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33rd European Photovoltaic Solar Energy Conference and Exhibition

EFFECTS OF SULFURIZATION TIME ON MOS2 ABSORBER LAYER FOR


THIN FILMS SOLAR CELLS APPLICATIONS

H. Rashid1, K.S. Rahman1, M.I. Hossain3, F.H. Alharbi3,4, N. Tabet3,4, M.A. Islam5 and N. Amin1,2*
1
Department of Electrical, Electronic and Systems Engineering, Faculty of Engineering & Built Environment, The
National University of Malaysia, 43600, Bangi, Selangor, Malaysia
2
Solar Energy Research Institute (SERI), The National University of Malaysia, 43600, Bangi, Selangor, Malaysia
3
Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Doha, Qatar
4
College of Science and Engineering, Hamad Bin Khalifa University, Doha, Qatar
5
Graduate School of Material Science, Nara Institute of Science and Technology, Ikoma, Nara 630-0101, Japan
*Corresponding author: nowshad@ukm.edu.my

ABSTRACT: Thin films of MoS2 were prepared on top of soda lime glass by using RF magnetron sputtering
technique and further sulfurized under different timing profiles with static gas pressure of Nitrogen in growth
chamber set at 370 torr at room temperature (RT). Four different time intervals i.e. 60 min, 90 min, 120 min and 150
min were considered at 597 °Ϲ. The effects of this parameter change were studied on absorber layer properties for
photovoltaic solar cell applications. The structural, topographical and morphological properties as well as cross
sectional thickness of MoS2 layers were analysed. MoS2 films were grown at RT at 100W RF power by sputtering.
As-deposited films exhibited two XRD peaks corresponding to (100) HEX and (110) HEX planes at 2θ = 33.4° and 59.5°
respectively, whereas post-deposition treatment (sulfurization) revealed four diffraction peaks corresponding to
(002)HEX, (100)HEX, (103)HEX and (110) HEX at 14.3°, 33.7°, 39.9° and 59.4° respectively. Thickness of sulfurized
films was measured within the range of 446.6 nm to 595.5 nm during FESEM while as-deposited film was measured
419.5 nm and surface was observed to be rough for films sulfurized for 60 min and 90 min. EDX results showed
S/Mo ratio as 3.01 for films sulfurized for 120 minutes whereas as-deposited film was with 2.44 ratio. Film
morphology was found to be very smooth with a low average surface roughness value of 0.98 nm for films sulfurized
for 150 min. Enriched ratio of S/Mo, XRD peaks validation and surface morphological results encouraged its
potential suitability for the use of MoS2 as absorber layer material for solar photovoltaic applications.
Keywords: MoS2 thin films, RF Sputtering, Absorber Layer, FESEM, XRD, AFM, Sulfurization.

1 INTRODUCTION addition, an ultrathin 2D TMDC layer does not suffer


from the disadvantageous anisotropic electronic
The prosperous segregation of graphene from properties intrinsic to their bulk counterparts (i.e. charge
graphite has directed to its widespread study in physics, carrier transport across the layers is three orders of
materials and nano engineering due to its extraordinary magnitude slower than the transport along the layer
electrical and mechanical properties. Yet, a lack of a band plane). Finally, given the inertness of the chalcogenide
gap limits its potential for electronic device applications surface, atomic layer heterojunctions (or vdW
and has encouraged the exploration of other two heterojunctions) can be constructed without lattice strain
dimensional (2D) layered materials. Among them, that can lead to defects and recombination [10].
transition metal dichalcogenides (TMDCs) such as MoS2, Sulfurization is a post depostion process of thermal
MoSe2, WS2 and WSe2 are the utmost studied materials. heating utilized for re-crystallization of deposited films to
TMDC materials possess an X-M-X (X are chalcogen improve the films quality as well as solar cell
atoms and M is transition metal atoms) crystal structure. performance parameters [11]. In this study, thin films of
In which, sandwich layers are coupled by weak van der MoS2 were deposited on top of soda lime glass (SLG) by
Waals (vdW) forces while the intra-layer bonding RF magnetron sputtering technique and further sulfurized
between M and X atoms have strong covalent bonding. under different timing profiles with static gas pressure of
The optoelectronic study of exfoliated flakes has Nitrogen in growth chamber. The structural,
formed the basis to understand their unique optical and topographical and morphological properties as well as
electrical properties [1-4]. First principle density cross sectional thickness of MoS2 layers were analysed.
functional theory (DFT) calculations accord with these
studies and show that the band structure of TMDC
change dramatically with material exfoliation owning to 2 EXPERIMENTAL SETUP
strong quantum confinement effects [5]. Specifically, the
bulk TMDC convert from an indirect bandgap Thin films of MoS2 were deposited by using RF
semiconductor to direct bandgap semiconductor when magnetron sputtering technique on top of SLG substrates
thinned to a single X-M-X layer, which results in a by using 99.99% pure MoS2 target, purchased from
drastic enhancement of enhanced photoluminescence [5- Applied Science Corporation, Republic of South Korea.
8]. It has also been shown that single or few layer TMDC The samples were cleaned in an ultrasonic bath within the
exhibit superior light harvesting characteristics compared fume hood for 10 minutes in methanol, acetone, then
with their bulk counterparts, due to strong light matter again in methanol and finally in deionized (DI) water for
interactions. For example, a single MoSe2 monolayer, 0.4 20 minutes. Dry nitrogen (N2) gas was further used to
nm thick was estimated to generate a maximum 4.6 ensure no marks of any liquid remain on the surface of
mA.cm–2 photocurrent under standard illumination cleaned substrate.
conditions, which is equivalent to the photocurrent During sputtering, the Argon (Ar) flow rate was
produced by 50 nm thick Si or 15 nm GaAs [9]. In maintained at 4.0 SCCM. The working pressure was

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33rd European Photovoltaic Solar Energy Conference and Exhibition

observed 3.20 × 10-3 kPa throughout the deposition. In


order to achieve substantial growth of MoS2 thin films,
the deposition was carried out for 60 min. The sputtering
conditions used are itemized in Table I.

Table I: Summary of parameters of MoS2 thin films

Parameters Conditions
Base Pressure (Torr) 4.2E-6
Operating Pressure (Torr) 2.4E-2
Deposition Temperature (°Ϲ) RT
Deposition Time (min) 60
Deposition Power: RF (W) 100
Argon Gas Flow Rate (SCCM) 3.5
Figure 1: XRD patterns for MoS2 films sulfurized at
Subsequently, the sulfurization processes were various processing times
performed in the presence of pure N2 gas (99.99%) in the
chamber with working pressure set at 370 torr. Summary 3.2 Surface Topology Analysis
of sulfurization process parameters is shown in Table II. The AFM analysis was performed to calculate
average surface roughness and RMS roughness data.
Table II: Summary of sulfurization parameters

Parameters Conditions
Base Pressure (Torr) 0.11
Operating Pressure (Torr) 370
Temperature (°Ϲ) 580
Ramp Rate (°Ϲ/min) 15
Background Gas N2
Sulfur (mg) 250
Sulfurization Time (min) 60, 90, 120, 150

3 RESULTS & DISCUSSION

In this section, the effects of sulfurization process or


deposition time has been discussed to realize the
structural, morphological and compositional properties of
MoS2.

3.1 Structural Analysis


The structural analysis was performed by using XRD
method and the patterns were obtained in the range of 10°
to 80° of 2θ diffraction angle. Fig. 1 illustrates XRD
patterns for MoS2 thin films sulfurized for various timing
profiles i.e. 60 min, 90 min, 120 min and 150 min. XRD
patterns revealed that the first peak of (002) orientation
around 14° is becoming sharper with the increase of
sulfurization process time. Two new peaks (103) and
(110) were introduced and become vigilant for the
samples sulfurized for 150 min. As well as, the peak of
(100) around 33° was turning more intense with the
increase of sulfurization processing time. It is well-
known that heating plays a vital role in the growth of
phases from amorphous to polycrystalline, which has
been observed in this study during the transition from as-
sputtered films to the increase in hold time. Films
sulfurized for 150 min demonstrated high crystallinity as
compare with as-sputtered films. There were total four
peaks observed such as (002), (100), (103) and (110),
maintained hexagonal structure of crystals of MoS2 with
confirmation of JCPDS card no. 37-1492.

Figure 2: AFM results obtained from sulfurization of


MoS2 films under different hold time and as-sputtered

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33rd European Photovoltaic Solar Energy Conference and Exhibition

The average surface roughness was observed to be in The surface of films was observed to be rough and
the range of 6 nm to 9 nm with an increasing trend as a „nano-flower‟ like structure was noticed. The thickness
function of sulfurization time. As sputtered films have was observed to be 487.5 nm for as-sputtered film and
RMS roughness value of 8.02 nm whereas the highest 542.1 nm, 524.8 nm, 465.20 nm and 596.70 nm for
value was observed for films sulfurized for 150 min. The sulfurization time of 60, 90, 120 and 150 min
obtained topological images are shown in Fig. 2. The respectively. No particular trend was observed in MoS2
summary of measured values of roughness is presented in films evolution with respect to processing time of
Table III. sulfurization.

Table III: Summary of parameters of MoS2 thin films 3.4 Compositional Analysis
The compositional ratio of Mo and S was calculated
Sulfurization Ava. Roughness RMS Roughness by EDX for sulfurized and as-sputtered thin films of
Process Time (Sa) – nm (Sq) - nm MoS2, the normalized values are summerized in Table
IV.
As-Sputtered 6.4443 8.0289
It can be seen that S/Mo ratio has an increasing trend
60 min 6.7637 8.5360
with sulfurization processing time. However, the ratio
90 min 6.8632 9.1434
was found to be increasing only till 120 min of
120 min 7.7396 10.7500
sulfurization, afterwards its decreasing drastically. This
150 min 9.0012 12.7370
could be due to more sulfurization time, causing S
elimination. In general, all the films found non-
3.3 Morphological Analysis
stoichiometric with S/Mo ratio of x: 1, where x is more
Fig. 3 is signifying FESEM images (surface and
than 2 in number.
cross-section) of as-sputtered and sulfurized films of
MoS2 with different process times.
Sulfurization Normalized Ratio
Process Time Mo S S/Mo
As-Sputtered 29.11 70.89 2.44
60 min 28.56 71.44 2.50
90 min 26.62 73.38 2.76
120 min 24.95 75.05 3.01
150 min 29.20 70.80 2.43

4 CONCLUSION

Thin films of MoS2 were deposited on top of SLG by


means of RF magnetron sputtering and subsequently
sulfurized under different time profiles i.e. 60, 90, 120
and 150 min in the presence of static gas pressure of N2
in the growth chamber for re-crystallization. XRD results
revealed four diffraction peaks corresponding to (002),
(100), (103) and (110) planes with hexagonal structure,
proving MoS2 presence. The peaks were found to be
intense as the sulfurization time increased; this is obvious
in satisfaction of re-crystallization. The films sulfurized
for 150 min have an intense and dominant peak
corresponding to (002) plane.
The average surface roughness was found to have an
increasing trend during AFM analysis and the values
observed in the range of 6 nm to 9 nm. The thickness of
films was witnessed 487.5 nm for as-sputtered film and
542.1 nm, 524.8 nm, 465.20 nm and 596.70 nm for
sulfurized films of 60, 90, 120 and 150 min respectively.
EDX results indicated non-stoichiometric films with
normalized S/Mo ratio more than 2. Films sulfurized at
150 min hold time are found to have intense and
dominant peaks, better re-crystallinity, bigger grains,
„nano-flower‟ like structure and S/Mo ratio more closer
to MoS2 compositional structure, which is evident for its
suitable use as absorber layer for thin film photovoltaic
applications.

Figure 3: FESEM images (surface and cross section) of 5 ACKNOWLEDGEMENT


MoS2 films, as-sputtered, sulfurized for 60, 90, 120 and
150 min This work was supported thankfully by Qatar National
Research Fund (QNRF) by the grant code of NPRP 6-
931-2-382.

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33rd European Photovoltaic Solar Energy Conference and Exhibition

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