Inorganic Chemistry Communications 123 (2021) 108329

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Inorganic Chemistry Communications

journal homepage: www.elsevier.com/locate/inoche

Short communication

Controlled Re doping in MoS2 by chemical vapor deposition

Debjit Ghoshal a, Rajesh Kumar b, Nikhil Koratkar c, d, *
a
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, United States
b
University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110078, India
c
Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, United States
d
Department of Material Science and Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, United States

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

Keywords: 2D materials have been extensively studied due to their unique optical and electronic properties. Compositional
Transition metal dichalcogenides doping in these materials could further enable useful utilization of these materials in electronics, optoelectronics
Doping and energy harvesting. However, scalable one pot synthesis of doped Transition Metal Dichalcogenides (TMDs)
Optoelectronics
has been challenging. Here we develop a facile approach for controlled one step Rhenium (Re) doping in
Chemical vapor deposition
multilayer Molybdenum Disulphide (MoS2) by powder Chemical Vapor Deposition (CVD). Interestingly, we find
the morphology of MoS2 is also dependent on the dopant concentrations with a flower like morphology observed
at higher doping concentrations. Further we demonstrate a clear correlation between the shift in PL and Raman
peaks as a function of Re doping concentrations. A red shift in PL is observed with increased concentration of Re
atoms. The ability to controllably dope thin layers of MoS2 could open up unique applications of this material in
areas hitherto unexplored.

1. Introduction
2D materials have shown tremendous potential due to their excep­
tional electronic and optoelectronic properties [1]. More recently these
materials have also found applications in spintronics, valleytronics and
twistronics due their unique symmetry breaking in the monolayer limit
[2,3]. 2D materials have also shown good performance in solvent sep­
aration, energy storage applications, optoelectronics and catalysis
[4–6]. Transistors made of 2D materials have shown promise due to
their atomically flat surfaces making them free from defects enabling
relatively free flow of charges with minimal scattering effects. However,
doping of these materials is critical for the use of these materials
commercially in the semiconductor industry [7,8]. Doped 2D materials
have shown promise in electronic devices and optical sensors [9,10].
Doping with iron has also paved way for magnetism in 2D materials
[11]. Infact, doping of these materials have even enabled better per­
formance of these materials in other applications like catalysis and en­
ergy harvesting [12]. Thus, strategies for scalable doping of these
materials could play a key role in improving the functionalities of these
materials [13].
However, scalable growth of these 2D materials itself still remains a
challenge. Reproducible growth of high quality defect free samples of
these materials is not well understood. Additionally, doping these ma­
terials remains a synthetic challenge. While efforts from previous
research have demonstrated the potential to dope these materials, the
doping process is still less controllable and needs elaborate under­
standing [14]. Also, very little has been done on doping few layers of
these atomically thin layered materials. Additionally, characterizing the
extent of doping is heavily dependent on elemental characterization
techniques like EDAX and XPS or high resolution electron imaging
techniques like HAADF-STEM imaging [15,16]. These techniques are
either elaborate or time consuming or need extensive sample prepara­
tions making them slow and inefficient in a commercial setup. In this
paper, we demonstrate a one pot synthesis of doped MoS2 with Re. Here
we also show the use of optical techniques for determining the extent of
doping in 2D materials. PL measurements at room temperature show a
clear relation between PL peak and extent of doping. Although the
Raman peaks are less sensitive to doping, the Eg mode shows a slight
upshift with higher doping. These optical techniques can be used as high
throughput techniques to verify the presence of dopants and can be used
as toolkits for devising effective strategies for TMDs doping.

* Corresponding author.
E-mail address: koratn@rpi.edu (N. Koratkar).

https://doi.org/10.1016/j.inoche.2020.108329
Received 7 October 2020; Received in revised form 29 October 2020; Accepted 29 October 2020
Available online 3 November 2020
1387-7003/© 2020 Elsevier B.V. All rights reserved.
D. Ghoshal et al.
Fig. 1. (a) Schematic for the growth process. (b) Temperature profile distribution inside the CVD furnace (c) Side view of the atomic structure of pristine 2H MoS2
and doped MoS2. The red atoms are the Re dopant atoms (d) Top view of doped 2H MoS2. Red atoms are the substitution doped Re atoms. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
Table 1
Precursor amounts (ReO3 and MoO3) and ratios for insitu doping.
Sample Set ReO3 (mg) MoO3 (mg) Ratio
Set 1 0.33 2 1:6
Set 2 0.66 2 1:3
Set 3 2 2 1:1
2. Experimental procedure
Specific amounts of precursor ReO3 was added as a source for Re
addition to MoO3 and S. The ratio of precursors (ReO3 to MoO3) in the
feed stream is adjusted to adjust the dopant concentration in the final
stream. S is always used in excess. The precursors (ReO3 to MoO3) are
heated to 700 ◦ C in a tube furnace with ReO3 placed upstream as shown
in the fig. The separation between the edges of the two boats is roughly
maintained at 2 cm. S is heated in a separate zone in the furnace with a
heating belt with the temperature maintained at around 200 ◦ C. Argon is
used as a carrier gas with a flow rate of 30 sccm. The temperature profile
in the furnace as a function of time is shown in Fig. 1. In the first stage,
the furnace is usually purged with Argon at a flow rate of 30 sccm. This is
followed by the ramping of the central zone of the furnace to a tem­
perature of 700 ◦ C as described earlier. The ramping rate is usually
maintained at 37 ◦ C/min. The furnace is maintained at this temperature
for 20 min. After the growth is done, the furnace is allowed to cool to
room temperature naturally without opening the lid of the furnace. The
flow rate of Argon is changed to 80 sccm after the growth is complete.
Morphology of the synthesized samples is analyzed using SEM.
Elemental analysis on the synthesized samples is done using EDAX
spectroscopy. A home-built confocal optical spectroscopy setup is used
for micro PL and Raman measurements. A 532 nm laser excitation was
used for the PL measurements.
3. Results and discussions
A schematic of the setup for the CVD growth of Re doped MoS2 is
shown in Fig. 1a. Fig. 1b shows the temperature profile of the heating
belt and the main heating zone of the furnace. A detailed description of
the process is provided in the previous section. MoS2 most commonly is
found in the 2H polymorphic phase. The side view of 2H polymorph of
undoped (left panel) is shown in Fig. 1c. Similarly, Fig. 1d shows the side
view of the 2H polymorph of doped bilayer MoS2 where the red atoms
2
Inorganic Chemistry Communications 123 (2021) 108329
indicate the dopant Re atom. The corresponding top view of the doped
bilayer 2H MoS2 is shown in Fig. 1e.
The mass ratios of the precursors (MoO3: ReO3) were adjusted to
tune the degree of doping. The specific mass ratios of the precursors used
are shown in Table 1. Sulfur was used in excess for all cases.
Rhenium was selected as a dopant as it has one extra electron in its
d orbital and hence is a potential n dopant for MoS2 (Fig. 2a). However,
controlled Re doping is challenging due to the difference in size of Mo
and Re which makes it difficult to incorporate Re in the lattice of MoS2.
Additionally, ReS2 most commonly exists in the distorted 1 T’ phase as
opposed to the 2H MoS2 making the doping of ReS2 challenging. While
some reports have shown Re doping of monolayer MoS2, these ap­
proaches are less controllable and reproducible. Re doping of multilayer
MoS2 has been even more elusive. The EDAX spectrum of pristine MoS2
and Re doped (0.4%) multilayer MoS2 is shown in Fig. 2b. The emer­
gence of Re peaks can be clearly seen in the spectrum of Re doped
samples. The quantitative information on elemental analysis in the
undoped samples is shown in Fig. S1. The quantitative information on
elemental analysis of the doped samples (0.1%, 0.2% and 0.4%) is
shown in Fig. S2. The Re doping percentage shows a clear increase with
increase in ReO3 precursor content. We thus demonstrate an easy one
step process to controllably dope Re into the MoS2 lattice. Due to dif­
ferences in nature of the chalcogen atoms to the transition metal atoms it
would be energetically impossible to introduce transition metal atoms at
the chalcogen sites. While previous studies have shown substitution
doping of the chalcogens, it has mostly been limited to chalcogen atoms
like Se and O. Thus, in agreement with previous reports we expect
introduction of Re atoms at the Mo sites via substitution doping.
The optical properties of the doped samples were investigated using
PL and Raman spectroscopy. While the PL spectrum showed a single
peak at 671 nm for the undoped samples, the doped samples showed the
emergence of a new red shifted peak. In agreement with previous re­
ports, the integrated PL intensity also quenched with increase in doping
concentration (Fig. 3b). Re doping in MoS2 results in n doping of MoS2.
The increased electron doping leads to shifting of the Fermi level as well
as increased conductivity. However, due to increased density of states of
the electrons, the non radiative channels increase and result in
quenching of the PL. Additionally, the emission of n doped MoS2 is
dominated by trions (not neutral excitons) and this leads to quenching as
well as shift in the PL spectrum. While the Raman spectrum was found to
be less sensitive to doping, with the Ag mode showing no change, a small
upshift can be seen in the Eg mode as shown in Fig. 3a. These results
D. Ghoshal et al. Inorganic Chemistry Communications 123 (2021) 108329

Fig. 2. (a) Positions of Mo and Re on the periodic table. Re has an extra electron compared to Mo. Additionally Re atom is larger. (b) EDAX spectrum (top: pure MoS2,
bottom: Re doped MoS2) showing Re doping with the introduction of ReO3 in the furnace.

Fig. 3. (a) Raman spectrum of MoS2 as a function of doping concentration (b) PL spectra of MoS2 as a function of doping concentration.

(a) (b)

5 µm 2 µm

Fig. 4. SEM image of (a) Undoped MoS2, (b) 0.4% Doped MoS2.

indicate that room temperature PL performed under ambient conditions
provides a convenient means to detect the doping concentration of the
TMD material.
The impact of doping on the morphology of the samples was inves­
tigated by looking at the samples under SEM (Fig. 4a–b). It was found
that the samples exhibited a regular triangular shape. Samples with
doping concentrations of 0.1% and 0.2% showed a similar morphology
with regular triangular crystals. Occasionally, hexagonal crystals were
also observed. However, at higher Re loading (0.4%), broken non-
uniform edges were observed. The EDAX spectrum from the corre­
sponding sample is shown in Fig. S2 (Spectrum 13). This could be
attributed to the difference in size of the Re atom compared to that of the
Mo atoms leading to lattice strain. This could also be possibly due to the
difference in structure of 1 T’ ReS2 to the 2H stabilized phase of MoS2.

3
D. Ghoshal et al.
More experiments need to be done to have a better understanding of the
influence of Re loading on the morphology of the samples.
4. Conclusions
We demonstrated a facile approach to systematically dope MoS2 with
Re atoms. The controlled doping was accomplished by varying the mass
ratio of the precursor associated with the dopant in the CVD furnace. The
introduction of dopant in the samples was verified using EDAX spec­
troscopy. We also demonstrated the use of high throughput optical
techniques like PL and Raman spectroscopy as tools for investigating the
incorporation of dopants in multilayer MoS2. While Raman spectrum
was found to be less sensitive with only the Eg mode showing a shift, PL
emission from the samples showed a clear correlation with the doping
density. Finally, we also demonstrated that the heavily doped samples of
MoS2 with Re show a different morphology compared to samples that
were lightly doped or undoped. This study could open up studies on
controlled doping of MoS2 and other 2D materials [17–20] with a vast
library of potential dopants and unravel unique approaches to charac­
terize the density of doping using high throughput optical character­
ization techniques suitable for commercialization of such approaches.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors acknowledge funding support from the USA National
Science Foundation (Award 1608171).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.inoche.2020.108329.
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