Optical and Microstructural Study

of Wide Band Gap ZnO@ZnS

Core–Shell Nanorods to be Used as Solar
Cell Applications

Peeyush Phogat , Shreya , Ranjana Jha , and Sukhvir Singh

Abstract Recently core–shell types of particles are found to be used for the improve-
ment of semiconductor efficiency, information storage, optoelectronics, catalysis
and quantum dots, etc. ZnS and ZnO are II–VI group semiconductors with a wide
band gap. Both materials show prominent applications in photocatalytic activity and
solar cells. In the present investigations an effort has been made to synthesize Zinc
Oxide@ Zinc Sulfide core–shell by a facile water bath route. X-ray diffraction data
revealed the presence of ZnO in high percentage with small amount of ZnS phase.
W–H plot and size–strain plot was used to evaluate the crystallite size and strain
for the as synthesized material. UV–Vis spectroscopy technique was used to record
the absorption. On analysis of absorption data revealed a band gap of 3.2 eV and
refractive index of 2.34 for the material. Microstructural investigations carried out
by TEM show rod and oval shaped core–shell particles having average particle size
with a length of 250 nm and breath of 150 nm. The shell thickness estimated from
TEM image is about 25 nm. Elemental compositional analysis of the as synthesized
material depicted the presence of zinc, oxide and sulfide.

Keywords Core–shell · Microstructure · Band gap · Refractive index

1 Introduction

The key to reach the source of unlimited power is renewable energy. One of the
promising aspects for unlimited energy is solar energy. Researchers are doing tremen-
dous amount of work to create a material which can provide us with optimal output
[1–3]. Novel material like Zinc Oxide (ZnO) Molybdenum di-sulfide (MoS2 ) and
Zinc Sulfide (ZnS) are good examples for solar materials [4, 5]. The problem we
face with novel materials was that they had higher photo exciton energy than there
nanocomposite counterparts [6]. Nanocomposite materials such as a core–shell have

P. Phogat · Shreya · R. Jha · S. Singh (B)

Research Lab for Energy Systems, Department of Physics, Netaji Subhas University of
Technology, Dwarka, New Delhi 110078, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 419
B. Sethuraman et al. (eds.), Recent Advances in Mechanical Engineering, Lecture Notes
in Mechanical Engineering, https://doi.org/10.1007/978-981-99-2349-6_38
420 P. Phogat et al.

solved that problem. Core–shell nanomaterials are the type of materials in which one
of the materials (core) is covered by another material (shell) and they form a layered
structure. Core–shell nanoparticles (CSNs) are a class of nanostructured materials
that have recently received increased attention owing to their interesting properties
and broad range of applications in catalysis, biology, materials chemistry and sensors.
In core–shell particles-based drug delivery systems either the drug can be encapsu-
lated or adsorbed onto the shell surface. The shell interacts with the drug via a
specific functional group or by electrostatic stabilization method. When it comes
in contact with the biological system, it directs the drug. In the present investigations
an effort has been made to study the parameters of these core–shell nanoparticles
for their further use in solar cell applications. With high surface to volume ratio and
low photo exciton energy level they became the new face of nanocomposites [7, 8].
For the application of solar energy ZnO and ZnS are proved to be good for anode
materials [9, 10]. ZnO is a semiconductor with a band gap of 3.37 eV. The novel
material show applications like piezoelectric, water splitting and solar cells [11, 12].
ZnS is also a semiconductor with a band gap of 3.54 eV. ZnS shows applications
in light emitting diode (LED’s), catalyst, anode material for solar cells, water waste
treatment and water splitting applications [13, 14]. Both ZnO and ZnS exhibits two
main structures, one of them is cubic in nature and known as zinc blend. The other one
is called wurtzite which is hexagonal in structure. Core–shell materials are preferred
over any other due to their property of high surface area and higher stability [15–17].
By adding a shell to a material it improves thermal stability and dispersibility of
core material [18]. ZnO@ZnS core–shell structures have already been studied for
their property of water splitting, photocatalytic application and hydrogen production
mainly [19, 20]. They show enhanced UV absorbance and many dye studies have
been performed on this unique material [16, 21]. Earlier studies revealed that the
core–shell nanomaterials synthesized using this technique show the formation of
dense shells [22], however the present study shows the formation of porous nature of
shell which is better for Dye-Sensitized Solar Cells. As shell being porous, the mate-
rial will exhibit properties of core as well as the shell. The present study shows the
synthesis of ZnO@ZnS core–shell through facile stirring without inducing any other
impurities in the sample. The reaction through which core–shell are synthesized is
a sacrificial synthesis in which the core material sacrifices its upper layer to create a
shell which is also called galvanic replacement [20]. Identification of phases of the as
synthesized material was carried out by using X-ray powder diffraction (XRD) tech-
nique. Crystallite size and strain were calculated through Debyes Scherrer formula
and W–H plot, respectively. Optical properties and the band gap of the sample were
investigated using UV–Vis Spectroscopy. Microstructural study was done by using
transmission electron microscopes (TEM). Elemental compositional analysis was
carried by using energy dispersive spectrometer, an attachment to TEM.
Optical and Microstructural Study of Wide Band Gap ZnO@ZnS … 421

2 Core–Shell Particles Synthesis

2.1 Chemicals Used for Synthesis

ZnO nanopowder of particle size in the range 10–30 nm with purity of 99.5% procured
from M/s Nanoshel. Sodium sulfide (Na2 S) was procured from M/s THOMAS
BAKER. Distilled water of 15Mega-Ohm resistance was used for cleaning and
synthesis purpose. All the solutions were prepared in distilled water only. Absolute
ethanol was used for cleaning and washing only.

2.2 ZnO@ZnS Core–Shell Preparations

ZnO nanopowder was dispersed in distilled water to make a solution of 0.5 M

(4.17 gm/100 ml). The solution was given a water bath at a temperate of 60 °C.
Simultaneously a solution of sodium sulfide was prepared with a molarity of 0.1 M
(4 gm/50 ml). Both the solutions were stirred using magnetic stirrers for one hour.
For core–shell formation the Na2 S solution was transferred to ZnO solution with the
help of a burette. The drop rate must be as slow as possible for regular core–shell
formation. The mixture was further stirred for four and half hours in a water bath
maintained at a temperature of 60 °C. Further the mixture was allowed to cool to room
temperature naturally followed by filtration using Whatman filter paper. Filtration
and washing was done three times with distilled water and three times with absolute
ethanol. Later on the sample was dried in a vacuum oven maintained at 600 mm of
Hg and a temperature of 120 °C. It was then allowed to cool overnight and ground
till fine powder was obtained.

3 Material Characterization

3.1 Instruments Specification

For XRD analysis X-ray diffractometer of PANalytical model X’pert PRO was
used in 2θ range of 10°–90° with Copper (Cu) Kα-radiation of λ = 1.5406 Å. For
optical analysis SHIMADZU UV-2600i, UV–Vis Photo spectrometer was used in
the source light range of 850–190 nm. Microstructural analysis was done on High
Resolution-Transmission Electron Microscopy (HR-TEM) with an attachment of
EDX of TALOS (THERMO SCIENTIFIC).
422 P. Phogat et al.

3.2 Result and Discussion

X-ray Diffraction Analysis. The as synthesized powder was analyzed through X-

ray diffractometer for the structure and phase identification. The raw data of XRD
was analyzed using Xpert High Score Plus software. Further data was smoothed by
low pass filter to remove any data below baseline. By setting peak intensity at three,
a total of fifteen peaks are identified. All the peaks are matched to two ICDD cards.
ZnO was matched to 98-009-4004 file where as ZnS was matched to standard file
98-005-2223. ZnO was identified as major phase for the material whereas sphalerite
(mineral name of ZnS) was found to be in very low percentage. Figure-1 represents
the XRD pattern of the as synthesized composite where in ZnO peaks are coded in
blue color and ZnS is coded with light green. After Rietveld refinement done on
the data, the hkl value identified as (010), (002), (011), (012), (110), (013), (020),
(112), (021), (004), (022), (014) and (023) were found to be matched with ZnO phase
having hexagonal structure. Some of the reflections in the XRD data which are coded
with green color found to be matched with the ZnS phase having cubic structure. The
XRD data revealed the formation of nanocomposite material in the form core–shell
morphology having two phases (Fig. 1).
Crystallographic parameters are known for ZnO and ZnS through ICSD data cards
but also determined for the as-synthesized material by using formula-

1 h2 k2 l2
For Cubic = + +
d2 a2 b2 c2
( )
1 4 h 2 + k 2 + hk l2
For Hexagonal 2 = 2
+ 2
d 3 a c

where d is interplaner-spacing in angstrom, hkl are planes and a, b, c are the lattice
parameters which are to be determined. Crystallographic parameters of both materials
can be seen Table 1.

Fig. 1 Rietveld analyzed data showing hkl values for ZnO@ZnS core–shell
Optical and Microstructural Study of Wide Band Gap ZnO@ZnS … 423

Table 1 Crystallographic parameters

Parameters ZnO(98-009-4004) ZnS(98-005-2223) As-synthesized ZnO@ZnS
a (Å) 3.2470 5.3830 ZnO = 3.2436, ZnS = 5.3723
b (Å) 3.2470 5.3830 ZnO = 3.2436, ZnS = 5.3723
c (Å) 5.2030 5.3830 ZnO = 5.1983, ZnS = 5.3723
Alpha (°) 90.0000 90.0000 ZnO = 90.0000, ZnS = 90.0000
Beta (°) 90.0000 90.0000 ZnO = 90.0000, ZnS = 90.0000
Gamma (°) 120.000 90.0000 ZnO = 120.000, ZnS = 90.0000

Crystallite Size and Strain. The XRD peaks thus obtained are signature of
different parameters such as crystallite size, micro strain and peak broadening.
Crystallite size was calculated by using well-known Debye Scherrer equation as
mentioned
Kλ
D=
βCosθ

where K is 0.9 and known as Scherrer constant, λ is the wavelength of X-ray source
(0.15406 nm), θ is known as Braggs angle and β is the value for Full Width at
Half Maximum, i.e., FWHM. Using these values average crystallite size (D) of this
particular material was calculated and found to be about 61 nm.
Williamson-Hall plot was used to find the size and strain of the material. As the
broadening of peak (can be denoted by β T ) is due to the effect of crystallites size
(β D ) and secondly on micro strain (β E ). Equation given below was used to calculate
crystallite size and micro strain.

Kλ
βT Cosθ = (ε × 4Sinθ ) +
D
where broadening of peak is given as βT, θ is known as Bragg’s angle, ε is average
lattice strain, K given by 0.9 and λ is the wavelength of XRD source also given
as 0.15406 nm. As from the equation we can compare slope and intercept (given in
Fig. 2) to find strain and crystallite size. The slope represents the strain in the material
and being negative it represents compression which is 0.00275. As for crystallite size
we compare intercept with Kλ/D to calculate D which comes to 16.5 nm which is
for the ZnS material as shell material crystallite size is very small for the material.
Crystallite size and lattice strain were calculated using size–strain plot (Fig. 3)
in which it is stated that profile is illustrated by strain through Gaussian function
and Crystallite size through Lorentzian function. The equation for size–strain plot is
given below.

Kλ ( 2 ) ∫2
(dhkl × βhkl × Cosθ )2 = × dhkl × βhkl × Cosθ +
t 4
424 P. Phogat et al.

Fig. 2 William-Hall plot for ZnO@ZnS core–shell

Fig. 3 Size–strain plot for ZnO@ZnS core–shell

The slope was equated to Kλ/t to calculate t which is average crystallite size.
The average crystallite size was found to be 66.9 nm. Whereas strain was calculated
by equating intercept to ε2 /4 which for the as synthesized material is 0.002158. As
synthesized powder was analyzed through X-ray diffractometer for the structure and
phase identification. The raw data of XRD was analyzed using Xpert High Score Plus
Optical and Microstructural Study of Wide Band Gap ZnO@ZnS … 425

software. Further data was smoothed by low pass filter to remove any data below
bas.
UV–Visible Spectroscopy (UV–Vis). UV–Vis spectroscopy is done through
diffusion reflectance spectroscopy (DRS), in which reflectance data is recorded in
the range of 850–190 nm. Using from Kubelka Munk theorem absorbance graph
was acquired. Figure 4a shows five absorbance peaks at 199.5, 204.5, 209, 306.5
and 362.5 nm. Among the five peaks, absorbance at 362.5 nm found to be maximum
showing that material has a potential for solar cell applications. For visible region
absorbance, a dye may be used with as synthesized ZnO@ZnS material to be appli-
cable in solar cell applications [22]. Tauc Plot of the as synthesized material was
plotted and band gap was calculated through linear fit as shown in Fig. 4b.
| |1
αhυ = A hυ − E g n

where A = Absorbance (a.u); α = Molecular extinction coefficient; h = plank’s

constant, υ = λ (wavelength)/c (speed of light), E g = Band Gap n = ½ (direct band
gap), 2(indirect band gap). The as synthesized material shows a band gap of 3.2 eV
as depicted in Fig. 4b, which is found to be lower than both of the individual novel
materials.
Refractive Index. Refractive index being an important part of the material prop-
erty as this show how velocity changes in that material. Refractive index is inversely
proportional to wavelength, higher the refractive index better for solar cell applica-
tion. To evaluate refractive index of as-synthesized material given below equation
was used.
/
n2 − 1 Eg
=1−
n +1
2 20

The as synthesized ZnO@ZnS care shell material showed a refractive index of

2.34. The reported refractive index of ZnO is 2.02, whereas for ZnS it is 2.36. The
as synthesized material has revealed the refractive index higher than that of ZnO and
close to ZnS.
Microstructural Analysis. Detailed microstructural features analysis of the as
synthesized material was carried out by using HR-TEM. TEM image shows the
presence of core–shell formation of the ZnO@ZnS material as depicted in TEM
images (Fig. 5a, b and c). Majority of the particles were found to be in nano rod
shapes however some irregular shape particles are also seen in the TEM image. The
shell formation was seems to be porous in nature but regular all along the core surface.
Figure 5b revealed the particle size of the order of 250 nm length and 150 nm in
width, in Fig. 5c shell thickness was observed in the range of 25 nm comparable to
the W–H plot data. Figure 5d shows the selected area electron diffraction pattern of
the corresponding area of the material revealing polycrystalline nature of the material
with the presence of both ZnS and ZnO phase. Figure 5e shows the high resolution
TEM image depicting the lattice fringes having d spacing of both core and shell
426 P. Phogat et al.

Fig. 4 a Absorbance data for ZnO@ZnS, b Tauc Plot for ZnO@ZnS

material which revealed that the core material is ZnO and shell material is ZnS.
TEM and HR-TEM images confirmed the formation of core–shell structure of the as
synthesized material ZnO@ZnS. Elemental compositional analysis of the same area
of material was carried out by using Energy Dispersive Spectrometer (EDS) which
showed the presence of zinc, oxygen and sulfur as depicted in Fig. 5f. Presence of
Optical and Microstructural Study of Wide Band Gap ZnO@ZnS … 427

a b c

200nm 50nm
100nm

d e f

Counts
2.00 1/nm 5nm
Energy(keV)

Fig. 5 a TEM image showing core–shell ZnO@ZnS b TEM image depicting porous shell around
the core at higher magnification. c TEM image showing shell thickness of ZnO@ZnS; d SEAED
pattern for ZnO@ ZnS, e high resolution TEM showing lattice fringes of core and shell of
ZnO@ZnS, f EDX pattern of core–shell ZnO@ZnS

oxygen along with zinc showed the presence of ZnO, whereas presence of sulfur
showed the ZnS existence which was also revealed in XRD pattern above.

4 Conclusion

ZnO@ZnS core–shell nanoparticles were synthesized using facile water bath route
for low cost synthesis. X-ray diffraction analysis reveals the presence of ZnO phase in
majority and ZnS in lower percentage. Crystallite size of the as synthesized material
was calculated using Debye–Scherrer equation; William-Hall plot and size–strain
plot revealed the crystallite size of the order 60–70 nm. The strain value was calcu-
lated and found to be 0.0025 approx. UV–Vis spectroscopy measurements showed
absorption in UV region with absorption peak at 362.5 nm and a band gap of 3.2 eV.
The refractive index of the as synthesized material was found to be 2.34. Microstruc-
tural investigation carried out using TEM shows core–shell formation with nanorods
morphology with a particle size of approx. 250 nm in lengths and 150 nm in breadth.
The shell thickness of the material was estimated nearly 25 nm. SEAD pattern confirm
the presence of ZnO and ZnS having polycrystalline nature. Elemental compositional
analysis of the material showed the presence of zinc, oxide and sulfur only. This study
of ZnO@ZnS core–shell material may be useful as anodic material for solar cells.
428 P. Phogat et al.

The material can also be used with organic dyes for Dye-sensitized solar cell (DSSC)
applications.

Acknowledgements We are thankful to honorable Vice-Chancellor, Netaji Subhas University of

Technology, Delhi, India for providing the essential resources for this research.

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Elevated Refractive Index of MoS2
Amorphous Nanoparticles
with a Reduced Band Gap Applicable
for Optoelectronics

Shreya , Peeyush Phogat , Ranjana Jha , and Sukhvir Singh

Abstract The present work reports the synthesis of MoS2 nanoparticles via a facile
ultrasonication-assisted hydrothermal route. The presence of 2-H hexagonal phase
of MoS2 is analyzed by XRD which shows diffused and broad pattern revealing the
low crystallinity of the synthesized sample. The crystallite size as calculated using
different methods like Debye Scherrer equation, Williamson-Hall (W-H) and size
strain plots comes out to be around 140 nm and the strain is negative which shows
the compression in the material. The optical studies carried out by UV–vis shows
the absorbance in UV and visible region. Absorbance data revealed the band gap of
0.9 eV and refractive index of 3.48. The high value of the refractive index makes
it a promising candidate for optoelectronic applications. FESEM images shows the
aggregation of MoS2 sheets formed in pebble like particles of micron sizes. Elemental
compositional analysis of the corresponding area of the sample revealed the presence
of Mo and S. TEM images also revealed the aggregation of thin sheets and selected
area electron diffraction pattern (SAEDP) shows the amorphous nature of the as-
synthesized materials which is also in good agreement with the XRD data.

Keywords Molybdenum disulphide · Hydrothermal method · Ultrasonication ·

Refractive index · Microstructure

1 Introduction

The synthesis of two-dimensional graphene in 2004 is a breakthrough in the synthesis

of 2-D materials before which it was believed that 2-D materials are not stable [1].
Since then, it is exploited to find applications in diverse fields [2, 3]. And rightly,
it changed the scenario of the electronics industry which further put the world in a
digital race. However, the zero band gap in graphene created a gigantic issue while
learning its usage in some applications like switches and others [4]. This limitation

Shreya · P. Phogat · R. Jha · S. Singh (B)

Research Lab for Energy Systems, Department of Physics, Netaji Subhas University of
Technology, Dwarka, New Delhi, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 431
B. Sethuraman et al. (eds.), Recent Advances in Mechanical Engineering, Lecture Notes
in Mechanical Engineering, https://doi.org/10.1007/978-981-99-2349-6_39
432 Shreya et al.

of graphene baffled scientists and they try to find a solution to the above problem.
Initially, numerous efforts have been made to increase the bandgap of graphene
layers but changing its bandgap changed its properties as well, which doesn’t solve
the problem [5, 6]. Then, transition metal dichalcogenides (TMDs) comes into the
picture as analogous materials with the semiconducting property and the exploration
of their applications in different fields including sensing, electronics, optical and
others starts.
TMDs are materials that have thickness comparable to graphene along with excep-
tional semiconductor properties. TMD layers consist of metal atoms, such as Molyb-
denum or Tungsten which is stuck between two layers of chalcogen atoms. The adja-
cent layers are bound together very weakly and thus layers can slide over each other
[7, 8]. This is the reason, why these materials are widely used for solid lubrication
too. They have hexagonal structures, which resemble the graphene. TMD monolayers
have direct bandgap [9, 10]. While for multilayer TMD, like bilayer or trilayer, the
bandgap is indirect. Thus, there is a need to separate monolayers from bulk.
MoS2 (as shown in Fig. 1) is vastly explored TMD due to its exceptional properties.
It has a 2-D layered structure similar to graphene. It has two possible structural forms,
2-H and 1-T in which 2-H shows semiconducting behavior. It shows cyclic stability
and has a high refractive index and thus a promising candidate for optoelectronic
applications [11]. A plenty of methods have been investigated in years to synthesize
MoS2 nanostructures including chemical vapor deposition (CVD), metal–organic
CVD (MOCVD), atomic layer deposition, vapor-phase synthesis, electrophoretic
deposition, solar ablation, etc. [12–15]. Most of these methods are expensive and
complex and thus the research of an inexpensive and simpler route is essential which
can give comparable high purity product. Our present work is devoted toward the
synthesis of 2-D MoS2 -based thin layers via economical and facile hydrothermal
route. The precursor solution is initially treated with ultrasonic waves for high reac-
tion rate and yield. The thin agglomerated sheets of MoS2 as formed show enhanced
refractive index which is generally found to be in the range 0.5–3.3 [16] and thus it
is considerable for optoelectronic applications.

Fig. 1 A schematic diagram

of MoS2
Elevated Refractive Index of MoS2 Amorphous Nanoparticles … 433

Table 1 List of chemicals & reagents used for the synthesis

S. No. Chemical and material Company
1 Sodium molybdate dihydrate (Na2 MoO4 .2H2 O) Loba Chemie Pvt. Ltd.
2 Molybdenum oxide (MoO3 ) Loba Chemie Pvt. Ltd.
3 L-cysteine (C3 H7 NO2 S) Sigma-Aldrich

2 Experimental Section

2.1 Chemicals and Materials

The list of chemicals and materials used to synthesize MoS2 is reported in Table 1. All
chemicals and reagents are of analytical grade and used without further purification.

2.2 Synthesis of MoS2 Nanoparticles

MoS2 is synthesized via a facile one-step hydrothermal route. MoO3 (0.5 g) is

dissolved in 20 ml DI water by ultrasonication for 30 min. Na2 MoO4 .2H2 O (2 mM)
and L-cysteine (4 mM) are dissolved in DI water. After this, the later solution is added
dropwise to the former solution of MoO3 along with continuous ultrasonication and
the final solution is again ultrasonicated for 20 min. Finally, the solution is kept in
Teflon lined autoclave at 200 °C for 12 h. After this, it was left for naturally cooled
down and washed with DI and ethanol several times. After drying it for 18 h, the
sample is collected and characterized using different techniques.

3 Results and Discussion

3.1 Structural Analysis

The structural analysis of the as-synthesized material is carried out by X-ray diffrac-
tion technique (XRD) (PANalytical X’pert PRO facility) (Fig. 2). The diffused and
low-intensity broadened peaks indicate the low crystallinity and amorphous nature
of the material. The peaks are indexed to the hexagonal structure of MoS2 with ICDD
database 00-002-0132. The lattice parameters are calculated using the formula,

| ( )2 | 1
1 4( 2 ) 2 a
= h + k + hk + l
2
d2 3 c a2
434 Shreya et al.

Fig. 2 XRD pattern of MoS2 nanoparticles

Table 2 A comparison of
Lattice parameters ICDD database value Calculated value
calculated parameters of
MoS2 with standard values a (Å) 3.1500 3.0623
b (Å) 3.1500 3.0623
c (Å) 12.3000 17.0959
α (˚) 90 90
β (˚) 90 90
γ (˚) 120 120

where d is d-spacing, (hkl) are miller indices and a, b, c are lattice parameters.
A comparison of standard parameters with calculated values is presented in Table
2. The difference in the value of ‘c’ is due to the error in calculations because of
the amorphous nature of material and broad diffused XRD pattern. (002) and (100)
peaks correspond to the periodicity along the c- and a-direction, respectively. The
calculated values of lattice parameters confirm the nano-sized particles. Further, the
average crystallite size calculated using the Debye Scherrer equation is 147.5 nm.
Other methods utilized to estimate crystallite size and strain of the sample are
W-H and size strain plot (as shown in Fig. 3a and b). The intercept of the W-H plot
is 0.00103 and is used to calculate the crystallite size as per the following equation,

kλ
D=
intercept

where k = 0.9 and λ = 0.154 nm is the Scherrer constant and wavelength used to
irradiate the
( material,
) respectively. It gives the value of crystallite size as 134.6 nm.
The slope βcosθ
4sinθ
gives us the value of strain in the material which is −7.56 × 10−5 .
The negative sign in the strain value indicates the compression in the material.
The intercept and slope of the size strain plot are also used to calculate the
crystallite size and strain of the sample using the following relations,
Elevated Refractive Index of MoS2 Amorphous Nanoparticles … 435

Fig. 3 a Williamson-Hall plot b size strain plot

Table 3 A comparison of
Methods Crystallite size (nm) Strain, e (×10−4 )
crystallite size and strain
calculated using different Debye Scherrer 147.5 –
methods equation
Williamson-Hall 134.6 −0.756
plot
Size strain plot 138.6 −10.66

kλ
crystallite size, t =
slope
/
strain, e = 4 ∗ intercept

Thus, the crystallite size calculated using the above formula comes out to be
138.6 nm. Moreover, the strain in the sample is estimated as −10.66 × 10−4 . A
comparison of crystallite size and strain calculated using different methods is shown
in Table 3.

3.2 Optical Studies

The optical study of the sample is carried out by analyzing absorbance plot (as shown
in Fig. 4a) obtained by UV–vis spectrophotometer (Shimadzu 2600i). A significant
absorbance is observed in UV and visible regions which makes it a good candidate
for optoelectronic applications. The absorbance data is further evaluated to get the
Tauc plot according to the following relation,

αhν γ = A(hν − E g )
436 Shreya et al.

Fig. 4 a Absorbance graph of MoS2 nanoparticles b corresponding Tauc plot

where α is the absorption coefficient, h is Planck’s constant, ν is the frequency, γ

denotes the nature of electronic transition, i.e., direct or indirect, A is the proportion-
ality constant, and E g is the band gap of the material. The graph between hν and (α
hν)2 is used to estimate the optical band gap to be 0.9 eV (Fig. 4b).
Refractive Index. The refractive index of a material is an important factor in deter-
mining the efficiency of a device and thus, it is essential to determine the refractive
index of the material. The refractive index is estimated using the following relation.
/
n2 − 1 Eg
=1−
n2 + 2 20

Putting E g as 0.9 eV, the refractive index is found to be about 3.48. A high value
of refractive index makes it a suitable candidate for optoelectronic applications.

3.3 Morphological Analysis

Surface Morphology using FESEM. The morphological study of the as-synthesized

sample is carried out by using FESEM (make JEOL) operated at 20 kV at suit-
able magnifications and areas. Figure 5a–c represents the SEM images recorded
at different magnifications. Though the images show agglomerated and aggregated
nanostructures, the nanosheets can be identified on the surface of the pebble like
structures. This might be the effect of using no reducing agent. EDX pattern is
recorded to confirm the elemental composition of as-synthesized material, which
shows the high-intensity peaks of Mo and S as depicted in Fig. 5d. The presence of
other elements like carbon is due to carbon tape on which MoS2 was loaded during
SEM characterization and a small amount of oxygen may be due to the hydrothermal
process.
Elevated Refractive Index of MoS2 Amorphous Nanoparticles … 437

Fig. 5 a–c FESEM images at different magnifications d EDX pattern of the corresponding area of
the sample

Microstructural characterization using TEM. The microstructural features asso-

ciated with MoS2 were investigated by using TEM (TECNAI 200 kV) as shown in
Fig. 6a. TEM image shows the thin layered structure of MoS2 and the corresponding
selected area electron diffraction pattern shows the amorphous nature of the material
(Fig. 6b). It shows diffused rings with no spots, confirming the amorphous structure
as confirmed by XRD data also.

Fig. 6 a TEM image showing layered structure b corresponding SAED pattern

438 Shreya et al.

4 Conclusions

The MoS2 nanostructures are successfully synthesized via an ultrasonication-assisted

hydrothermal route. The ultrasonication treatment increases the synthesis rate and
yield of the product. XRD analysis shows the formation of the hexagonal phase of
MoS2 indexed to ICDD reference data 00-002-0132. The crystallite size as calculated
using the Debye Scherrer equation is found to about 147 nm. The crystallite size is
also calculated using W-H and size strain plot which comes out to be 134 and 138 nm,
respectively. The strain in the material is studied using W-H and size strain plot which
shows compression in the material of the order of 10–4 . Lattice parameters a, b and
c are also calculated which are 3.0623, 3.0623 and 17.0959 Å, respectively, and
are comparable to the ICDD database values. UV–vis studies show that MoS2 is
absorbing light in UV and visible regions. The absorbance data is used to calculate
the band gap using the Tauc plot and it comes out to be 0.9 eV. The refractive index
is also calculated using the band gap and it is found to be 3.48. The morphological
analysis is carried out by FESEM and TEM. FESEM images show the aggregated
layered structures and the EDX pattern shows high-intensity peaks of Mo and S.
The TEM image also shows the aggregated structure and the corresponding SAED
pattern shows diffused rings confirming the amorphous nature of the material. A high
refractive index of MoS2 makes it a suitable material for optoelectronic applications.

Acknowledgements The authors are thankful to the vice chancellor, NSUT for providing the
essential resources required for the research. One of the authors, Shreya is also thankful to him for
providing financial support during the research work.

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