Materials Science Forum Submitted: 2023-05-17

ISSN: 1662-9752, Vol. 1099, pp 119-125 Accepted: 2023-06-26

doi:10.4028/p-G1CCxq Online: 2023-10-05
© 2023 Trans Tech Publications Ltd, Switzerland

Impedance Study of Zinc Sulphide Quantum Dots via One Step Green
Synthesis
Peeyush Phogata, Shreyab, Ranjana Jhac and Sukhvir Singhd,*
Research Lab for Energy System, Department of Physics, Netaji Subhas University of Technology,
Dwarka, New Delhi-110078, INDIA
a
peeyush.phogat@gmail.com, bshreyasharma.aug15@gmail.com, cdrranjanajha@gmail.com,
d
sukhvirster@gmail.com

Keywords: Quantum Dots, Band Gap, Electrochemical Study, Green synthesis, Nyquist Plot.

Abstract. ZnS quantum dots were synthesized using green synthesis route which are cost effective
and eco-friendly. X-ray diffraction study revealed the formation of single phase ZnS. Crystallite
size and strain in the as synthesized material were calculated through Williamson-Hall and Size-
Strain plot. UV-Vis spectroscopy investigations revealed the absorption region and optical band gap
for the ZnS with refractive index analysis. Microstructural analysis of material was done using high
resolution transmission electron microscope (HRTEM) which confirms the presence of quantum
dots. Selected area electron diffraction pattern (SAEDP) of the corresponding area revealed the
polycrystalline nature of as synthesized ZnS with fine crystallites oriented along (111) and (022)
planes. Results of analysis of lattice fringe spacing’s of fine crystallites are found to be in good
agreement with SAEDP data. Elemental compositional analysis was carried by using EDS as an
attachment of TEM which showed the presence of Zinc and Sulphur only. Nyquist plot reported
Warburg impedance which suggests the material for solar cell applications.

Introduction
The advancement in solar cell technology with green synthesis is a promising and tenable approach
to solve energy catastrophe and environmental problems. Green synthesis being environmentally
friendly and eliminate toxic waste and use ecological solvent is one of the best sample preparation
method[1], [2]. Whereas quantum dots material shows unique properties from their larger counter
parts, such as change in band gap and particle size. Quantum dots show significant changes in
optical properties owing to their ability to work in IR region, longer lifetimes and high extinction
coefficient[3]–[7]. Zinc Sulphide (ZnS) is an II–VI semiconductor with a direct band gap of
3.6eV[8]. The reason for quantum dot synthesise is due to their unique property of band gap tune
ability, which is very helpful in solar application. ZnS is a known anode material for solar cells. The
material shows a variety of applications like piezoelectric, water splitting and photo catalysis[9]–
[11]. ZnS nano-structures show expansion in surface to volume ratio i.e., surface area increases and
decrease the interfacial recombination. Thin film of the material can be synthesized using various
techniques[12].
This present study highlights on the synthesis of ZnS quantum dots by green synthesis.
Identification of phase of ZnS was carried out by using X-ray powder diffraction (XRD). Optical
properties and the band gap of the sample was analysed using UV-Vis Spectroscopy.
Microstructural investigations are done by using transmission electron microscopes (TEM).
Electrochemical studies were carried out by using three electrode systems and working electrode is
prepared through spin coating.

Synthesis of Quantum Dots

Chemicals used for Synthesis: Zinc Oxide (ZnO) nanopowder was procured from SRL Chemicals.
Sodium sulphide (Na2S) was procured from M/s THOMAS BAKER and Distilled water of
15Mega-Ohm resistance from M/s ELIX Millipore for cleaning and synthesis. Absolute ethanol
was used only for cleaning and washing.

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications Ltd, www.scientific.net. (#625004867, Indian Inst. of Technology, Roorkee, India-09/10/23,10:26:54)
120 Dielectric, Semiconductive and Conductive Materials

Synthesis. Initially a solution of 0.122M was prepared for ZnO nanoparticles. After some time
the solution was placed in a water bath at a temperature of 60oC. Simultaneously Na2S solution of
0.341M was stirred at room temperature. After some time Na2S solution was transferred to ZnO
solution drop wise. The mixture was then stirred for next four hours with water bath maintained at
60oC. The mixture was centrifuged at 8000RPM and washed with distilled water and ethanol. The
sample was then dried in vacuum at a temperature of 70oC.
Preparation of Working Electrode. Working electrode of ZnS film was made on a FTO
(Fluorine doped tin oxide) glass slide. It was prepared by spin coating with a spinning cycle of 40
seconds at 2000RPM. After one cycle, the film was heated at 70°C for 5 min. The spinning to
preheating procedure was repeated for fifteen cycles to get suitable thickness for impedance study.

Material Characterization
X-Ray Diffraction Analysis. X-ray diffraction (XRD) analysis was carried out using x-ray
diffractometer (make: PANalytical model X'pert PRO). X-ray diffraction pattern was recorded in
the 2θ range of 10o to 90o with Copper (Cu) Kα-radiation (λ=1.5406 Å). XRD data showed
characteristics of single phase ZnS material with (111), (002), (022), (113), (222), (004), (133),
(024) and (224) planes. Raw data was an exact match for ICDD card no: 01-077-2100. The
diffraction pattern revealed cubic crystal structure of as-synthesized material. All the reflection
peaks in the diffraction data found to belongs to ZnS only suggesting high purity synthesis of ZnS
through green synthesis. Lattice parameter, a, of the as synthesized ZnS have been calculated as
a=5.3483Å using equation (1) which is found to be close with the standard crystal parameter of ZnS
as a =5.4145Å as specified ICDD file. This shows that there is little shifting from standard values.
1 ℎ2 𝑘𝑘 2 𝑙𝑙2
𝑑𝑑2
= 𝑎𝑎2 + 𝑏𝑏2 + 𝑐𝑐 2 (1)
Where d represents the interplaner spacing and a,b,c are crystal parameters. Figure-1 shows the
XRD pattern with respective peaks with (hkl) values. Sharp peaks show the high crystallinity of the
material, Crystallite size of ZnS was calculated by using Debye-Scherrer equation as shown below
𝐾𝐾𝐾𝐾
𝐷𝐷 = 𝛽𝛽𝛽𝛽𝛽𝛽𝛽𝛽𝛽𝛽 (2)

Where D is crystallite size, k=0.9(constant), λ=0.1540nm, β is full width at half maxima

(FWHM), whereas θ is angle corresponding to the peaks of ZnS. The average crystallite size of the
as synthesized ZnS was found to be about 14nm.

Fig. 1 XRD pattern of the as synthesized ZnS

Williamson Hall Plot. Williamson Hall plot was plotted to verify the average crystallite size of
the material and to calculate the strain present. Equation-3 shows Williamson Hall equation[13].
𝐾𝐾𝐾𝐾
𝛽𝛽𝑇𝑇 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 = (𝜀𝜀 × 4𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆) + 𝐷𝐷
(3)
 Materials Science Forum Vol. 1099 121

In the above equation, βT constitutes two factors i.e., crystallite size broadening and microstrain
broadening, whereas ε shows strain, k=0.9(constant), λ=0.1540nm, β mean full width at half
maxima (FWHM) whereas θ is angle corresponding to peaks of ZnS. Figure-2(a) represents
Williamson Hall plot and when equation-3 compared with linear standard equation (y=mx+c), then
slope gave the strain present in the material and intercept was equated to show crystallite size. The
average crystallite size found from W-H plot was about 11nm with the strain of -0.0012.
Size-Strain Plot. Size-Strain plot also verify the range of strain with the average crystallite size
for the material. Equation-4 is known as Size Strain equation which gave strain by Gaussian
function and crystallite size by Lorentzian function[14].
𝐾𝐾𝐾𝐾 2 𝜖𝜖 2
(𝑑𝑑ℎ𝑘𝑘𝑘𝑘 × 𝛽𝛽ℎ𝑘𝑘𝑘𝑘 × 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶)2 = 𝑡𝑡
× (𝑑𝑑ℎ𝑘𝑘𝑘𝑘 × 𝛽𝛽ℎ𝑘𝑘𝑘𝑘 × 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶) + (4)
4

Figure-2(b) depicts size-strain and showed slope with intercept. When equated with equation we
find the strain of 0.0153 and average crystallite size of 9nm. From Debye-Scherrer equation, W-H
plot and Size-Strain Plot all showed that average crystallite size of material were found to be in a
range of 9 to 14nm.
a b

Fig. 2(a) William Hall Plot for as synthesized ZnS (b) Size-Strain Plot for as synthesized ZnS.
UV-Visible Spectroscopy. The UV-Visible response of the as synthesized ZnS material was
recorded on SHIMADZU UV-2600i spectrometer in the range of 850nm to 190nm. For future
application of ZnS material in solar field, we needed to know the absorption for the material and its
optical band gap. That was done through diffuse reflectance spectroscopy (DRS). The recorded
reflectance data was used for Kubelka Munk theory. Figure-3(a) shows multiple absorption peaks in
the UV region with most intense peak at 325nm. Using Tauc plot, the optical band gap of material
was estimated which is shown in figure-3(b). The optical band gap of the material came out to be
3.43eV.
a b

Fig. 3(a) Absorption peaks for as synthesized ZnS (b) Tauc plot for the estimation of band gap of
ZnS.
Refractive Index. Refractive index shows inverse relation with wavelength, which signifies that
larger the refractive index of material better would be the property showed by material for solar
applications. To know the refractive index we used equation-5
122 Dielectric, Semiconductive and Conductive Materials

𝑛𝑛2 −1 𝐸𝐸𝑔𝑔
𝑛𝑛2 +1
= 1 − �20 (5)

Where Eg is optical band gap and n is refractive index. The calculated refractive index for as
synthesized ZnS material was 1.95.
Microstructural Analysis. The detailed micro structural features of the synthesized ZnS
nanoparticles were studied using HR-TEM (make: THERMO SCIENTIFIC, model: TALOS) with
an attachment of EDX. TEM images as shown in figure-4(a), depicting the particle size in the range
8-15nm are found to be in good agreement with XRD data. Figure-4(b) represents the HRTEM
image showing lattice fringes which were analysed and found to be belongs to ZnS. Figure-4(c)
shows the selected area electron diffraction (SEAD) pattern of the corresponding area of the
material depicting polycrystalline nature of the as synthesized ZnS material. Elemental
compositional analysis of the material was done with Energy Dispersive Spectrometer (EDS) which
shows a large amount of Zinc and Sulphur present in the sample as depicted in figure 4(d).

a b

20nm 5nm

c d

1.00 1/nm

Fig. 4(a) TEM images showing ZnS quantum dots (b) High resolution TEM image showing lattice
fringes of ZnS quantum dots (c) SEAED pattern for ZnS depicting polycrystalline nature (d) EDX
pattern for showing the presence of Zn and S.
Potentiostatic Electrochemical Impedance Spectroscopy (PEIS). The PEIS study was done
using Bio-logic SP-240 Potentiostat. A three-electrode system was setup, where Calomel electrode
was taken as reference electrode, platinum was counter electrode and the prepared electrode of ZnS
quantum dots was used as working electrode. All the electrodes were placed in 1M KOH solution.
In PEIS we study the current response of the working system in the range of 0.01 to 105 Hz. Figure-
5(a)&(b) represent Nyquist and Bode plot to understand the response. Figure-5(a) shows Nyquist
plot between real and imaginary part of impedance. The semicircle response for this plot was pretty
standard which showed the presence of capacitance with resistor behaviour of the system. The Z-
fitted data create Randel’s’ Circuit [figure-5(a)] which showed R1 was resistance offered by
electrolyte(Rs), R2 was resistance offered by film(Rf) and R3 was resistance offered by charge
transfer(Rct). Whereas W is Warburg diffusion. Table-1 showed the corresponding value of the
above. The deviation of semicircle is called Warburg diffusion which showed that material had
diffusion behaviour. Being diffusion controlled the material showed a good prospect for solar cell
application as diffusion of excitons controls the current in material. The z-fitting do not match the
 Materials Science Forum Vol. 1099 123

standard pattern as at low frequency the reactants diffuse farther, thereby increasing Warburg
impedance[15].
a b c

Fig. 5(a) Nyquist Plot for ZnS quantum dots (b) Bode Plot for ZnS quantum dots (c) Randle’s
Circuit for working system.
Table-1
Parameters Values
R1[Resistance offered by electrolyte(Rs)] 16.92Ohm
C1[Capacitance across electrolyte] 27.36e-6 F
R2[Resistance offered by film(Rf)] 15.272 Ohm
C2[Capacitance across film] 1.662e-6 F
R3[Resistance offered by charge transfer(Rct)] 26.11 Ohm
W[Warburg Impedance] 2 801 Ohm.s-1/2

Bode plot represent the gain and phase of a system as a function of frequency. The graph depicts
that only one maxima gain can be seen in mid frequency region. The maxima is near -80o. As for
magnitude it is depicted that at lower frequency there is high amplitude and at higher frequency
showed lower magnitude. Using Bode plot we can say whether the control system is stable or
unstable based on the values of these parameters. Here only one phase maxima and decrease in
magnitude with frequency show system stability[16].
I-V Characteristics. The I-V study was done on two-electrode system. I-V curve for ZnS
material synthesized by Choudapur.et.al shows a current response of 0.05mA for -1 Volt to 1 Volt
[17] whereas studies performed by us shows a good current response of 75mA for -1 Volt to 1Volt
as depicted in figure-6. This made the green synthesized ZnS a novel material due to its current
response against given voltage.

Fig. 6. I-V Characteristics of as synthesized ZnS quantum dots.

124 Dielectric, Semiconductive and Conductive Materials

Conclusion
ZnS quantum dots were successfully synthesized using green synthesis method. XRD study
confirmed the synthesis of single phase ZnS powder with good crystallinity. Using Debye-Scherrer
equation, Williamson Hall plot and Size-Strain plot, crystallite size and strain of the material was
determined which came out to be in the range of 9-14nm for size and -0.0012 to 0.0153 range for
strain. UV-Vis spectroscopy showed absorption in the UV region with a band gap of 3.43eV and a
low refractive index of 1.95. Microstructural analysis showed the presence of quantum dot with
particle size of the order of 9nm. Elemental compositional analysis using EDX revealed the
presence of Zinc and Sulphur only indicating the purity of the as synthesized ZnS. Nyquist plot for
working thin film electrode showed Warburg impedance establishing diffusion behavior for the
material with Randle’s circuit. The as synthesized ZnS material may be used in solar cell
application.

References
[1] S. Kaur, S. Sharma, A. Umar, S. Singh, S. K. Mehta, and S. K. Kansal, “Solar light driven
enhanced photocatalytic degradation of brilliant green dye based on ZnS quantum dots,”
Superlattices Microstruct., vol. 103, pp. 365–375, 2017, doi: 10.1016/j.spmi.2016.10.046.
[2] R. Jha, M. Bhushan, and R. Bhardwaj, Studies on Synthesis and Various Characteristics of
Green Materials for Energy Conversion Applications. Springer International Publishing,
2020.
[3] K. F. Lin, H. M. Cheng, H. C. Hsu, L. J. Lin, and W. F. Hsieh, “Band gap variation of size-
controlled ZnO quantum dots synthesized by sol-gel method,” Chem. Phys. Lett., vol. 409, no.
4–6, pp. 208–211, 2005, doi: 10.1016/j.cplett.2005.05.027.
[4] A. Zazueta-Raynaud, R. Lopez-Delgado, J. E. Pelayo-Ceja, M. E. Alvarez-Ramos, and A.
Ayon, “Utilization of down-shifting photoluminescent ZnO quantum dots on solar cells,”
Mater. Res. Express, vol. 4, no. 7, 2017, doi: 10.1088/2053-1591/aa7824.
[5] D. Sharma, R. Jha, and S. Kumar, “Quantum dot sensitized solar cell: Recent advances and
future perspectives in photoanode,” Sol. Energy Mater. Sol. Cells, vol. 155, pp. 294–322,
2016, doi: 10.1016/j.solmat.2016.05.062.
[6] J. C. Melendres-Sánchez et al., “Zinc sulfide quantum dots coated with PVP: applications on
commercial solar cells,” J. Mater. Sci. Mater. Electron., vol. 32, no. 2, pp. 1457–1465, 2021,
doi: 10.1007/s10854-020-04916-0.
[7] M. Shi et al., “‘Bottom-up’ preparation of MoS2 quantum dots for tumor imaging and their in
vivo behavior study,” Biochem. Biophys. Res. Commun., vol. 516, no. 4, pp. 1090–1096,
2019, doi: 10.1016/j.bbrc.2019.06.162.
[8] M. Bhushan, R. Jha, R. Bhardwaj, and R. Sharma, “Visible light emission and enhanced
electrocatalytic activity of pure ZnS nanoparticles synthesized via thermal decomposition
route,” Bull. Mater. Sci., vol. 44, no. 4, 2021, doi: 10.1007/s12034-021-02546-8.
[9] F. Amirian, M. Molaei, M. Karimipour, and A. R. Bahador, “A new and simple UV-assisted
approach for synthesis of water soluble ZnS and transition metals doped ZnS nanoparticles
(NPs) and investigating optical and photocatalyst properties,” J. Lumin., vol. 196, pp. 174–
180, 2018, doi: 10.1016/j.jlumin.2017.12.005.
[10] H. Zhao, Y. Dong, P. Jiang, X. Wu, R. Wu, and Y. Chen, “Facile preparation of a ZnS/ZnO
nanocomposite for robust sunlight photocatalytic H2 evolution from water,” RSC Adv., vol. 5,
no. 9, pp. 6494–6500, 2015, doi: 10.1039/c4ra13203c.
 Materials Science Forum Vol. 1099 125

[11] S. Ummartyotin and Y. Infahsaeng, “A comprehensive review on ZnS: From synthesis to an

approach on solar cell,” Renew. Sustain. Energy Rev., vol. 55, pp. 17–24, 2016, doi:
10.1016/j.rser.2015.10.120.
[12] Shreya, A. Yadav, R. Khatri, N. Jain, A. Bhandari, and N. K. Puri, “Double Zone Thermal
CVD and Plasma Enhanced CVD Systems for Deposition of Films/Coatings with Eminent
Conformal Coverage BT - Advances in Manufacturing Technology and Management,” 2023,
pp. 273–283.
[13] R. Sharma et al., “Controlled growth of α-MoO3 nanostructures with enhanced optical and
electrochemical properties without capping agents,” Ceram. Int., vol. 46, no. 14, pp. 23084–
23097, 2020, doi: 10.1016/j.ceramint.2020.06.085.
[14] M. Bhushan, R. Jha, R. Bhardwaj, and R. Sharma, “Graphene-doped ZnS nanoparticles
synthesized via hydrothermal route for enhanced electrocatalytic performance,” Int. J. Appl.
Ceram. Technol., vol. 18, no. 5, pp. 1510–1526, 2021, doi: 10.1111/ijac.13801.
[15] R. Bhardwaj, R. Jha, M. Bhushan, and R. Sharma, “Comparative study of the electrochemical
properties of mesoporous 1-D and 3-D nano- structured rhombohedral nickel sulfide in
alkaline electrolytes,” J. Phys. Chem. Solids, vol. 144, no. April, p. 109503, 2020, doi:
10.1016/j.jpcs.2020.109503.
[16] P. PHOGAT, S. Shreya, R. JHA, and S. Singh, “Diffusion Controlled Features of Microwave
Assisted ZnS/ZnO Nanocomposite with Reduced Band Gap,” ECS J. Solid State Sci.
Technol., 2023, [Online]. Available: http://iopscience.iop.org/article/10.1149/2162-
8777/acc426.
[17] V. H. Choudapur, S. B. Kapatkar, and A. B. Raju, “Structural and Optoelectronic Properties
of Zinc Sulfide Thin Films Synthesized by Co-Precipitation Method,” Acta Chem. Iasi, vol.
27, no. 2, pp. 287–302, 2019, doi: 10.2478/achi-2019-0018.