Fall 2022

University of Eastern Finland

Atif Abbas

An Analysis of Structural and Optical Properties Undoped ZnS and

Doped (with Mn, Ni) ZnS Nano Particles
 Preface

I am writing this report as part of my coursework for University of Eastern Finland. The purpose of
this report is self-understanding about how to write a report. This report entails the findings of the
study on the structural and optical properties of ZnS in certain conditions.
 Table of Contents

Sr. No. Title Page #

i Abstract………………………………… i
1 Introduction…………………………….. 1
2 Methods and Materials…………………. 1
2.1 Experimental Design…………………… 2
2.2 Microstructure Studies…………………. 2
2.2.1 XRD Studies……………………………. 2
2.2.2 Electron Diffraction Studies……………. 2
2.2.3 SEM Studies…………………………… 3
2.2.4 Photo Luminescence Studies…………… 4
2.2.5 Optical Absorbance Study……………… 4
2.2.6 Raman Studies………………………….. 5
3 Conclusion……………………………… 7
References……………………………… 8
 List of Figures
Fig. Description Page #
1 (a) XRD diffractogram of ZnS; (b) XRD diffractogram of ZnS-Mn……………………………………. 3
2 (a) SAED of ZnS; (b) SAED of ZnS-Ni; (c) SAED of ZnS-Mn………………………………………… 3
3 (a) SEM micrograph of ZnS-Ni; (b) SEM micro- graph of ZnS-Mn…………………………………… 4
4 (a) PL spectra of Zn-S, ZnS-Ni; (b) PL spectra of Zn-S, ZnS-
Mn………………………………………. 5
5 (a) Absorbance spectra of ZnS; (b) Absorbance spectra of ZnS-Ni; (c) Absorbance spectra of ZnS-Mn 6
6 Raman spectra…………………………………………………………………………………………… 6
 List of Abbreviations

Abbreviations Full name

XRD X-ray Diffraction
HRTEM Hi-resolution Transmission Electron Microscopy
SEM Scanning Electron Microscopy
PL Photo-luminescence
SAED Selected area electron diffraction
UV-VIS UV visible
PVA Polyvinyl Alcohol
 Abstract

Devices made of semi-conductors and optoelectronics have several uses for nanoparticle behavior.
ZnS nano-crystals were chemically produced into a polyvinyl alcohol matrix at various weight
percentages. Optical characteristics of both un-doped and doped with ZnS nano-crystalline
materials were examined. Hi-resolution Transmission Electron Microscopy (HRTEM) and X-ray
diffraction (XRD) were used to describe the nanostructure (HRTEM). Scanning electron
microscopy was used to study surface morphology (SEM). According to the Debye-Scherrer
formula, the mean particle sizes of ZnS, ZnS-Ni, and ZnS-Mn are approximately 2.3 and 2.5 nm for
undoped and doped ZnS, respectively. These average particle sizes were discovered by TEM to be
6.51, 7.3, and 12 nm, respectively. At surrounding conditions, the peak of the photoluminescence
(PL) emission spectra was measured at 375 nm, and the peak for Ni was measured at 433 nm. At
ambient temperature, Mn's photoluminescence (PL) emission spectra again reached their maximum
at 334 nm, whereas Mn-dependent emission was discovered at 580 nm. These numbers
demonstrated successful doping. The presence of a dopant in the nano-crystallites was also
confirmed by PL investigations. Utilizing a UV-VIS Spectrophotometer, optical absorption
experiments revealed a significant absorbance at 400 nm with an inclination for blue shift. A set of
four clearly defined rings that correspond to the diffraction from various planes of the nano
crystallites are visible in selected area electron diffraction (SAED). A well-crystalline ZnS doped
with Ni and Mn was visible in the HRTEM image. The well-crystalline forms of ZnS were
confirmed by XRD analyses and Raman spectra.
1. Introduction:

Nano materials have distinct physical and chemical characteristics than equivalent bulk
materials, such as optical absorbance, fluorescence, catalytic activity, electrical and thermal
conductivity, etc. Due to the quantum size confinement in nanostructures and the incredibly
high surface-to-volume ratio in comparison to bulk materials, nanoparticles have unique
features that make it possible to maintain a significant portion of atoms or molecules in lower
reactive bounds. Researchers have become interested in the production and characterization of
nano crystals produced using various substances. Low-dimensional semiconductors, especially
nanostructured ZnS composites, have drawn a lot of attention due to their advantageous
photoluminescence characteristics. Chemical growth process is a very simple, economical,
efficient, and convenient method among the various researchers. Doped ZnS nano materials are
widely employed in optical sensors, electroluminescence devices, digital displays, and other
applications. The intrinsic surface states of the particles and the type of chemical processing
used in their manufacture determine the photo luminescent characteristics and efficiency of ZnS.
Research is also being done on these films' use in light-emitting materials and on their optical
characteristics (Thi et al., 2010). When crystallite dimensions are reduced, a blue shift in the
optical light emission in the blue-red spectral region is seen. With the aid of instruments such as
the X-ray Powder Diffractometer (XRD), Scanning Electron Microscopes (SEM), High
Resolution Transmission Electron Microscopes (HRTEM), Photo-luminescence Spectrometer
(PL), UV Visible Spectrophotometer (UV-VIS), etc., we are attempting to characterize the
properties of ZnS with various doping agents (Ni and Mn).

2. Methods and Materials:

2.1 Experimental Design:

In the synthesis in order to create ZnS nanoparticles, Polyvinyl Alcohol (PVA) was used as the
matrix. PVA and ZnCl2 were dissolved in various weight percent solutions in deionized water,
and the mixtures were agitated for three hours at 70°C at 200 rpm in a magnetic stirrer. The
solution was allowed to dissolve completely overnight, and it was discovered to be transparent.
Once the entire solution started to look milky, a 2 weight percent Na2S solution was added.
Overnight, the solution was stored in a dim chamber. The nanostructure inserted itself into the
gap as soon as it was produced. This is how the chemical reaction happened:
 2

ZnCl2 + NaS2 = ZnS + 2NaCl

NiCl2.6H2O was weighed out with deionized water to create various concentrations of ZnS:Ni
solution. The resulting solution was combined with another PVA and ZnCl2 solution. Then, at a
constant temperature of 70 °C, the solution was agitated at 200 rpm in a magnetic stirrer. The
solution was supplemented with 0.08 M weight% Na2S solution. The discovered precipitation
was cleaned with deionized water and taken for analysis.

MnCl2.4H2O was combined by weight% with deionized water to create various concentrations
of ZnS:Mn solution. The resulting solution was combined with another PVA and ZnCl2
solution. Then, at a constant temperature of 70 °C, the solution was agitated at 200 rpm in a
magnetic stirrer. The solution was supplemented with 0.08 M weight% Na2S solution. The
discovered precipitation was cleaned with deionized water and taken for analysis.

2.2 Microstructure Studies

2.3 XRD Studies:

The powder used for the XRD analyses in Figures 1(a) and (b) was used. Using Cu K α
radiation, a diffractogram was produced using a Philips X'pert Pro Powder diffractometer with
an operating voltage of 40 kV and a current of 20 mA.

The pattern shown fit inside the nano range, it was discovered. The films were identified as
polycrystalline by XRD patterns (Goudarzi et al., 2009). The presence of the planes (111),
(220), and (311) corresponded nicely with the JCPDS card No. 05-0566. Using the Scherrer
formulas, the average particle size corresponding to the FWHM was determined and discovered
to be 2.3 nm.

0.94 
Dp =
1/2 cos 

. 2.2.2 Electron Diffraction Studies

With the use of HRTEM, selected area electron diffraction (SAED) was carried out. A set of
three clearly defined rings were also seen in the SAED photo of undoped ZnS (Figures 2 (a)–(c)),
which is likewise in good agreement with the XRD data. These rings correspond to the planes
(111), (220), and (311) in the case of undoped ZnS.
 Intensity
(a) (b)

Figure 1: (a) XRD diffractogram of ZnS; (b) XRD diffrac- togram of ZnS-Mn

Figure 2: (a) SAED of ZnS; (b) SAED of ZnS-Ni; (c) SAED of ZnS-Mn

2.2.3 SEM Studies

Figure 3 displays images of the nano-crystalline thin film acquired with a (JEOL, JSM-6360)
SEM. When the PVA-prepared film's surface morphology was examined, it was discovered that
none of the particles had formed precisely spherical. The film's surface was smooth, consistent,
and without any cracks, according to the study. ZnS-Ni and ZnS-Mn particles were discovered to
have diameters ranging from 7 to 16 and 7 to 15 nm, respectively.
 4

Figure 3: (a) SEM micrograph of ZnS-Ni; (b) SEM micro- graph of ZnS-Mn

2.2.4 Photo Luminescence Studies

Using an F-2500 FL Spectrophotometer, photo luminescence investigations of nan-ocrystalline

doped and un-doped samples (Figure 4) were carried out at room temperature. The excitation
wavelength used in all measurements was 240 nm. Emission spectra for ZnS revealed a large peak
at 378 nm and a second, smaller broad peak at 451 nm, while peaks for ZnZ-Ni (0.5%) and ZnS-
Ni appeared at 375 nm and 433 nm. For Mn, the emission spectra revealed two large peaks, one at
346 nm and the other at 468 nm.
The thin ZnS:Mn film's PL spectra showed yellow-orange emissions. At 580 nm, Mn dependent
yellow emission was seen, serving as more evidence of good Mn doping. Intensity decreases from
the blue emission (at 468 nm) to the orange emission (at 580 nm) (Singh et al., 2004). ZnS:Ni
emissions showed yellow-orange emissions in PL spectra.

2.2.5 Optical Absorbance Study

ZnS's optical absorbance (Figure 5) was measured at room temperature using a Hitachi-U3210
Double Beam Automated Spectrophotometer, where optical absorbance was measured over the
wavelength range of 200 to 800 nm. Strong absorption at that wavelength was visible. ZnS's
absorption peaked at a wavelength of 287 nm. Strong absorption at that wavelength was visible.
ZnS's absorption peaked at a wavelength of 287 nm.
 Figure 4: (a) PL spectra of Zn-S, ZnS-Ni; (b) PL spectra of Zn-S, ZnS-Mn

The quantum confinement effect on the nanoparticles was attributed to the peak of the
absorption's blue shift in comparison to bulk. Utilizing a UV-VIS Spectrophotometer, optical
absorption measurements revealed a significant absorption toward the blue shift. A prominent
peak can be seen in the optical absorbance spectra of ZnS-Ni (0.5%, 1.0%) at 400 nm. It is
possible to discriminate between the spectra of Ni-doped and undoped ZnS nano-crystals. The
electronic absorption spectra of ZnS are affected, which suggests that Ni doping has an impact. If
the doping level is modest, this would be feasible.
2.2.6 Raman Studies
The sharp ZnS is seen in a well-crystalline condition in Figure 6. The typical ZnS Raman
scattering peaks at 58 cm, 335 cm, and 347 cm are linked to the LO phonon mode. A second peak
at 264 cm 1 is associated with the TO phonon mode of ZnS (Lan et al., 2003).
 6

Figure 5: (a) Absorbance spectra of ZnS; (b) Absorbance spectra of ZnS-Ni; (c) Absorbance spectra of
ZnS-Mn

Figure 6: Raman spectra

3. Conclusion:

Chemical methods have been used to create Ni and Mn-doped and undoped ZnS nano-crystalline
films. The creation of doped and un-doped nanoparticles is shown by the structural and optical
characterization of the films performed with the aid of XRD, TEM, SEM, SAED, UV-VIS
spectrophotometer, and PL. Impurities or defect states may be responsible for the emission bands
at 377 nm, 449 nm (both for 0%), 375 nm, and 433 nm (both for 0.5% Ni), as well as 382 nm for
1% Ni. Similar to ZnS-Mn, defect states may be responsible for the emission bands at 375 nm and
451 nm. The transition of Mn23d +'s shell may be responsible for the third emission band at 496
nm. A well-crystalline condition of ZnS was suggested by the strong Raman peak, which is in
good accord with the XRD finding.
 8

References:
Thi, T. N., Van, B. H., Ben, P. V., 2010. Study of microstructure and optical properties of PVA-
capped ZnS : Cu nanocrystalline thin films. Nonlinear Optical Physics & Materials. 19, 237-245.

Goudarzi, A., Aval, G. M., Park, S. S., Choi, M. C., Sahraei, R., Ullah, M. H., Avane, A., Ha, C.
C., 2009. Low temperature growth of nanocrystalline Mn-doped ZnS thin films prepared by
chemical bath deposition and optical properties. Chem. Mater. 21, 2375-2385.

Singh, S. P., Perales Perez, O. J., Tomar, M. S., Mata, O. V., 2004. Synthesis and characterization of
nanostructured Mn-doped ZnS thin films and nanoparticles. Phys. Stat. sol. 4, 811-814.

Lan, C., Hong, K., Wang, W., Wang, G., 2003. Synthesis of ZnS nanorods by annealing precursor ZnS
nanoparticles in NaCl flux. Solid State Communications. 125, 455-458.