International Journal of Mechanical and Production

Engineering Research and Development (IJMPERD)

ISSN(P): 2249-6890; ISSN(E): 2249-8001
Vol. 5, Issue 3, Jun 2015, 27-34
TJPRC Pvt. Ltd.

INVESTIGATION ON SYNTHESIS, STRUCTURAL AND OPTICAL PROPERTIES

OF ZNO NANOPARTICLES PREPARED BY SOLGEL PROCESS
A. VANAJA1 & K. SRINIVASA RAO2
1
2

Department of Physics, Lingayas University, Faridabad, Haryana, India

Department of EIE, Lakkireddy Balireddy College of Engineering, Mylavaram, Andhra Pradesh, India

ABSTRACT
In present work Sol-gel method is used to synthesize ZnO nanoparticles with Zinc chloride and potassium
hydroxide as starting materials. x and optical properties of the ZnO nanoparticles were investigated. The crystalline phases
such as strain, grain size, phase composition and defect structure of pure ZnO phase is determined using X Ray Diffraction
(XRD). The images of morphology of samples are verified using Scanning electron microscopy (SEM) .The presence of
functional groups were analyzed by Fourier Transform Infrared (FTIR) spectroscopy. The absorption spectrum was
obtained from UV-Vis optical absorption spectra. The emission peaks were detected by PL spectrum. XRD and SEM
confirmed the formation of ZnO Nanoparticles. The UV-vis absorption spectra of the ZnO nanoparticles showed blue-shift
in wavelength corresponding to bulk. This study reveals the usefulness of ZnO nanoparticles in optoelectronic devise
applications.

KEYWORDS: ZnO Nanoparticles, XRD, SEM, FTIR, Optical Absorption

INTRODUCTION
Nanoparticles are particles between 1 and 100 nanometers in size. Nanoparticles are of great scientific interest as
they are a bridge between bulk materials and atomic or molecular structures.Nanoparticle research is currently an area of
intense scientific interest due to a wide variety of potential applications in biomedical, optical and electronic fields.
Metal oxide nanostructures are among the most common and widespread nanomaterials on Earth. Many of the
naturally occurring nanoparticles are metal oxides too, they are in our soils, our waterways, our consumer products and in
our homes.For example Zinc oxide,Iron oxide ,Titanium oxide nanoparticles have also been indentified on the Moon, on
Mars and in space .They possess control particle sizes, surface faceting and crystallographic quality.They are stable at high
temperatures These are resistant to solvents and are easily regenerated
Transition metal oxides display exciting and important physical properties such as high temperature
superconductivity, colossal magnetoresistance and ferroelectricity. We are developing new chemistry of the transition
metal oxides, addressing targets such as lead-free replacements for the widely used ferroelectric lead zirconate titanate and
new multiferroic materials where properties such as ferroelectricity and ferromagnetism are coupled in the same material.
In addition to conventional ceramic synthesis methods we are developing low-temperature synthesis routes, synthesis of
complex oxide materials in nanoparticle form, and the application of high pressure synthesis routes to new transition metal
oxides.
Transition metal oxides have many applications as catalyst Ternary Transition Metal Oxide Nanoparticles with
www.tjprc.org

editor@tjprc.org

28

A. Vanaja & K. Srinivasa Rao

Spinel Structure for the Oxygen Reduction Reaction ( Rou Jun Toh1 et al.17 April 2015 DOI: 10.1002/celc.201500070)
, sensor, Synthesis of nickel nitroprusside coordination nanoparticles by simple means: Its characterization and use as
electrochemical sensor for sulfide estimation in sewage and water samples( Samrat Devaramani etal.. Int. J. Electrochem.
Sci., 9, 4692 4708, 2014) as adsorbents The Utility of magnetic iron oxidenanoparticles stabilized by carrier oils in
removal of heavymetal ions from waste water( K. L. Palinisamy et al. Vol. 1, Issue 4, Sep 2013, 15-22). ThreeDimensional Magnetic Correlations in Multiferroic LuFe2O4, (A. D. Christianson et al, Phys. Rev. Lett. 100(10), 107601
(2008)
Among all the semiconductors, Zinc oxide (ZnO) is a unique material that exhibits semiconducting, piezoelectric,
and pyroelectric multiple properties. Using different processing techniques, various nanostructures of ZnO such as
Nanowires, Nanorods, Nanocombs, Nanorings, Nanobows, Nanoparticles,Nanobelts, and Nanocages have been
synthesized under specific growth conditions. ZnO semiconductor has several unique properties such as good transparency,
high electron mobility, wide band gap, and strong room temperature luminescence.Due to thse this powder is widely used
as an important raw material for many applications as the design of varistors( Bioelectrochemical Properties of the ZnO
Nanorods Modified by Au Nanoparticles Hsueh-Tao Chou1 Int. J. Electrochem. Sci., 10 (2015) 519 - 528,gas sensors,
synthesis of zinc oxide nanoparticles on graphene-carbon nanotube hybrid for glucose biosensor applications (Boopathi
subramani,Biosensors and bioelectronics , 12/2014; 62:127133),paints Preparation and properties evaluation of ZnO
nanoparticles Edita Brestnajdrova et al , 12. - 14. 10. 2010, Olomouc, Czech Republic, EU). luminescent oxides rubber,
paints, ceramics, and others. Due to its vast areas of application, various synthesis methods have been employed to
synthesize ZnO such as grow a variety of ZnO

Nanostructures. spray pyrolysis ,Solvothermal ,Hydrothermal ,Ball

milling method and Wet Chemical method etc . In this paper ZnO nanoparticles are produced synthesized using Sol-gel
method
Due to its simplicity, low cost , Low tempetaure (<350) ,possibility for doping ,powders with various
morphologies sol-el synthesis of ZnO nanoparticles is preferred in the present work .The particles size, morphology,
crystallinity and optical emission and absorption properties were carried out by using X-Ray diffraction, Scanning Electron
Microscope, Photo Luminescence spectroscopy and Ultraviolet-visible spectroscopy.

EXPERIMENTAL METHODS
Materials
Zinc chloride (ZnCl2), potassium hydroxide (KOH) and ethanol (C2H6O) were purchased and used without further
purification.
Synthesis of Zinc Oxide Nanoparticles
In this experiment, 0.4 M aqueous ethanol solution of zinc chloride (ZnCl2) was kept under constant stirring using
magnetic stirrer to completely dissolve the zinc chloride for one hour and 0.8 M aqueous ethanol solution of sodium
hydroxide (NaOH) was also prepared in the similar way with stirring of one and half hours. After complete dissolution of
zinc chloride, 0.8 M aqueous solution of sodium hydroxide is added under high speed constant stirring drop by drop
touching the walls of the vessel. The reaction continued for 2 hrs after complete addition of sodium hydroxide. The
dripping of the ZnCl2 and NaOH solutions in an aqueous alkaline solution results in immediate precipitation of ZnO and
the colour of the suspension changes from transparent to white. The beaker was sealed at this condition for 2 h. After the

Impact Factor (JCC): 5.6934

NAAS Rating: 2.45

Investigation on Synthesis, Structural and Optical Properties of

ZnO Nanoparticles Prepared by Solgel Process

29

completion of reaction, the solution was allowed to settle for overnight and further, the supernatant solution was detached
carefully. The remaining solution was centrifuged for 10 min and the precipitate was removed. The solution centrifuged for
10 min and the precipitate formed was separated .By washing with ethonal and distilled water ,the unwanted impurities
were removed and then the precipitate dried in an vacuum oven at a maximum temperature of 70C for several hours. After
drying Zn (OH)2 is completely converted to into ZnO explained by the Equation below.
Zn(OH)2 ZnO+H2O
Characterization of Nanoparticles
The properties of Nanoparticles were analyzed by performing various characterizations. Confirmation of pure
ZnO phase is verified with XRD. The XRD patterns for the ZnO nanoparticles were recorded using an X-ray
diffractometer (PANLYTICAL) using secondary monochromatic CuK radiation of wavelength = 0.1541 nm at 40
Kv/50mA in the scan range 2 = 20 to 90o. The shape and morphology of the samples were investigated using scanning
electron microscope (SEM with EDXA, Sirion) .The images also has been used for compositional analysis of the prepared
ZnO nanoparticles. A drop of nanoparticles dissolved in methanol was placed on a copper grid. The FTIR spectra was
recorded in the Range 450-4000 cm -1 using The Perkin Elmer Spectrum1 FT-IR instrument .The optical absorption
spectra of ZnO nanoparticles was recorded using a Varian Cary 5E UV-VIS NIR spectrophotometer .The
photoluminescence (PL) spectrum of the ZnO nanoparticles dissolved in methanol has been measured using a
spectrofluorometer (F-2500 FL Spectrophotometer, Hitachi).

RESULTS AND DISCUSSIONS

X-Ray Diffraction Spectroscopy

Figure 1: XRD Pattern of ZnO Nanoparticle

Figure 1 represents the X-ray diffraction pattern of ZnO nanoparticles. The X Ray diffraction can estimate
average grain size,lattice parameters ,Full width half maximam (FWHM ) .The line broadening clearly indicates the
presence of particles in nanorange . The pattern consists of diffraction peaks located at 31.946, 34.631, 36.448 47.755,
56.769, 62.928 ,66.45, 68.09, 69.19, 77.17 and 81.56 corresponding to lattice planes (100),(002) ,(101) ,(102) ,(110)
,(103) ,(200) ,(112), (201) respectively . The peaks can be indexed for wurtzite type hexagonal structure of ZnO from
www.tjprc.org

editor@tjprc.org

30

A. Vanaja & K. Srinivasa Rao

JCPDS Powder diffraction card file.

The average ZnO nanoparticle diameter was calculated using Scherrers formula

(1)
Where 0.89 is Scherrers constant,
is the wavelength of X-rays,
is the Bragg diffraction angle
is the full width at half-maximum (FWHM) of the diffraction peak corresponding to plane <101>.
From all diffraction patterns, it is very clear that the plane (101) is found to be more intense than other peaks.
More intensity of the plane (101) indicates the direction of crystal growth along the c axis (direction [0001]) of the ZnO
wurtzite structure. The average particle size of the sample was found to be 19.6 nm which is derived from the FWHM of
more intense peak corresponding to 101 planes located at 36.448 using Scherrers formula
Scanning Electron Microscopy

Figure 2: SEM images of ZnO Nanoparticles at Different Magnifications

The morphology and size of the synthesized ZnO particles were studied by scanning electron microscopy (SEM).
Figure 2 represents the SEM pictures of prepared ZnO nanoparticles at different magnifications. These pictures confirm the
formation of ZnO .The high resolution SEM images show the presence of nanoparticles.The SEM images represent the
agglomeration of particles and also with narrow particle size distribution. It is also be seen that the samples synthesized
were nanoflakes which were turned to the particles when observed at different magnifications. Zinc oxide nanoparticles are
prone to aggregate due to the large surface area and high surface energy
Impact Factor (JCC): 5.6934

NAAS Rating: 2.45

Investigation on Synthesis, Structural and Optical Properties of

ZnO Nanoparticles Prepared by Solgel Process

31

Fourier Transform Infrared Spectroscopy

FTIR spectroscopy is performed in order to quickly establish the presence or absence of the various vibrational
modes present in synthesized particles .The Figure 3 Shows the FTIR spectrum of the synthesized ZnO nanoparticles
acquired in the range of 500-4000 cm-1.Various modes of vibration are observed at different regions of FTIR spectrum.
From FTIR spectra it is clear that The fundamental modes of vibration near 3700 cm-1 correspond to the O-H stretching
vibration, around 2000 cm-1 corresponds to C-H stretching vibration and around 1400cm-1 corresponds to C=O
asymmetric C=O stretching vibration. FTIR images clearly show that the characteristic absorption peak of Zn-O are nearer
to 400 cm-1 and also authenticates presence of ZnO.

Figure 3: FTIR Spectrum of ZnO Nanoparticles

UV-Visible Optical Absorption Spectroscopy
UV-visible absorption spectroscopy is such a powerful technique to determine the optical properties of the
semiconducting nanoparticles.Optical properties of Zno Nanoparticles become important when size reduced to nanoscale .
Figure 4 shows the room temperature UVvis absorption spectra of the ZnO nanoparticles from 200 nm to 1000 nm.The
spectrum reveals absorption peak around 356nm with an intrinsic band gap around 1.7 eV due to the large exiton binding
energy at room temperature .This observed blue shift is due to the quantum confine effect among the individual
nanoparticles .In addition, sharp peak shows that the particles are in nanosize, and the particle size distribution is narrow.

www.tjprc.org

editor@tjprc.org

32

A. Vanaja & K. Srinivasa Rao

Figure 4: UV-Visible Spectrum of ZnO Nanoparticles

Photoluminescence Spectra
The photoluminescence originates from the recombination of surface states. The strong photoluminescence
indicates that the surface states remain very shallow, as quantum yields of band edge will decrease exponentially with
increasing depth of surface state energy levels .Figure 5 shows room temperature photoluminescence spectra of nano ZnO
powder over wavelength range 350-700 nm. The spectra have been recorded with 300 nm excitation at room temperature
.The PL spectra of ZnO nanoparticles exhibits broad visible emission band extending from 400nm-700nm with two
dominant blue emission peaks at 540 nm and 600 nm. It can be attributed to the transition between singly charged oxygen
vacancy and photo excited hole or Zn interstitial related defects.from spectra it is also clear that the ZnO can emit
luminescence over the entire visible range.

Figure 5: Room Temperature PL Spectra of ZnO Nanoparticles

CONCLUSIONS

In the present study ZnO nanoparticles were synthesized via Sol Gel route with zinc chloride ,KOH further
analyzed through X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy,
optical absorption and Photo luminescence spectroscopy techniques

The XRD analysis demonstrates that nanoparticles have the hexagonal wurtzite structure. SEM images showed
the morphology and size of the ZnO nanoparticles.

The FTIR spectrum revealed the functional group assignments of the ZnO nanoparticles. The UV-vis absorption
spectra of the ZnO samples exhibit a blue-shift in cut off wavelength with respect to the bulk PL emission of the
sample nearly covers the full visible range attributed to the deep level emissions which can be considered to be
promoted by the morphology and size of nanoparticles formed.

The Sol-gel route employed in this work is simple, cost effective and free of pollution and therefore, the technique
can be extended to prepare many other important semiconducting metal oxide nanoparticles. These ZnO
nanoparticles can be used in different industrial applications viz., luminescent material for fluorescent tubes,
active medium for lasers, sensors etc

Impact Factor (JCC): 5.6934

NAAS Rating: 2.45

Investigation on Synthesis, Structural and Optical Properties of

ZnO Nanoparticles Prepared by Solgel Process

33

ACKNOWLEDGEMENTS
The authors would like to thank SAIF IIT Chennai and Center for nanoscience and Technology ,Satyabhama University
Chennai For proving the facilities for Characterization

REFERENCES
1.

Mr. B. Sudheer Kumar, International Journal of Engineering Research & Technology (IJERT) Vol. 1 Issue 6,
August - 2012 ISSN: 2278- 0181,

2.

T. Satyanarayana, K. Srinivasa Rao and G. Nagarjuna, ISRN Nanotechnology, 2012 (2012) 1-6

3.

T.V.Kolekar, H.M.Yadav, S.S.Bandgar And P.Y.Deshmukh Indian Streams Research Journal ISSN 2230-7850
Volume-1, Issue-1, Feb-2011

4.

DLukovicGolic1, IOP PUBLISHING Nanotechnology 22 (2011) 395603 (9pp)

www.tjprc.org

editor@tjprc.org

www.tjprc.org

editor@tjprc.org