomena [5,6]. Manganese sulfide (MnS) is a wide gap dilute
magnetic semiconductor material (Eg = 3.1 eV) that is
of potential interest in short wavelength optoelectronic
applications such as in solar selective coatings, solar cells,
sensors, photoconductors, optical mass memories [7–9].
Therefore, the knowledge of the optical properties of thin
films is of significance for many applications. MnS thin
films or powders can be found in several polymorphic
forms: the rock-salt type structure (a-MnS) which is the
most common form, by low temperature growing tech-
ite (c-MnS) structure [10,11]. It has been found that b and c
types MnS can transform irreversibly to the stable a type
MnS at 100–400 °C [12–16]. Most of the optical studies
of the MnS have been carried out in bulk crystals [17,18].
There are fewer reports in the literature describing the
structural properties of MnS by chemical bath deposition
[19,20]. The physical behavior of MnS films prepared by
radio-frequency sputtering method has also been investi-
gated [21,22] but not much work has been done on optical
properties of MnS thin films prepared by chemical bath
deposition. In this study, the structural, and optical prop-
erties of manganese sulfide films that were deposited by
the chemical bath deposition technique, were investigated.
The optical constants of the film were determined from
spectrophotometric measurements of transmittance.
2. Experimental details

*
Corresponding author. Tel.: +90 322 338 62 69; fax: +90 322 338 60
Manganese sulfide thin films were deposited on commer-
70. cial microscope slides using CBD method at room temper-
E-mail address: cgumus@cu.edu.tr (C. Gümüsß). ature. Before the deposition the substrate was etched with

0925-3467/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.optmat.2006.04.012
1184 C. Gümüsß et al. / Optical Materials 29 (2007) 1183–1187
diluted hydrochloric acid (5%), cleaned in deionized water,
with propanol, methanol, washed with deionized water and
finally dried in air. Aqueous solutions of manganese ace-
tate [Mn(CH3COO)2] was used as manganese source, thi-
oacetamide (CH3CSNH2) as sulfur source, ammonia/
ammonium chloride (NH3/NH4Cl) (pH = 10.55) as buffer,
triethanolamine [N(CH2CH2OH)3] and trisodium citrate
(C6H5Na3O7) as complexing agents for depositing MnS
thin films. Each deposition was carried for 24 h. The depo-
sition rate was about 8.6 nm/h. For thicker films the sam-
ples were placed in new unused bath. This step was
repeated for 24 h periods until the required thickness was
obtained. The physical characterization of the films have
been reported elsewhere [23]. The optical transmission data
in the wavelength range of 200–1100 nm were recorded on
Lambda 2S ultraviolet/visible spectrophotometer (Perkin
Elmer) at room temperature.
3. Results and discussion
MnS thin films or powders can be found in several poly-
morphic forms: the cubic modification having the rock-salt
type structure (a-MnS) which is the most common form at
ambient conditions, by low temperature growing tech-
niques it crystallizes into the zinc-blende-type (b-MnS) or
wurtzite-type structure (c-MnS) [24,25]. The CBD derived
MnS films in the previous studies at room temperature
were amorphous [19,20]. We have succeeded to prepare
crystalline c-MnS thin film by CBD at room temperature
and suitable deposition conditions to obtain MnS film were
identified [23].
The variation of film thickness with time is shown in
Fig. 1. Initially for the first 24 or 45 h the increase of the
film thickness is slow, deposition rate goes up and the film
thickness increases linearly with deposition time. We could
not observe the interference fringes from transmission spec-
1200
o
27 C
1000
800
Thickness (nm)
600
400
200
40 50 60 70 80 90
Time (hours)
Fig. 1. Film thickness versus duration of deposition for MnS thin films
obtained by the chemical bath deposition technique. The bath temperature
is indicated in the figure.
trum for the first 24 h deposition due to very thin film, but
the following deposition periods of 48, 72 and 96 h give
good transmission spectra with interference fringes. In
order to explain the growth mechanism of MnS film the
three competing processes can be considered; homogenous
deposition, heterogeneous precipitation and ion-by-ion
growth. Homogenous deposition makes poorly performing
films because they are formed from adsorption of MnS par-
ticles and not by ion–ion deposition [26]. We have opti-
mized the heterogeneous process by preparation of the
glass surface with adequate cleaning and etching. As a
result of good substrate, film quality is strongly affected
by the initial nucleation process. Under the suitable process
conditions, nucleation centers took place on the substrate
surface results from preferential adsorption of either
Mn2+ or S2 ions. Condensation of Mn and S ions on this
initial layer results in faster deposition rate after the first
24 h. The basic mechanism of film formation was supposed
to be an ion-by-ion condensation of Mn2+ and S2 on the
substrate from an aqueous medium. Multiple dips in fresh
baths every 24 h period were successful in obtaining thicker
ordered films. Fresh complexing agent provides us with
enough amounts of manganese and sulfide ions which
resulted in a continuous increase of the film thickness.
Growing mechanism of MnS thin films by CBD was
reported in Lokhande et al. [20] and in Fan et al. [19]. In
contrast to our results they are reporting very fast deposi-
tion rate at room temperature with homogenous precipita-
tion resulting in amorphous films. The reported MnS films
growth rate are 200 nm [19] and 300 nm for 120 and 30 min
[20] deposition time respectively. In the present case, we
have deposited 1120 nm MnS film in 96 h at room temper-
ature. Our deposition rate was slower than the previous
studies [19,20] and the process was based on the slow
release of Mn2+ and S2 ions in solution, which then con-
densed in an ion–ion basis on the substrate. The deposition
of MnS takes place through the condensation of the man-
ganese and sulfide ions on this initial layer which acts as a
catalytic surface resulting well ordered films.
The thickness of the film was calculated using the fol-
lowing relation:
  1
nðk1 Þ nðk2 Þ
t¼ 2  ð1Þ
k1 k2
where n(k1) and n(k2) are the refractive indices at the two
adjacent maxima (or minima) at k1 and k2.
Fig. 2 shows X-ray diffraction (XRD) patterns of the
MnS thin films, which were prepared using two different
complexing agents at room temperature. The film prepared
using solutions of manganese acetate [Mn(CH3COO)2] as
manganese source, thioacetamide (CH3CSNH2) as sulfur
100 source, ammonia/ammonium chloride (NH3/NH4Cl) as
buffer, triethanolamine [N(CH2CH2OH)3] as complexing
agent was mainly amorphous or poor crystalline (see
Fig. 2a). In contrast, another film prepared by adding triso-
dium citrate (C6H5Na3O7) into the complexing agents was
 C. Gümüsß et al. / Optical Materials 29 (2007) 1183–1187 1185

transmittance greater than 85% for the wavelength values

over 400 nm. A sharp ultraviolet cut-off observed at

(002)
approximately 325 nm agrees well with the previous results
[29,30]. It is important to note that transmission spectrum
Intensity (arb. units)

of MnS thin film in Fig. 3 shows higher transmittance value

10 20 30 40
2θ (degree)
Fig. 2. X-ray diffraction pattern of MnS thin film deposited on glass
substrate at room temperature. (a) Preferential orientation of the
crystalline grain, with the c-axis perpendicular to the plane of the
substrate is observed and (b) trisodium citrate used as complex agent.
well crystallized (see Fig. 2b). The film deposited in this
way is smoother and shows more pronounced (0 0 2) tex-
ture. The XRD pattern can be attributed to the pure wutrz-
ite-type c-MnS. Similar effect of trisodium citrate was also
reported previous results for other monochalcogenides
[27,28]. In Fig. 2 it is important to note that trisodium cit-
rate is a very effective complexing agent in the preparation
of good crystalline MnS films.
Fig. 3 shows spectrophotometric transmittance of c-
MnS film on glass substrate system. The spectrum has
not been corrected for the glass substrate absorption. It
can be seen that the film is highly transparent in the visible
range of the electromagnetic spectrum with an average
100
(b)
and more interference fringes than previous result [19] it
provides us to apply envelope method for the calculation
of optical parameters. In Fig. 3 oscillations are observed
due to the interference fringes originating from multiple
internal reflections within the films. The transparent region
of the spectrum is useful because the interference of light
(a)
gives periodic variations including peak maximum points
TM and peak minimum points Tm, which are called enve-
lopes. In order to calculate the optical parameters of the
MnS film such as refractive index n, thickness t and extinc-
50 60 70
tion coefficient k from Fig. 3 we have used the envelope
method [31,32]. According to the method put forward by
Manifacer et al. the refractive index n is given by
h i1=2
1=2
n ¼ N þ ðN 2  n20 n2s Þ ð2Þ
where
n20 þ n2s TM  Tm
N¼ þ 2n0 ns
2 T MT m
n0 is the index of refraction of the surroundings (air) and ns
the index of refraction of the substrate (glass). Eq. (2) can
be used to calculate the refractive index n and the results of
our calculation have been plotted as a function of wave-
length in the region of 400–1100 nm in Fig. 4. The refrac-
tive index varies from 2.05 to 1.92 in the visible range
(400 nm < k < 700 nm). The value of refractive index we
have obtained n  1.92 is nearly constant for the wave-
length range of 600 nm < k < 1100 nm. This result is con-
sistent with the previous report of c-MnS film grown by
radio-frequency sputtering technique [21] and to the best
of our knowledge there is no other report of CBD at room
TM

2.06

Tm
2.04
Transmission (%)

2.02
Refractive index, n

50 2.00

1.98

1.96

1.94

1.92
0
200 300 400 500 600 700 800 900 1000 1100 1.90
Wavelength, λ (nm) 300 400 500 600 700 800 900 1000 1100 1200
Wavelength, λ (nm)
Fig. 3. Optical transmittance spectrum of MnS with envelope. The peak
maximum points TM and peak minimum points Tm, are indicated. Film Fig. 4. Variation of refractive index n versus wavelength at room
possess high optical transmission in the visible range. Deposition temperature for MnS film. The value of n is nearly constant for the
temperature is indicated in the figure. Visible–IR region.
1186 C. Gümüsß et al. / Optical Materials 29 (2007) 1183–1187

temperature to compare this value. They have reported the 0.24

value of n  2.03 which is slightly higher than our result 0.22

[21]. The difference may be due to different surface
0.20
morphology.
The absorption coefficient a of MnS films was deter-

Extinction coefficient, k
0.18
mined from transmittance measurements. The calculation 0.16
of the absorption coefficient of the film in this region was
calculated using the following expression: 0.14

1 0.12
a¼ lnðT Þ ð3Þ
t 0.10

where T is the normalized transmittance, t is the film thick- 0.08

ness. These absorption coefficient values were used to
0.06
determine optical energy gap. Fig. 5 shows the plot of a2
versus hm, where a is the optical absorption coefficient 300 400 500 600 700 800 900 1000 1100 1200
and hm is the energy of the incident photon. The energy Wavelength, λ (nm)
gap (Eg) was estimated by assuming a direct transition be-
Fig. 6. Calculated extinction coefficient k, as a function of wavelength k.
tween valence and conduction bands from the expression: The extinction coefficient is calculated from the values of a and k. The
value of k ranges from 0.07 to 0.21.
ahm ¼ Kðhm  Eg Þ1=2 ð4Þ
where K is a constant, Eg is determined by extrapolating size of the MnS thin film is evaluated by means of the
the straight line portion of the spectrum to ahm = 0. From Scherrer formula,
this drawing, the optical energy gap, Eg = 3.88 eV is de- 0:94k
duced. This value is in agreement with previously reported g¼ ð5Þ
B cos hB
data of MnS film [30].
The extinction coefficient k can be obtained by solving where k, hB and B are the X-ray wavelength (0.15418 nm),
the X = eat absorption equation, were a is the absorption Bragg diffraction angle and FWHM of (0 0 2) diffraction
coefficient of the film and defined as a = 4pk/k [29]. The peak (in radians), respectively. The calculated values are
extinction coefficient k is estimated from the values of a 29.8 and 22.2 nm for crystalline and poor crystalline
and k. The calculated results are presented in Fig. 6. It c-MnS films respectively. The grain size was found to in-
can be observed from the graph that the value of extinction crease with crystalline properties of the film. Thus, the film
coefficient is in the range of 0.07–0.21 and shows systematic deposited with trisodium citrate chemical bath decreases
increase with the increase of the wavelength (400– the density of nucleation centers resulting in large grains.
1100 nm). Deposition time and manganese sulfide film The reflectivity of MnS films was not measured experi-
thickness were studied for the bath composition with triso- mentally. After having obtained the values for n and k, it
dium citrate (C6H5Na3O7) at room temperature. was thought worthwhile to calculate the reflectivity value
The (0 0 2) reflection in X-ray diffractogram is fit by R at different wavelengths from the classical relation:
Lorentzian line shape and from the full width at half max-
imum (FWHM) of the (0 0 2) peak fit the mean crystallite
12.5

3. 0 12.0
Reflectance (%)

2. 5
11.5

2. 0
α2.1010 (cm-2)

11.0
1. 5

1. 0 10.5

0. 5
10.0

0. 0 300 400 500 600 700 800 900 1000 1100 1200
Wavelength, λ (nm)
3.0 3.2 3.4 3.6 3.8 4.0 4.2
Energy (eV) Fig. 7. Calculated reflection spectra of crystalline (d) and poor crystalline
(j) MnS thin films. Poor crystalline film has higher value of reflectivity
Fig. 5. Plot of a2 versus photon energy hm for the MnS thin film. than crystalline film.
 C. Gümüsß et al. / Optical Materials 29 (2007) 1183–1187
2
ðn  1Þ þ k 2
R¼ ð6Þ
ðn þ 1Þ2 þ k 2
In order to complete the calculation of the optical con-
stants we have used Eq. (6) to determine R. Fig. 7 shows
calculated reflectance values of R for both MnS thin films.
The main differences observed in the Visible–IR region are
that the transmittance increases and reflectance decreases
continuously for the MnS film. It can be seen from Fig. 7
that the poor crystalline film shows a higher value of reflec-
tivity than crystalline MnS film due to large grain size. The
deposited c-MnS thin films on glass substrate represent
highly transparent features and could be of considerable
interest as a windows layer material in solar cells.
4. Conclusion
MnS thin films were fabricated on glass substrate at
room temperature by CBD. The effect of solution concen-
tration on structural properties of MnS thin films was stud-
ied. Crystalline c-MnS thin films were deposited in which
trisodium citrate was used as complex agent. On the con-
trary amorphous or poor crystalline MnS film has been
deposited without trisodium citrate as complex agent. We
have concluded that trisodium citrate has a significant
influence on the crystallization of the film. The MnS film
exhibits wurtzite-type crystal preferred orientation along
(0 0 2) plane. The average optical transmittance values of
films were higher than 85% in the visible wavelength range.
The optical band gap of the film was estimated to be
3.88 eV. The wavelength dependence of the index of refrac-
tion, the extinction coefficient and the thickness of the MnS
thin film were calculated from the transmission curve using
the envelope method.
Acknowledgement
This work was supported by Cukurova University under
FEF2004BAP3 project number.
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