Integrated Ferroelectrics

An International Journal

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Morphology and structure of WS2 nanosheets

prepared by solvothermal method with
surfactants

Deqing Zhang, Tingting Liu, Yixuan Jia, Jixing Chai, Xiuying Yang, Junye Cheng
& Maosheng Cao

To cite this article: Deqing Zhang, Tingting Liu, Yixuan Jia, Jixing Chai, Xiuying Yang, Junye
Cheng & Maosheng Cao (2018) Morphology and structure of WS2 nanosheets prepared
by solvothermal method with surfactants, Integrated Ferroelectrics, 188:1, 24-30, DOI:
10.1080/10584587.2018.1454759

To link to this article: https://doi.org/10.1080/10584587.2018.1454759

Published online: 24 May 2018.

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INTEGRATED FERROELECTRICS
, VOL. , –
https://doi.org/./..

Morphology and structure of WS nanosheets prepared

by solvothermal method with surfactants
Deqing Zhanga , Tingting Liua , Yixuan Jiaa , Jixing Chaia , Xiuying Yanga ,
Junye Chengb , and Maosheng Caoc
a
School of Materials Science and Engineering, Qiqihar University, Qiqihar, China; b Center of
Super-Diamond and Advanced Films, Department of Physics and Materials Science, City University
of Hong Kong, Hong Kong, China; c School of Materials Science and Engineering, Beijing Institute
of Technology, Beijing, China

ABSTRACT ARTICLE HISTORY

In this work, a modified solvothermal method has been Received  September 
developed to synthesize few layers of tungsten disulfide- Accepted  February 
nanosheets(WS2 -NS). Different types of surfactants were also
KEYWORDS
employed in the modified solvothermal method with respect Solvothermal synthesis;
to the original procedure. As-prepared WS2 samples were WS -nanosheets; growth
characterized by XRD, TEM, and Raman spectrum. The results mechanism
showed that the obtained WS2 -NS were consisted of 1–10 atomic
layers. Importantly, the effects of surfactant on the morphology
formation of WS2 -NS were investigated. A possible growth
mechanism is presented to explain the formation of WS2 -NS.

1. Introduction
During the past years, tremendous attention has been paid to two-dimensional lay-
ered materials. Besides graphene [1], layered graphene-like materials also gained
quite a lot of interest, such as transition metal dichalcogenides(TMD) [2] and topo-
logical insulators. The element layer of TMD consists of transition metal atoms
sandwiched between the upper and lower layers of sulfur atoms. The atoms were
connected by strong covalent bonds, while the layers were weakly held together
by Van Der walls forces [3]. Therein, WS2 was a representative of TMD which
can be processed by chemical and physical methods [4, 5] into a two-dimensional
nanosheet structure. Furthermore, WS2 -NS with atomic scale thickness may exhibit
special and interesting properties in contrast with those of their bulk compounds
[6]. Due to the peculiar electron configuration and high specific surface area,
WS2 -NS has potential application in catalytic hydrogen production [7], electrode
devices [8] and energy storage devices [9].
To date, various methods have been reported to prepare the WS2 -NS, includ-
ing mechanical exfoliation, chemical exfoliation, chemical vapor deposition and

CONTACT Maosheng Cao caomaosheng@bit.edu.cn; Junye Cheng jycheng-c@my.cityu.edu.hk

Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ginf.
©  Taylor & Francis Group, LLC
 INTEGRATED FERROELECTRICS 25

hydrothermal method. Late et al. [10] obtained the few layers WS2 -NS by repeat-
edly folding a piece of adhesive scotch tape with WS2 powder. Coleman et al.
[11] developed a reliable surfactant-assisted liquid exfoliation method to pro-
duce WS2 -NS. In the present work, in order to meet the requirements of WS2 -
NS used in potential fields, a one-step solvothermal method was proposed to
stably and efficiently prepare WS2 -NS. The effects of surfactants on the mor-
phology and structure were studied, and the possible growth mechanism was
discussed.

2. Experimental

2.1. Synthesis of WS2 nanosheets

All chemicals were analytical degree and used without further purification.In a typi-
cal process, 0.198 g of tungsten chloride (WCl6 ) and 0.675 g of sodium diethyldithio-
carbamate were dissolved in 36 ml of absolute ethanol, and the resulting solution
was stirred for 30 min and transferred to a 100 ml of para-polyphenylene (PPL) liner
stainless steel autoclave which was afterwards sealed tightly, and heated at 220°C for
18 h. Then the reaction kettle was taken out and cooled to room temperature. The
black precipitates were retrieved from the solution by centrifugation and washed
with distilled water and ethanol for several times, and finally dried in vacuum at
60°C for 12 h. To better distinguish the samples, the precipitates obtained using
no surfactants was named as sample I, while precipitates obtained with the addi-
tion of cetyltrimethyl ammonium bromide (CTAB, 0.06 g) and polyvinyl pyrroli-
done (PVP, 0.06 g) were named as sample II and sample III, respectively. In our
experiment, the reaction routes for the synthesis of WS2 could be expressed as
follows [12]:

W6+ + R = W4+ + R∗ (1)

+ ∗
W 4+
+ S = WS2 S (2)
+ ∗
W 6+
+ RS = WS2 RS (3)

where R is a reducing agent, S is a vulcanizing agent, RS also acts as a vulcanizing

agent having a reducing property, R∗ , S∗ and RS∗ are generated are substances after
the reaction.

2.2. Characterization
The X-ray diffraction(XRD) patterns were recorded using German Bruker-AXS D8
X-ray diffractometer with Cu Kα radiation (λ = 0.1546 nm). The morphology of the
as-synthesized products were characterized by transmission electron microscopy
(TEM, Hitachi, H-7650). Raman spectroscopy measurements were carried on a Lab
RAM HA Evolution.
26 D. ZHANG ET AL.

Figure . XRD patterns of (A) sample I, (B) sample II and (C) sample III.

3. Results and discussion

3.1. Morphology and structure of WS2 -nanosheets

In order to confirm the composition of the samples, the XRD pat-

terns of WS2 -nanosheets were showed in Figure 1. As presented in
Figure 1, A, B, and C are the XRD patterns of the WS2 heterostructures prepared
without adding surfactants and adding different kinds of surfactants, respectively. It
shows the similar XRD patterns whether the surfactant is CTAB, polyvinyl pyrroli-
done or no surfactant, indicating that the surfactants added to the system have no
effect on crystallization of WS2 -NS. When the diffraction angle is located in 15°,
28°, or 39°, there aren’t obvious diffraction peaks. The curve of B was the smoothest
and the degree of crystallization was also the best. All samples present representative
peaks indexed to the hexagonal WS2 structure (JCPDS card No.87-2417).
TEM was employed to investigate the obtained samples. As presented in Figure 2,
(A) was the TEM result of sample I prepared without adding surfactants. (B) and (C)
were the TEM images of the product obtained by adding CTAB. Figure 2(D) was
the result of sample with the addition of PVP surfactant. These results show that the
surfactants in the preparation of WS2 process by hydrothermal method have great
influence on the morphology of samples. The sample I observed was with a diam-
eter of 300 nm. The special layered structure of the irregular shape of WS2 cannot
be clearly seen, and the product of WS2 was still in the black agglomerated state
demonstrating that no addition of surfactant will result in the bulk phase. However,
as shown in Figure 2(B) and (C), when the CTAB was added, a plate-like struc-
ture consisting of nanosheets was formed. The length of the nanosheet was ∼400
to 900 nm, and the black agglomerates presented in Figure 2(A) tend to disappear,
leading to higher transparency of nanosheets. In Figure 2(D), when the PVP was
added, the rod-shaped nanostructures of WS2 appear with larger middle width and
the thinner ends, and there isn’t lamellar structure.
Raman spectroscopy was further applied to characterize the layered structure of
the WS2 .According to previous reports, the bulk crystal WS2 shows two Raman
 INTEGRATED FERROELECTRICS 27

Figure . TEM images of (A) sample I, (B and C) sample II and (D) sample III.

peaks at 355 and 421 cm−1 corresponding to the well know active Raman modes
in-plane E1 2 g and out-of-plane A1 g . With the decrease of the number of crys-
tals layers, the two peaks are red-shifted and blue–shifted respectively and close to
each other. As show in Figure 3, the two peaks of sample I appeared at 355.1 and
420.2 cm−1 , which is consistent with bulk crystal WS2 . The sample II is a plate-like
structure composed of regularly arranged nanosheets and possesses certain thick-
ness as compared with few layer nanosheets, so these two peaks appeared at 359.1
and 420.2 cm−1 respectively. The E1 2 g peak and A1 g peak of sample III appeared

Figure . Raman spectra of (A) sample I, (B) sample II and (C) sample III.
28 D. ZHANG ET AL.

at 362.1 and 417.2 cm−1 respectively and Raman shift between these two peaks is
55.1 cm−1 . Referring to Late et al. [10], the thickness of sample III is about 1–10
atomic layers. Hence, independent of the TEM measurements, these results provide
an additional confirmation of the few layer characteristics of sample III.

3.2. Experimental mechanism

With tungsten chloride as the tungsten source and sodium diethyldithiocarbamate

as the sulfur source of the reaction, the crystal growth mechanism in the solution
was often very complicated, and the actual solution crystallization process was still
unclear [13]. In our experiments, the mechanism for the synthesis of tungsten disul-
fide (WS2 )crystals was the oxidation-reduction reaction. WS4 2- as an intermediate
product in the synthesis process formed by the rapid reaction of tungsten hexachlo-
ride (WCl6 ) and sodium diethyldithiocarbamate in anhydrous ethanol solution. At
the initial stage of synthesis, a large amount of tiny crystal core nanoparticles of tung-
sten disulfide (WS2 ) first formed. When the free enthalpy of this system became neg-
ative, the gain of the surface energy compensates for the energy of the lattice growth
[14], so the crystal particles would further grow until the initial nuclei began to
develop into larger nanocrystals. With the further increase in reaction time, many
new nuclei continued to form and many irregular nanoparticles emerged. Thus,
when no surfactant was added, the nano-sized tungsten disulfide (WS2 ) nuclei grew
into a black agglomerated layered structure that was easy to be ignored as shown in
Figure 4(A).
Although the crystal growth mechanism and the crystallization process in the
solution were very complicated, we mainly discuss the effect of surfactants on
the above process. According to the previous study [15], cetyltrimethylammonium
bromide (CTAB) is often used as a controlled molding and stabilizer, which has
been shown to be a “soft template” in solution to form different conformations by

Figure . Illustration of WS reaction mechanism diagram.

 INTEGRATED FERROELECTRICS 29

self-assembly and then to synthesize various components of the nanomaterials.

The surfactants usually have a hydrophilic head group and many hydrophobic tail
groups. When the solution of the surfactant reaches a certain concentration, it will
self-assemble to form micelles. As presented, nano-CTAB molecules tend to form
lamellar micelles if the concentration reaches the critical micelle concentration. In
order to maintain the energy of the low system [15], the layered micelles were aggre-
gated together to form ordered monodisperse nanocrystals, spontaneously with the
presence of van der Waals forces between the surfactants of CTAB, leading to the
assembly of the ordered structure [16]. The ordered assembly provides a specific
microenvironment for chemical reactions, where the resulting WS2 sheet-like lamel-
lar nanocrystals gradually grew and stacked together to eliminate surface energy
(Figure 4(B)).
It is known that polyvinylpyrrolidone (PVP) molecule possesses a butyrolactone
structure, containing hydrophilic and polar groups. The environment at both ends
of the amide group in the molecule was not the same, and the oxygen atom was
exposed from the molecular model. In addition, its nonpolarity from the molecular
ring, long chain of the methylene (–CH2 –) and the sub-methylene (–CH=) groups
makes itself oleophilic. Thus, PVP provides an insertable long chain for the matrix.
More importantly, PVP can be easily dissolved in anhydrous ethanol so that tung-
sten WS2 nano-particles easily accumulate and grow. In the hydrothermal synthe-
sis process, the addition of PVP allows the reaction system to form a certain space
to limit the stacking of WS2 nanoparticles. So many small WS2 crystal cores with
PVP surfactant inlaid in the system form rod-shaped structure with narrow width
at both ends of rod-like structure but large width at the middle of the rod-like struc-
ture (Figure 4(C)). This experiment demonstrates that use of surfactants plays a very
important role in crystal growth. Overall, the synthesis method was both effective
and simple, and can be used for the preparation of other transition metal sulfide
materials, and two-dimensional layered nanostructures.

4. Conclusions
In summary, WS2 -NS were successfully prepared by a simple one-step solvothermal
process. The thickness of the prepared nanosheets with addition of PVP was con-
firmed to be 1–10 atomic layers by TEM images and Raman spectra. The experimen-
tal results of samples with different surfactants added suggested that the surfactants
played an important role in the growth of WS2 -NS. When using cetyltrimethy-
lammonium bromide as a surfactant, WS2 presented a sheet-like structure. Fur-
thermore, a possible growth mechanism was proposed to explain the formation of
WS2 -NS. Considering the simple synthetic process and thinness of WS2 -NS, we
believe this work will open an avenue for industrial production of WS2 -NS.

Funding
This work was supported by the National Natural Science Foundation of China under Grant
No.51272110, 51772160.
30 D. ZHANG ET AL.

References
1. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang et al., Electric field effect in
atomically thin carbon films, Sci. 306 (5696), 666–9 (2014).
2. K. S. Novoselov, D. Jiang, F. Schedin, T. J. Booth, V. V. Khotkevich et al., Two-dimensional
atomic crystals, Proc. Natl. Acad. Sci. U S A. 102 (30), 10451–3 (2005).
3. C. Lee, Q. Li, W. Kalb, X. Z. Liu, H. Berger et al., Frictional characteristics of atomically thin
sheets, Sci. 328 (5974), 76–80 (2010).
4. J. W. Seo, Y. W. Jun, S. W. Park, H. Nah, T. Moon et al., Two-dimensional nanosheet crystals,
Angew. Chem. Int. Ed. 46 (46), 8828–31 (2007).
5. B. K. Miremadi and S. R. Morrison, The intercalation and exfoliation of tungsten disulfide,
J. Appl. Phys. 63 (10), 4970–4974 (1988).
6. R. A. Gordon, D. Yang, E. D. Crozier, D. T. Jiang, and R. F. Frindt, Structures of exfoliated
single layers of WS2 , MoS2 , and MoSe2 , in aqueous suspension, Phys. rev. b. 65 (12), 125407
(2002).
7. X. Huang, Z. Yin, S. Wu, X. Qi, Q. He, Q. Zhang et al., Graphene-based materials: synthesis,
characterization, properties, and applications, Small 7 (14), 1876–1902 (2011).
8. R. Bhandavat, L. David, and G. Singh, Synthesis of surface-functionalized WS2 nanosheets
and performance as li-ion battery anodes, J. Phys. Chem. Letters. 3 (11), 1523–1530 (2012).
9. Z. Zeng, Z. Yin, X. Huang, H. Li, Q. He, G. Lu et al., Single-layer semiconducting nanosheets:
high-yield preparation and device fabrication, Angew. Chem. 50 (47), 11093–7 (2011).
10. D. J. Late, Temperature dependent phonon shifts in single-layer WS2 , ACS. Appl. Mater. &
Interfaces. 6 (2): 1158–1163 (2014).
11. R. J. Smith, P. J. King, M. Lotya, C. Wirtz, U. Khan, S. De et al., Large-scale exfoliation of
inorganic layered compounds in aqueous surfactant solutions, Adv. Mater. 23 (34), 3944–8
(2011).
12. T. Ye, H. E. Tian, S. Jing et al., Synthesis of MoS2 layered material by hydrothermal method
and its structural characterization [J], Acta. Chim. Sinica. 62 (18): 1807–1810 (2004).
13. C. Pacholski, A. Kornowski, and H. Weller, Angew. Chem. Int. Ed. 41, 1188–9 (2002).
14. M. Niederberger and H. CÖlfen, Phys. Chem. Chem. Phys. 8, 3271–87 (2006).
15. S. Cao, T. Liu, S. Hussain et al., Hydrothermal synthesis of variety low dimensional WS2 ,
nanostructures[J], Mater. Letters. 129 (1):205–208 (2014).
16. J. P. Ge, W. Chen, L. P. Liu, and Y. D. Li, Chem. Eur. J. 12, 6552–8 (2006).