EFFECT OF SONICATION TIME ON

OPTICAL PROPERTIES OF LIQUID

EXFOLIATED MOS2

Submitted by,

AARATHI KRISHNA G
Indian Institute of Science Education and Research
Tirupati
Tirupati – 510571, India

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CERTIFICATE FROM THE SUPERVISOR
This is to certify that the work contained in this project report entitled “Effect of
sonication time on optical properties of liquid exfoliated MoS 2” submitted by
Aarathi Krishna G to Indian Institute of Science Education and Research,
Thiruvananthapuram towards partial requirement of Summer Internship 2019 has
been carried out by her under my supervision and that it has not been submitted
elsewhere for the award of any degree.

Thiruvananthapuram – 695551 Dr. Bikas Chandra Das

July 2019 Project Supervisor

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DECLARATION
I hereby declare that the work contained in this project entitled “ Effect of
sonication time on optical properties of liquid exfoliated MoS2” was carried out
by me under the supervision of Dr. Bikas Chandra Das, Assistant professor, School
of Physics, Indian Institute of Science Education and Research, Thiruvananthapuram
towards partial requirement of Summer Internship 2019. In keeping with the
general practice of reporting the scientific observations, due acknowledgement has
been made whenever the work is based on the findings of other investigations. The
contents of the report have not been submitted and will not be submitted elsewhere
for the award of any internships or degree or diploma.

Thiruvananthapuram- 695551 Aarathi Krishna G

July 2019

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ACKNOWLEDGEMENTS
There are many people to thank for their love and support during the last two months
who made my life easier in IISER TVM.
First of all, I thank Dr. Bikas Chandra Das, Assistant Professor, School of Physics,
IISER TVM for his kind and patient guidance during the project period.
I would also like to thank all PhD students for their guidance and help. Thank you,
Litty, Anju, Krishna, Navnith, Sandhya and Anubhav.
I extend my gratitude to my lab mates Nikhil and Mohammed Yaseen for their
support and help.
Thank you all.

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Contents
CERTIFICATE FROM THE SUPERVISOR ..........................................................2

DECLARATION .......................................................................................................3

ACKNOWLEDGEMENTS .......................................................................................4

CHAPTER 1 ..............................................................................................................6

1.1 TRANSITION METAL DICHALCOGENIDES .............................................6

1.1.1 MOLYBDENUM DISULPHIDE………………………………………..7

1.1.2 SYNTHESIS TECHNIQUES.....................................................................7

CHAPTER 2 ..............................................................................................................9

2.1 LIQUID PHASE EXFOLIATION OF MoS2 ..................................................9

2.1.1 CHEMICALS AND MATERIALS ...........................................................9

2.1.2 SYNTHESIS PROCEDURE ......................................................................9

2.1.3 PROBE SONICATION ..............................................................................9

2.2 SPECTROSCOPY TECHNIQUES ................................................................10

2.2.1 UV-VIS SPECTROSCOPY .....................................................................10

CHAPTER 3 ...........................................................................................................11

3.1 CHARACTERIZATION OF MoS2 SAMPLE ...............................................11

3.1.1 UV-VIS SPECTROSCOPY .....................................................................11

CONCLUSION ........................................................................................................15

REFERENCES.........................................................................................................16

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Chapter 1
INTRODUCTION

1.1 TRANSITION METAL DICHALCOGENIDES

Two-dimensional metal dichalcogenides especially MX2 (M=Mo, W etc. and X=S, Se, Te) have
attracted much interest because of its laminar graphene-like packing structure and also of its
versatile optical and electrical properties.1 Discovery of graphene has attracted many researchers
to 2D nanomaterial studies. Interesting properties have been observed when graphite is reduced to
its 2D counterpart graphene due to quantum confinement effects. But its application in the field of
electronics is reduced due to its zero band gap energy. Here comes the importance of transition
metal dichalcogenides which has a sizeable band gap, semiconducting characteristics and large
surface area. Structurally TMDs are layered where one layer of M atoms are sandwiched between
two layers of X atoms and also having strong covalent interactions in the plane and weak van der
Waals interaction between two layers.2 Furthermore, the TMDs exhibit indirect band gap to direct
band gap transition with a decreasing number of layers.3 The band gaps are also tunable with layer
thickness. It has potential application in the field of catalysis,4 energy storage,5 sensing 6
and
electronics.

Figure 1: Atomic structure of TMDs, bulk and monolayer. T=Mo,W and X=S, Se

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1.1.1 Molybdenum Disulphide(MoS2)
Molybdenum Disulphide films fabricated by liquid exfoliation methods have significant potential
for various applications. Due to the widespread in nature as Molybdenite, MoS2 has been one of
the most studied transition metal dichalcogenides. In the single layer of MoS 2 film, Mo(+4) and
S(-2) are arranged to a sandwiched structure by covalent bonds in a sequence of S-Mo-S whereas
the sandwiched layers are interacted by relatively weak van der Waals interaction. Generally, each
layer has a thickness of 0.65nm. The band gap varies from 1.23 eV in bulk to 1.8 eV in
monolayers.9 High concentration dispersions of few to monolayered MoS2 in N-Methyl
Pyrrolidone can be obtained by liquid phase exfoliation. For MoS2, the surface tension of NMP
(40 mJ/m2) is similar to estimated surface energies of few-layered MoS2 (46.5 mJ/m2). Mechanical
agitation via probe sonication is then sufficient to overcome the van der Waals interaction between
the layers and suspend the TMDs in the solvent.10

Figure 2: 1T, 2H and 3R structure of MoS2

1.1.2 SYNTHESIS TECHNIQUES

Exfoliation can be achieved mechanically using the scotch tape method which gives pure and clean
flakes, but the yield is low. Liquid phase exfoliation techniques are used to produce monolayers
on a large scale. Solvents like NMP, ethanol, water, DMF are mainly used for exfoliation. The
surface tension of a suitable solvent should match the surface energy of the TMD. Adding ionic
species like perchlorate or Li-ion enhances the exfoliation as well as increases the electronic
conductivity of the sheets.8The obtained will be mostly monolayers and is considered as an
efficient way of producing monolayers.

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 a b

c
Figure 3: a) Scotch tape method b) Liquid phase exfoliation c) Li-intercalated exfoliation

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CHAPTER 2
EXPERIMENTAL DETAILS
In this chapter, all experimental techniques related to this report will be explained in detail for the
synthesis of liquid exfoliated MoS2 and as well as their optical characterizations.

2.1 LIQUID PHASE EXFOLIATION OF MoS2

2.1.1 CHEMICALS AND MATERIALS

Molybdenum Disulphide (MoS2) and N-methyl Pyrrolidone (NMP, 99%) were purchased from
Sigma-Aldrich and all the chemicals were used as received without further purification.

2.1.2 SYNTHESIS PROCEDURE

To synthesize liquid exfoliated MoS2, we used MoS2 powder and N-Methyl Pyrrolidone as the
solvent.

2.1.3 PROBE SONICATION

2 mg/ml MoS2 solution was prepared by adding 120 mg MoS2 powder in 60 ml NMP. MoS2
dissolved in NMP was a dark grey solution. Then the solution was probe sonicated with a 13 mm
flat tip operating at 750W for different time intervals. The temperature was set to 5 0c. After
sonication, the solution was kept untouched for 24 hrs for the bulk particles to settle down. The
dark grey supernatant was pipetted out and centrifuged at 4000rpm for 45 min at room temperature.
The light yellow supernatant was pipetted out which contains exfoliated MoS2 in NMP. The dark
grey sediment which is the bulk is discarded.

Figure 4: Process of Exfoliation via sonication followed by centrifugation.

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2.2 SPECTROSCOPY TECHNIQUES

2.2.1 UV-VIS SPECTROSCOPY

Electronic UV-VIS absorption spectra of the exfoliated MoS2 in NMP was recorded with a
PerkinElmer LAMBDA 950 UV/VIS/NIR spectrophotometer. Before taking the absorbance of the
sample the baseline correction was done using NMP. The instrument measures the intensity of the
beam passing through the sample (I) and compares it with the intensity of the reference beam(I0).
The absorbance of light by the molecules is based on the Beer-Lambert law,

𝐼0
𝐴 = 𝑙𝑜𝑔 ( ) = 𝜖𝑏𝑐
𝐼

where ϵ is the molar absorptivity with units of L mol - 1 cm - 1, b is the path length of the sample in
centimetres and c, the concentration of a given solution expressed in mol L – 1.

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CHAPTER 3
RESULTS AND DISCUSSIONS
The results of the experiment conducted are listed in the following section. Different optical
properties are studied by different spectroscopic studies.

3.1 CHARACTERIZATION OF MoS2 SAMPLE

3.1.1 UV-VIS SPECTROSCOPY

Absorption spectra were taken of all MoS2 solutions sonicated for different time intervals. The two
peaks between 600 and 700 nm in the spectrum indicate successful exfoliation of MoS2. These
peaks arise from the direct gap transitions at the K point of the Brillouin zone.11 The two peaks
with little energy difference are due to the spin-orbital splitting of the valence band.12 Additional
peaks at 440 nm are attributed to the optical transition between the density of states peaks in the
valence band and conduction bands.11 In the 1 hr sonicated sample, these peaks are absent,
indicating the absence of exfoliated sheets. Figure 5 is in good agreement with the reported
absorption spectra of nanosheets synthesized via other sonication methods.11 The spectrum is
characterised by mainly four peaks, the details of which is given in Table 1.

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Figure 5: UV-VIS absorbance spectra of exfoliated MoS2

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 Sonication Peak1(nm) Peak 2(nm) Peak 3(nm) Peak 4(nm)
time(hr)
1 - 434 - -
6 379 435 609 670
9 380 437 610 672
12 385 441 613 675
15 384 436 611 670
18 383 435 610 669
21 382 434 608 668
24 381 431 607 667
Table 1: Peak positions in the absorption spectrum

(a) (b)
Figure 6: a).Redshift of the peaks as sonication time increases. b) Blue-shift of the peaks from 15 hr
sonicated sample onwards

As we increase the sonication time, we can see a red shift in all four peaks. However, after 12
hours sonication time, all the peaks shift to shorter wavelengths.(Figure:7). The first peak at long
wavelength corresponds to the lowest optical bandgap of 1.8 eV higher than the corresponding
bulk value of 1.2 eV. Increase in bandgap is a clear indication of quantum confinement in
nanosheets.11

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Figure 7: Peak shift v/s Sonication time graph for all 4 characteristic peaks.

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CONCLUSION
In summary, MoS2 was exfoliated from the bulk via probe sonication for different time
intervals, and the optical properties were studied by UV-VIS Spectroscopy with changing time. In
the 1 hr sonicated sample, the characteristic peak of MoS2 monolayer was absent because of not
providing a sufficient amount of time required for successful sonication. From 6 hrs sonication
time samples onwards we can see the two characteristic peaks between 600 and 700 nm, which
corresponds to the direct transition between valence and conduction band. As the sonication time
increases, first all the peak shift to longer wavelengths. However, from 12 hrs sonicated sample
onwards, they shift to shorter wavelengths. More optimization is required for device fabrication.

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Chim, Giulia Galli, Feng Wang, Emerging Photoluminescence in Monolayer MoS2. Nano
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Materials (Basel)(2017).
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Umar Khan, Karen Young, Alexandre Gaucher, Two-Dimensional Nanosheets Produced
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(2011).
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