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Enhanced Sulfurization Reaction of Molybdenum Using a Thermal

Cracker for Forming Two-Dimensional MoS2 Layer
Published on 23 May 2018. Downloaded by Kings College London on 25/05/2018 12:29:46.

Received 00th January 20xx,

Accepted 00th January 20xx
Dae-Hyung Cho,*a,b Woo-Jung Lee,a Jae-Hyung Wi,a Won Seok Han,a Sun Jin Yun,a,c Byungha Shin b
DOI: 10.1039/x0xx00000x a,c
and Yong-Duck Chung
www.rsc.org/

We propose a method to fabricate two-dimensional (2D) molybdenum disulfide (MoS2) layers for overcoming issues in
typical fabrication processes by promoting the sulfurization reaction of molybdenum (Mo). A thin sputtered-Mo layer was
sulfurized using a sulfur (S) thermal cracker for forming 2D MoS2 layers. The effects of key process parameters such as
cracking-zone temperature (TC-zone), thickness of sputtered-Mo layer, and Ar pressure during deposition of Mo layer were
systematically investigated. A degree of thermal treatment of evaporated S vapor is controlled by varying the TC-zone. The
higher TC-zone enabled to easily form thin MoS2 layers at low substrate temperature of 250 °C due to the greatly enhanced
sulfurization reaction. The thickness of the final MoS2 layers was controlled by changing the initial thickness of the
sputtered-Mo film. Ultra-thin MoS2 film about 2-layer-thick was obtained by sulfurizing a 2-Å-thick Mo film. The chemical
state of the MoS2 layers largely depended on the Ar pressure during the sputtering process of the initial Mo. Lower Ar
pressure enhanced the MoS2 formation due to more efficient substituting MoS2 phase for MoO3 phase. By using the S
thermal cracker, we demonstrate the method to easily fabricate the 2D MoS2 layer, excluding some problematic issues
such as toxic and expensive reactants, non-vacuum condition susceptible to contamination, and high substrate
temperature.

controllability of flakes, despite of excellent quality. On the

1. Introduction
Nowadays, interest in molybdenum disulfide (MoS2) has been
drastically increasing for applications of electronic and
optoelectronic devices because there are indirect-to-direct band-
gap transition and extreme mobility improvement by thinning
the MoS2 toward monolayer. The monolayer MoS2 transistors
have been reported showing extremely high carrier mobility.1-5
The two-dimensional (2D) MoS2 has been also studied for
various applications of optoelectronic devices, such as
phototransistors,6-9 sensors,10-12 photovoltaic cells,13,14 and
water splitting devices.15-17
There are several ways of obtaining the 2D MoS2 layers
including a mechanical exfoliation,18-20 a chemical
exfoliation,21-24 and a vapor phase growth.25,26 However, these
conventional MoS2 fabrication methods are not without some
drawbacks. The exfoliation method is very difficult to apply for
large-scale fabrication due to limited size and poor thickness
other hand, the typical vapor phase growth, especially that
involves with sulfurization process, employs non- or low-
vacuum equipment (e.g. furnace),27,28 highly toxic H2S gas,29,30
and very extremely high temperatures (over 800 °C).25,31 High
vacuum process can improve reproducibility of the MoS2
quality by avoiding contamination species existing in lower
vacuum level. H2S gas is very toxic and poses safety concerns
limiting its use in not only research laboratories but also
industrial production. Alternatively thermally evaporated
elemental source with a carrier gas can be used but the
sulfurization method typically requires the use of high S
background pressure, therefore, consuming a huge amount of S
source and carrier gas such as argon or nitrogen. Also, the
elevation of substrate temperature raises the manufacturing cost
and induces the performance degradation of some fragile
devices. These drawbacks of the conventional methods are
mainly from the fact that the molybdenum (Mo) precursors
(Mo,29,32 MoO3,31,33 MoO2,34 MoCl5,35 or Mo-Au alloy36) tend
to be chemically stable in the presence of S vapor. Therefore,
the formation of MoS2 requires substantial thermal energy (high
temperature), high process pressure, and/or highly reactive gas
such as H2S instead of S. Therefore, a new method to form 2D
MoS2 films that is vacuum compatible, safe, and cost-effective
is highly desirable.

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Figure 1. Schematic illustration of the MoS2 fabrication process. Firstly, the thin Mo films
are sputtered directly onto substrates. Then the Mo films are sulfurized using the S
thermal cracker. The hot cracking zone induces a chemical cracking of the vaporized S
molecules into more activated smaller molecules.

In this work, we suggest a method to form 2D MoS2 layers
by sulfurizing a thin Mo layer using a thermally cracked S
source. By using highly reactive cracked S species, the method
alleviates a high thermal budget needed to form MoS2 and also
removes the need of using toxic H2S gas. We analyzed the
effect of the S vapor cracking temperature on the formation of
MoS2 thin layers at low and medium substrate temperatures
(Tsub) of 250 °C and 550 °C. Also, the dependence of MoS2
properties upon deposition condition of the initial Mo layer was
investigated. The present work offers an interesting finding that
controlling the temperature of S vapor heating and the
properties of initial Mo layer were important factors for
improving the quality of MoS2 thin layers.
were < 1.0×10-5 Torr, < 1.0×10-4 Torr, and 10 min, respectively. The
cracker consisted of a reservoir zone (R-zone) and a cracking zone
(C-zone) in series. In the R-zone, a typical Knudsen cell, the solid S
granules (Materion, 99.9%) evaporated to a vapor phase of S at
temperature of 150 °C. The evaporation flux of S can be controlled
by changing the temperature of R-zone. The evaporated vapor S
went through the hot C-zone heated up to 1000 °C. The C-zone is a
quartz tube with a length of about 20 cm surrounded by spiral
tungsten filaments. The highest TC-zone of 1000 °C was found to be
the most efficient to make S reactive to metal, based on our previous
works.37,38 The Tsub of 250 °C and 550 °C were used in this work.
The Tsub were measured using a calibrated thermocouple wafer of
Mo-coated soda-lime glass (SLG).

2. Experimental
2.1. Mo sputtering
The 2D MoS2 layers were fabricated in a two-step process including
Mo sputter-deposition and sulfurization. Firstly, angstrom-scale-
thick Mo layers were deposited directly on SiO2-terminated
substrates (soda-lime glass or SiO2/Si) using a magnetron DC
sputtering system (SNTEK). An extremely low deposition rate to
control the film thickness in a few angstroms was achieved with a
very low DC power density of 0.6 W/cm2 (50 W was applied to
10.16 cm-diameter target). The Mo thickness was controlled using
different deposition times. The 2-, 5-, 10-, 20-, and 30-Å-thick Mo
films were obtained using the deposition times of 6, 15, 30, 60, and
90 sec. In the Mo sputtering process, the base pressure and substrate
temperature were < 1.0×10-7 Torr and ambient temperature,
respectively, using a Mo sputter target (99.95%, Materion, USA).
2.2. Sulfurization using S cracker
The prepared Mo thin layers were sulfurized using a downward S
thermal cracker (JMON, SCS-500D) in a vacuum chamber. In the
sulfurization process, base pressure, working pressure, and duration
2.3. Characterization
The Raman spectroscopic measurement (514 nm, Horiba Jobin
Yvon, ARAMIS) revealed the layer number of MoS2 films. The
value of peak (E12g)-to-peak (A1g) distance accurately indicated the
tMoS2.39 The average excitation power and the spectral resolution
were 1.25 mW and 0.9 cm-1, respectively. The optical absorbance
and reflectance measurement (UV-VIS spectrophotometer, Hitachi
U-4001) were carried out to observe the exciton energies40 of the
fabricated MoS2 and the optical properties of Mo films. The
morphology of the MoS2 layer was obtained by atomic force
microscopy (AFM) measurement (Park Systems, XE-100) with the
lateral resolution of 30 nm. The thickness, crystallinity, and
elemental distribution of the MoS2 layers were observed using the
high-resolution transmission electron microscopy (HRTEM) with an
energy-dispersive X-ray spectroscopy (EDS) (FEI, Tecnai G2 F30 S-
Twin). The chemical bonding states of the MoS2 thin layers and their
phase evolution after the sulfurization were revealed by X-ray
photoelectron spectroscopy (XPS) measurement (ULVAC-PHI, PHI-
5000 Versaprobe) with an X-ray beam size of 100 µm2 and a take-
off angle of 90 ° using an electron-neutralizing gun. The sheet
resistance of the Mo initial films were measured by a 4-point probe
system (CHANG MIN CO. LTD, CMT-SR200N).

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Figure 2. The Raman spectra of the MoS2 films prepared using
different Tsub and TC-zone. The Tsub of 250 °C and 550 °C and the
TC-zone of 400 °C and 1000 °C were used. The peak intensities of
E12g and A1g largely depended on the Tsub and TC-zone. The E12g
and A1g peaks emerged with the elevated TC-zone of 1000 °C when
Tsub = 250 °C. At the higher Tsub of 550 °C, the intensity increased
when increasing the TC-zone from 400 °C to 1000 °C.
3. Results and discussion
The S cracker dissociates the vaporized S molecules to chemically
active smaller S molecules. The large S molecules such as S8, S7,
and S6 are dominant species in S vapor at a relatively low
temperature of approximately 150 °C; however, the number of
smaller molecules, such as S2, S3, and S4, rapidly increases at
temperatures above 500 °C.41,42 Thus, the S vapor, which passes
through the C-zone, is believed to become very reactive species. In
our previous works, the S thermal cracker of the same design
successfully enhanced the S reaction with a metallic Zn film by
increasing the temperature of the C-zone.37,38 Based on the same
technique, sputtered thin Mo layers were sulfurized by a thermal S
cracker to form MoS2 layers. The schematic of the MoS2 fabrication
process and the S cracker is shown in Figure 1.
In order to verify the effect of the S cracking on the MoS2
formation, the sulfurization processes were carried out at two
Figure 3. The effect of tMo observed by a Raman spectroscopic measurement. The tMo were varied from 30 Å to 2 Å. (a) The Raman spectra
of MoS2 layers with different tMo. (b) The peak positions of E12g and A1g, and their difference value of E12g - A1g as a function of tMo. (c)
The estimated MoS2 thickness at different tMo.
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different C-zone temperatures (TC-zone) of 400 °C or 1000 °C and at
two different Tsub of 250 °C or 550 °C. The higher Tsub presents a
situation where higher thermal energy is directly provided to the Mo
layer during the sulfurization, while the higher TC-zone provides a
larger number of reactive S species onto the Mo surface. Both high
Physical Chemistry Chemical Physics Accepted Manuscript
Tsub and high TC-zone are likely to enhance the Mo-S reaction to form
MoS2 layers. However, since high Tsub may cause the degradation of
underlying materials, lowering Tsub is desired. We investigated if
increasing TC-zone can assist to lower the Tsub. In our previous study,37
the elevation of TC-zone had successfully enhanced the Zn-S reaction
while keeping Tsub the same.
Figure 2 shows the Raman spectra of the MoS2 films prepared
under different Tsub and TC-zone. The thickness of Mo (tMo) was 30 Å.
The signals of in-plane (E12g) and out-of-plane (A1g) Raman
vibration modes were clearly observed except the sample fabricated
at Tsub = 250 °C and TC-zone = 400 °C. The E12g and A1g peaks
emerged with the elevated TC-zone of 1000 °C even at the lower Tsub
of 250 °C. At the higher Tsub of 550 °C, the Raman intensity
enhanced when the TC-zone increased from 400 °C to 1000 °C, as
anticipated by the enhanced activity of the S. The differences
between the E12g and A1g peaks in few monolayers of MoS2 are
known to be under 24 cm-1.39 The measured differences were about
25 cm-1, which indicated that the fabricated MoS2 was in the bulk
state. The broad and asymmetric peaks at 460 cm-1 indicate a
superposition of the second-order 2LA(M) vibration mode and first
order optical phonon mode A2u.43,44
To achieve thinner MoS2 with 2D-scale, the tMo was varied from
30 to 2 Å by reducing the Mo sputter deposition time from 90 to 6
sec. The values of tMo were derived from the deposition rate
measured from a deposition of thick Mo films. The Mo films on
SLG substrates were sulfurized at Tsub = 550 °C and TC-zone = 1000
°C with consideration for the highest Raman intensity in Fig.2. As
shown in Figure 3(a), the Raman spectra with different tMo illustrate
that the difference between E12g and A1g peaks was decreased by
decreasing the tMo. The peak frequencies of E12g and A1g and their
differences are shown in Figure 3(b). As tMo decreased from 30 Å to
2 Å, the peak frequency of E12g increased from 383.3 to 386.1 cm-1
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Figure 4. The effect of tMo observed by an optical absorption measurement. (a) The absorption spectra of
MoS2/SLG samples prepared from different tMo. The absorbance increased as tMo increased. The exciton
peaks of A, B, and C were clearly observed. (b) The differentiated absorbance data for clear assignment
of exciton peak positions of A and B. (c) The corresponding picture of the fabricated MoS2/SLG samples
with different tMo and tMoS2. The MoS2 layers are yellowish and much transparent in thinner MoS2
samples.
while the peak frequency of A1g decreased from 408.4 to 407.4 cm-1. becomes smaller, the band-gap widens because of more dominant
Also the frequency difference decreased from 25.1 to 21.3 cm-1, role of the quantum confinement effect.26,50 The positions of A and B
which indicates that the MoS2 thickness (tMoS2) reduced. Lee et al. exciton peaks were derived by differentiating the absorbance spectra,
reported the correlation between the frequency difference and the as shown in Figure 4(b). The local minima in the wavelengths of the
number of MoS2 layers.39 By comparing our frequency difference differentiated spectra were assumed to be the position of A and B
values to the reported data,39 the estimated numbers of MoS2 layers exciton peaks in the original absorbance spectra. Similar to C
were plotted in Figure 3(c). The thinnest MoS2 of about 2-layers was exciton peak, A and B peaks also exhibited blue shift. When the
achieved using the tMo of 2 Å. By increasing tMo, the tMoS2 linearly tMoS2 reduced from the bulk to 4-layers, the peak position shifted
increased and became almost bulk over tMo of 20 Å. The ratio about ~ 40 and ~ 10 meV in A and B exciton peaks, respectively.
between MoS2 layer numbers and tMo was not constant because the This larger shift of A peaks than B peaks is attributed to that the shift
Mo roughness was believed to change with tMo. of the A exciton peak originated only from the increase of the first
exciton level while the valence band splitting energy caused the B
UV-Visible spectrophotometric analysis was carried out to exciton to barely change.40 Although the A and B exciton peaks were
observe the absorption spectra of the MoS2 films with various very weak for tMoS2 of 2-layers and 3-layers, both peaks seemed to
thicknesses, as shown in Figure 4(a). The tMoS2 estimated from shift to a higher energy (lower wavelength) than the thicker MoS2.
Figure 3(c) is denoted in the legends of Figure 4(a) and (b). The The results of the peak shift around 1.9 eV matched well with the
exciton resonance peaks of A, B, and C appeared at around 660 nm, shift of photoluminescence of A peaks in a previous work; the
620 nm, and 420 nm, respectively.45 The overall absorbance measured absorption resonances correlated with the direct-gap hot
decreased in the entire wavelength range as the tMoS2 decreased. The luminescence.51 Figure 4(c) presents photographs of MoS2/SLG
C exciton peak showed blue shift from 430 nm (~ 2.88 eV) to 390 samples with different tMo. The samples become more transparent
nm (~ 3.18 eV) with decreasing tMoS2. The C peaks at around 2.8 eV with thinner tMo due to the absorbance reduction as shown in Figure
are known to be due to the transition in nesting bands between the Γ 4(a).
and Λ positions of the Brillouin zone.40,45,46 Although the C peaks
locate at slightly higher energy compared to previous works,45 the To improve the quality of MoS2 layers, the Ar pressure (PAr,Mo)
tendency of blue-shift with decreasing tMoS2 matches well with other during the sputtering process of the initial Mo metal was varied from
reports.47,48 The slightly higher energies of C peaks than previous 40 to 4 mTorr. The PAr,Mo used in the samples of Figures 2 – 4 was
works seemed to be originated from the imperfect film quality due to 40 mTorr. Upon varying PAr,Mo, the deposition time was adjusted to
the residual structural disorder with poor crystallinity as compared to result in the same tMo because the deposition rate varies with PAr,Mo.
the pristine mechanically exfoliated monolayers.47,49 When the tMoS2 The deposition time of Mo were about 15, 13, and 11 sec at PAr,Mo of

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Figure 5. (a) The Raman spectra of the MoS2 layers prepared with different PAr,Mo. The higher PAr,Mo of 4 and 10 mTorr greatly enhanced the
Published on 23 May 2018. Downloaded by Kings College London on 25/05/2018 12:29:46.
Raman intensity than the PAr,Mo of 40 mTorr. (b) The AFM image of MoS2/SiO2/Si sample prepared with PAr,Mo of 4 mTorr. The line profile
across the boundary with SiO2 (left dark region)- and MoS2 (right bright region)-terminated surfaces is shown in inset. (c, d) The cross-
sectional HRTEM image of MoS2 layer prepared at 4 mTorr. (e) The corresponding EDS elemental mapping image of Mo Kα (red) and S
Kα (green) dots.
40, 10, and 4 mTorr, respectively. The TC-zone and Tsub were 1000 °C
and 550 °C, respectively, during the sulfurization. Figure 5(a)
displays the Raman spectra of MoS2 layers formed with different
PAr,Mo of 40, 10, and 4 mTorr. The peak intensities of 4 and 10
mTorr samples were greatly higher than that of 40 mTorr,
maintaining peak positions of E12g and A1g frequencies. It means that
the decrease of PAr,Mo dramatically improves the formation of 2D-
MoS2 layer. An AFM image of the MoS2 layer with PAr,Mo of 4
mTorr is shown in Figure 5(b). The MoS2-coated area was easily
distinguished from the edge area on which Mo metal was not
deposited. The line profile across the both area indicated the tMoS2
was about 23 Å which corresponded to about 3 layers.39 The
thickness measured by AFM agrees well with the result of the
Raman peak difference of about 22.7 cm-1 which also corresponded
to the thickness about 3 layers. The AFM image and the line profile
indicate the MoS2 films consists of some grain or island structures
with an insufficient lateral homogeneity. This was likely attributed to
the fact that the initial thin Mo was grown in island structures rather
than in layer-by-layer structures due to the surface energy difference
between the Mo and the underlying SiO2 substrate. The cross-
sectional images of the MoS2 layer were obtained by a HRTEM as
shown in Figure 5(c) and (d). The 2.5-nm-thick continuous MoS2
atomic layer parallel to the SiO2 substrate was observed. The fine
crystalline microstructure was hardly seen which was attributed to
the relatively poor crystallinity of the MoS2 layers as discussed the
absorption results. The well-defined MoS2 layer was verified by the
EDS elemental color mapping of Mo and S. The Mo signal was
relatively weak because the Mo Kα was used due to the same
characteristic X-ray energies of Mo Lα and S Kα.
To investigate the effect of PAr,Mo on formation of MoS2 layer, the
chemical states of the bare Mo layer and MoS2 layers grown at
different PAr,Mo of 40, 10, and 4 mTorr were identified by XPS.
Figure 6(a) shows the fitted Mo 3d spectra of the Mo layer before
sulfurization. In 3d orbital, clearly distinguishable two peaks are
detected with 3d5/2 and 3d3/2 due to the spin orbit splitting; the peak
intensity ratio of 3d5/2-to-3d3/2 is about 3/2 and peak separation
energy of 3d5/2-to-3d3/2 is approximately 3.2 eV.52 In the fitting
results of Mo 3d spectra, there was no elemental Mo 3d5/2 metal peak
around 228 eV but three different Mo oxide states were observed
(binding energy was read from the 3d5/2 peak); (i) Mo4+ (related to
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Physical Chemistry Chemical Physics Accepted Manuscript
the MoO2 at ~230 eV), (ii) Mo5+ (assigned to Mo2O5 at ~231.5 eV),
and (iii) Mo6+ (derived from MoO3 at ~232.9 eV).52-54 The chemical
states of Mo layer are comprised of the most Mo6+ states of
approximately 99%; i.e., the MoO3 phase seemed to be natively
formed after the Mo deposition due to the air exposure prior to the
sulfurization reaction as proposed in equation (1), while the peaks of
MoO2 and Mo2O5 states were negligible.55
2Mo(s) + 3O2(g) → 2MoO3(s) (1)
After sulfurization, the chemical states in MoS2 layer depending
on PAr,Mo were investigated by fitting the Mo 3d peak as shown in
Figure 6(b). There are three different Mo states in MoS2 layer: Mo-I
(~ 229.6 eV), Mo-II (~ 231.0 eV), and Mo-III (~ 232.8 eV),
corresponding to the MoS2, MoS3, and MoO3, respectively.56-58 With
decreasing PAr,Mo, the MoS2 state (Mo-I) was dominantly formed
while the MoO3 (Mo-III) and MoS3 (Mo-II) states became lesser. As
compared to the Mo 3d of Mo layer, the three 3d5/2 peak positions in
MoS2 layer shifted toward lower binding energy due to the lower
bonding strength of Mo-S than Mo-O,52 which clearly demonstrates
that the sulfurization process successfully converted the MoO3 phase
into the MoS2 phase especially at lower PAr,Mo of 4 mTorr. Notable
thing is the presence of two S states of S-I (~ 226.5 eV) and S-II (~
229.5 eV) arisen from the S in MoS2 and elemental S, respectively.52
The peaks of S-I and S-II were derived from the S 2s orbital. With
decreasing PAr,Mo, both states of S-I and S-II were increased. It is
expected result of the generation of the S-I state with the formation
of MoS2, whereas the S-II state has been rarely reported in MoS2
layers. For more detailed analysis, the Mo and S chemical states are
quantified using relative concentration values obtained from the
fitting results, as shown in Figure 6(c). The concentration of the
MoS2 states drastically increased from 17.5% to 85.7% whereas the
MoO3 phase decreased from 81.9% to 14.2%, as decreasing PAr,Mo
from 40 mTorr to 4 mTorr. The MoS3 concentration showed a very
low values near zero with little change. Based on these fitting
results, we proposed a possible processes as follows in equation (2)
– (4).
2MoO3(s) + S(g) → 2MoO2(s) + SO2(g) (2)
MoO2(s) + 2S(g) → MoS2(s) + O2(g) (3)
MoO2(s) + 3S(g) → MoS2(s) + SO2(g) (4)
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Figure 6. The XPS spectra of bare Mo layer before sulfurization and MoS2 layers
prepared with different PAr,Mo. (a) The fitted Mo 3d spectra of pure Mo layer consisted of
Mo4+, Mo5+ and Mo6+. (b) The variation of Mo 3d spectra of MoS2 layer as a function of
PAr,Mo, fitted with different states of Mo (Mo-I: MoS2, Mo-II: MoS3, Mo-III: MoO3) and S
(S-I: S in MoS2, S-II: elemental S). (c) Relative concentration of various Mo (solid line)
and S (dashed line) phases distributed in MoS2 layer as a function of PAr,Mo..

The MoO2 phase was formed first by reduction of MoO3 during
the sulfurization (2).34,59 Then the MoO2 was likely to be converted
to MoS2 by a single displacement reaction (3)34 or a double
displacement reaction (4).30,59 The highly reactive S vapor promoted
the S molecules to substitute the oxygen in MoO3 for the MoS2
formation. Interesting findings is the dependence of chemical
reaction on PAr,Mo of Mo layer during the sulfurization using the S
thermal cracker. As PAr,Mo is decreased, the S atoms seems to be
more actively incorporated into the Mo layer, resulting in the
transformation from MoO3 into the MoS2. At higher PAr,Mo of 40
mTorr, however, the diffusion of S molecules into the Mo layer is
impeded, thus an amount of unreacted S atoms exists with the high
intensity of S-II states. Moreover, considering the substantial S-II
states at every PAr,Mo, we assumed that the supplied S molecules
were too abundant to react Mo atoms due to the very thin Mo layer,
and thus, unreacted S atoms remained in the MoS2 layer.
The most MoS2 thin layers are known to show trigonal prismatic 2H
or octahedral 1T phases depending on their fabrication method and
post-treatment. We concluded that there are much dominant 2H
phase in the fabricated MoS2 considering the XPS and Raman results.
As shown in Fig. 6(b), the binding energy of the fitted Mo4+ 3d5/2
peaks of MoS2 phases are about 229 eV and the peaks are sharp
without any shoulder at lower binding energy. The Mo4+ 3d5/2 is
generally observed at 229 eV in a 2H phase, whereas the Mo4+ 3d5/2
binding energy of the 1T phase is known to be about 228 eV which
is about 1 eV lower than the 2H phase. If there are some mixed
phase of 2H and 1T, the peak shows doublet peaks.47,60 Moreover,
the 1T-phase MoS2 exhibits dominant J1 peak (~ 153 cm-1) in Raman
spectra.61-63 In the Raman spectra, however, the J1 peak was not
observed (not shown). The formation of 2H-phase-dominant MoS2
layers were likely attributed to that the 2H phase is more
thermodynamically stable than the 1T or 3R phases at the
temperature used in this proposed process.47,64,65
To observe the optical and electrical properties of initial Mo layer
depending on PAr,Mo, thin Mo films were deposited on the SiO2/Si
substrates. Because the angstrom-scale-thick Mo used for the MoS2
fabrication was too thin to characterize and distinguish their
properties, the thicker 20-nm-thick Mo films were prepared for clear
property difference between each sample. Figure 7(a) shows the
reflectance of the Mo films formed by different PAr,Mo and figure
7(b) illustrates their sheet resistance (Rsheet) and roughness kurtosis
(Rku). The reflectance decreased as increasing PAr,Mo in the full range
of wavelength. The Rsheet, measured by a 4-point probe, dramatically
increased as increasing PAr,Mo; about 10 times increased from 4
mTorr to 10 mTorr and then about 10,000 times increased from 10
mTorr to 40 mTorr. Moreover, the Rku, observed by an AFM,
increased from 3.3 to 3.9 as increasing PAr,Mo from 4 mTorr to 40
mTorr. The Rku describes the sharpness of peaks on the film
morphologies: the higher Rku indicates that the Mo surface is
spikier.66 The measured Rku represent that the higher PAr,Mo induced
spikier and sharper shapes of Mo film surfaces. Thus, the Mo films
produced at higher PAr,Mo were believed to reduce the reflected light
in direction of perpendicular to the surface (lower reflectance) and
much lengthen the electrical paths (higher Rsheet). These results are

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 Page 7 of 9 Physical Chemistry Chemical Physics
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Figure 7. (a) The reflectance spectra of the Mo/SiO2/Si samples with different PAr,Mo
when the incident light was perpendicular to the Mo surfaces. (b) The sheet resistance
(Rsheet) and the roughness kurtosis (Rku) of the Mo/SiO2/Si samples as a function of PAr,Mo,
and (c) the corresponding pictures of the samples (c).
likely to be due to the fact that the Mo films at lower PAr,Mo
contained fewer voids and are formed more densely with larger
crystallite onto substrates because the kinetic energy, hence surface
mobility of Mo adatoms increases at a lower working pressure.67,68
Thus, the higher quality Mo film sputtered at lower PAr,Mo is seemed
to enhance the MoS2 formation with remaining less MoO3 and
elemental S, as shown in figure 6(c). Figure 7(c) displays the picture
of the corresponding samples with different colors due to the
reflectance variation.
4. Conclusions
The proposed sulfurization method successfully enabled to
form MoS2 thin layers. The sputtered Mo films were sulfurized
using the thermal S cracker. The 2D MoS2 layers were easily
formed at relatively low substrate temperatures of 250°C – 550
°C using the cracking-zone temperature of 1000 °C. As
increasing the cracking-zone temperature, the Raman intensity
increased at the same substrate temperature. The layer number
of MoS2 was able to be controlled by changing the initial Mo
film thickness. The 2-layers of MoS2 was obtained using 2-Å-
thick Mo film. Moreover, the quality of the MoS2 layers largely
depended on the argon working pressure in the Mo sputter-
deposition. Lower Mo working pressure enhanced the MoS2
formation via more efficient substituting MoS2 phase for MoO3
phase. Studied MoS2 fabrication process is production-
favorable because it includes non-toxic and cheap materials,
low substrate temperature, and vacuum condition with little
contamination. We found a possibility to improve the MoS2
quality by investigating the dependence of Mo properties and
also the S vapor cracking temperature. The proposed method is
expected to be easily adapted to other 2D transition metal
dichalcogenides by varying the sputtered transition metals and
evaporated chalcogen vapors.
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Physical Chemistry Chemical Physics Accepted Manuscript
Acknowledgements
This work was supported by Institute for Information &
communications Technology Promotion (IITP) grant funded by
the Korea government (MSIP) (2016-0-00576, Fundamental
technologies of two-dimensional materials and devices for the
platform of new-functional smart devices).
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