COMAPARATIVE STUDY OF PURE ZINC OXIDE, COPPER

DOPED ZINC OXIDE FOR IMPROVED ABSORPTION

SPECTRA AND CONDUCTIVITY STUDIES FOR SOLAR
APPLICATIONS
Presented by
G. Venkata Ravi
Regd no. 314207238007

Under the Esteemed Guidance of

Dr. B. Kishore Babu
Assistant Professor
Dept. Of Engineering Chemistry
A.U. College of Engineering (A)
Visakhapatnam
 INTRODUCTION
• Nanotechnology is engineering at the atomic level.
• It is the collective term for a range of technologies technologies,
techniques and process that involve the manipulation of matter at the
smallest scale(from 1 to 100nm)
APPLICATIONS
 SOLAR CELLS

• Optical nanostructures have a major role to play in improving the efficiency

of solar cells by increasing the absorption of incident light, especially for
thin-film applications.

• Light harvesting in efficient solar cells strongly depends on the photonic

absorption of nanoparticles.

• Zinc Oxide nanoparticles have received potential interest due to their vast
applications in solar, luminescence, food industry and catalyst industry.
 SOLAR CELLS

• The ZnO nanoparticles have unique properties like wide band gap
energy, large excitation energy, optical transparency and it also acts as
a functional material near UV emission.

• Doped Zinc Oxide nanoparticles are now mostly using in solar

applications by increasing their photonic absorption by doping with
different metals at different concentrations.
 ZINC OXIDE

The requirements which can be fulfilled by ZnO for solar applications:

• High transparency in the visible and near infrared spectral region
• Good contacts to the active semiconductors (absorber layer)
• Possibility for preparation of tailored surfaces with suitable light scattering
properties for light trapping
• Low material costs, nontoxicity, and abundance in earth crust
ZnO properties were enhancing when it is doped different metals
 Mie’s
LITERATURE scattering simulation
SURVEY
The Mie theory is used for:
• the analytical solution of Maxwell’s equations for the scattering of
electromagnetic waves,
• To calculate relationships between UV attenuation efficacy and
particle size.
• To get the absorption spectrum.
 ABSTRACT

• This work portrays the preparation of pure zinc oxide, copper doped
zinc oxide by using Controlled Precipitation method. The structural
characterization of the samples was investigated by X-ray diffraction,
FE-SEM and FT-IR.

• Conductivity studies of pure zinc oxide, copper doped zinc oxide

were studied by D.C and A.C characterization.
 ABSTRACT
ABSTRACT

• Absorption spectra studies of pure zinc oxide, copper doped zinc

oxide were investigated by UV-VIS characterization.

• Optical absorption spectra of pure and Cu- doped ZnO is validated by

modified Mie scattering theory.
 LITERATURE REVIEW
Synthesis of ZnO:
• Co-precipitation method [12, 16, 22, 24, 25, 27, 29]
• Sol-gel method [5, 3]
• CVD [49, 51]
 PRECURSORS:
• Zinc nitrate [12, 22, 24]
• Zinc acetate [29, 16]
• Zinc sulphate [1, 25]
• Diethylzinc(DEZ) [49]
 LITERATURE REVIEW
 Cu doped Zinc Oxide Synthesis:
Precipitating agents:
• KOH
• NaOH
• Na2CO3
Dopant precursors
• Copper acetate [15, 16, 23]
• Copper chloride [17]
• Copper nitrate [22, 24]
• Copper sulphate [25, 29]
 SHORT COMINGS
• It is difficult to produce zinc oxide nanoparticles using CVD AS It is
convenient to produce only films

• Sol gel method involves both chemical and physical processes which
increase the preparation time.

• Zinc nitrate, Zinc sulphate precursors giving prism and flower like
structure which exhibits less planar conductivity.
 OBJECTIVES OF THE PRESENT WORK
• Co-precipitation method is opted to synthesis ZnO and Cu doped ZnO
nanoparticles
• KOH and Na2 CO3 are opted as precipitating agents
• Zinc nitrate used as precursor for synthesis of pure zinc oxide
nanoparticles
• Zinc sulphate and copper sulphate are opted as precursors for synthesis of
Copper doped zinc oxide nanoparticles
 SYNTHESIS

Synthesis of ZnO nanoparticles:

• 0.4M of KOH and 1M of zinc nitrate
solution has been prepared using
distilled water maintained PH value at
12.
• The solution is stirred for 2 h at 3000C
using Magnetic Stirrer until the solution
becomes transparent.
Contd..
• The reacted solution is
dried at 600C overnight to
yield milky-white ZnO
nanoparticles.

• The calcinated powder is

grinded for 2hrs in mortar.
Contd….
Copper Doped ZnO nanoparticle Synthesis:
• Copper doped ZnO nanoparticles has been synthesized by co-precipitation
method.

• First, prepare 1M solution of sodium carbonate under heating and stirring

(solution 1).

• Prepare 1M zinc sulphate solution under heating and stirring (solution 2).
Contd…

• The copper sulfate was added to the zinc sulphate solution to obtain
3% copper doped ZnO. Then this mixer of copper sulfate and zinc
sulfate was added drop wise to the solution 1.

• After adjusting the pH value to 11 the final solution was stirred under
heating for 30 minutes.
Contd…
• Then jelly greenish precipitate forms
this was separated by filtration.

• Then washed several times with

distilled water till obtaining the pH
value of 7 and dried in air.

• Then the sample was heated for 3

hours at 500°c in air.
 Characterization
X-ray Diffraction Analysis of ZnO nanoparticles
X-ray Diffraction Analysis of Cu doped ZnO nanoparticles
Contd…

• The diffraction pattern is recorded and radius 2θ values of 23.578 and

36.328 are observed.

• In the XRD characterization waveforms, we can observe the shift in

peaks of Cu doped ZnO pattern those are due to dopant Copper in
ZnO.
Contd…
• The crystalline size of the sample can
be obtained from the broadening of Sample Crystalline Size
the peaks according to the Scherrer
formula,
ZnO 42.4nm
k𝜆
L=
𝛽cosθ
Cu Doped ZnO 21.84nm
where L is the crystalline size, λ is
the X-ray wave length used, k is the
shape factor of the average crystallite, β
is the full width at half maximum
(FWHM) in radians and θ is the angle
corresponding to the peak position.
FE-SEM analysis of ZnO
FE-SEM analysis of Cu doped ZnO
 FE-SEM analysis
• The pure ZnO nanoparticles shows the synthesized nanoparticles are
homogeneous, uniformly distributed over the surface and good connectivity
between the particles containing the mixer of spheroid-like and rod-like particles
in which spheroid-like particles are dominant with grain size around 10–38 nm.

• The grain size was decreased with the doping of Cu. The surface morphology of
the Cu doped ZnO sample which has slightly lesser grain size than the undoped
ZnO. The shape of the particles is the mixer of spheroid-like and rod-like particles
and hence rod-like particles are dominant with grain size around 10–25 nm.
 FTIR analysis of ZnO
400

350

300

250
% Transmittance

200

150

100

50

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenumber(cm−1)
ANALYSISFTIR
OF analysis of CuZnO
Cu DOPPED doped ZnO
350

300

250
% Transmittance

200

150

100

50

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenumber(cm−1)
 FTIR analysis
• The FT-IR showed the formation of functional groups like O-H stretching, O-H bending, CO
adsorption on the surface of oxide, Zn–O bond and characteristic stretching mode of Cu-O.

• The broad peak in higher energy region at 4000 - 3000 cm−1 is due to O-H stretching and peak in
the lower range at 1384 - 1651 cm−1 is due to O-H bending. All other peaks are attributed to the
characteristic of the prepared pure and Cu doped ZnO nanoparticles.

• The bands appeared near at 1900 - 2354 cm−1 indicates the CO adsorption on the surface of
oxide. Similarly, the bands at 780 - 980 cm−1 might be due to the peroxide formation (M-O-O-M).

• A broad band has been observed at around 490 cm-1 for the pure ZnO corresponding to the
formation of Zn–O bond. The broad band in the coupled Cu doped ZnO at 545 cm-1 is assigned to
the characteristic stretching mode of Cu-O.
 D.C Conductivity
7.00E-06

6.00E-06

5.00E-06
From the D.C conductivity studies it

Conductivity(S/m)
shown that the materials both ZnO 4.00E-06

and Cu doped ZnO behaves as a ZnO

3.00E-06
Cu doped ZnO
conductive materials and D.C
Conductivity of Cu doped ZnO is more 2.00E-06

than Pure ZnO.

1.00E-06

0.00E+00
30 40 50 60 70 80
Temparature (ºc)
AC Conductivity
Capacitance vs Temperature
Impedance vs Frequency
Tangent loss vs Frequency
 AC Conductivity
• AC conductivity is determined using the relation

𝜎AC = C 𝜔 tan𝛿

Where C is the capacitance, ω is the angular frequency and tan δ is the loss factor.

• The variations of capacitance, impedance and tangent loss with frequency in pure and Cu-doped
ZnO are shown. They shows that in Cu doped sample, the impedance increases or in other words,
the A.C conductivity decreases. However, at higher doping the impedance decreases.

• From equation, it can be observed that AC conductivity is directly proportional to the capacitance
and also tangent loss. The variations of the capacitance and tangent loss also show a decrease at
Cu doping.
UV-Vis Spectroscopy of ZnO nanoparticles
UV-Vis Spectroscopy of Cu-ZnO nanoparticles
 UV-Vis Spectroscopy

• The absorption spectra of both pure and Cu doped ZnO samples were
shown that the absorption of the samples was increased with doping
of Cu.

• for pure ZnO absorption spectra was ended at 620nm wavelength

range but for Cu doped ZnO was more than 620nm.
Mie scattering: experimental vs. theoretical
Contd…
• The Mie scattering absorption spectra is given by,

2 ∞ 2
∝= σ 2𝑛 + 1 [𝑅𝑒 𝑎𝑛 + 𝑏𝑛 − ( 𝑎𝑛 + 𝑏𝑛 2 )]
𝑥 2 𝑛=1

2𝜋𝑟
where, 𝑥 = , r is the particle radius, 𝜆 is the wavelength and m the complex refractive
𝜆
index of the sphere relative to the ambient. The Mie coefficients are given by 𝑎𝑛 and 𝑏𝑛 .

• The MATLAB simulation was performed by taking the complex ZnO refractive index as 2.003+0.07i
for a particle radius r = 19nm. It is superimposed with experimental absorption spectra then both
of them are better fitted in the wavelength range 330nm to 360nm. The additional resonant peak
arises from the resonant surface waves on a sphere.
Mie scattering: experimental vs. theoretical
Contd…

• The MATLAB simulation (curve b) shows that for a complex refractive index 1.99 +
0.01i, particle radius r = 12.5nm, the light scattering from Cu doped ZnO
nanoparticles show a better fit using the Mie theory in the wavelength range 330
to 380nm.

• The other wavelength side of the fitted curve is not perfectly matching with the
experimental curve due to the fact that for simulation the nanoparticles are
considered to be perfect spheres.
 CONCLUSION

• From the XRD results, the crystal size of copper doped ZnO is less
than the pure ZnO.

• From the D.C Conductivity we measured conductivity values; it shows

that the material behaves as a conductive material and D.C
Conductivity of Cu doped ZnO is more than Pure ZnO.
Contd…

• From the A.C Conductivity we measured conductivity values; it shows

that the Cu doped ZnO has comparatively less A.C conductivity than
pure ZnO.

• But in solar cells solar energy converted into D.C current so D.C
conductivity is more important for solar cell applications.
Contd…..

• FE-SEM studies of ZnO synthesized nanoparticles are homogeneous,

uniformly distributed over the surface and good connectivity between
the particles with grain size around 10–38 nm.

• The Cu doped ZnO sample has particles with grain size around 10–25
nm, which is slightly lesser grain size than the undoped ZnO.
Contd…..
• UV-VIS studies of ZnO and Cu doped ZnO are showing that the absorption
of Cu doped ZnO is higher than the pure ZnO.

• The MATLAB Simulation using Mie scattering theory; the absorption

spectra of ZnO and Cu doped ZnO are matching with the mie absorption
spectra so absorption spectra is verified.

• It shows that Cu doped ZnO materials can be used in solar applications to

improve photocurrent generation.
 APPLICATIONS

• semiconductor for various applications such as UV emitters and

photodetectors, light-emitting diodes (LEDs), gas sensors, field-effect
transistors, and solar cells.

• ZnO resists radiation, and hence, it is a suitable semiconductor for

space technology applications.
Contd…

• Cu doped ZnO are applicable in solar applications to improve the

energy conversion efficiency.

• CdS quantum dot solar cells are sensitized with Cu doped ZnO
nanorod thin films.
 FUTURE SCOPE

• At present work, only Cu dopant at one particular concentration i.e.,

3% is used to dope ZnO.

• The scope of the work in future can be widened to include different

types of dopants such as Al, Ni etc.,

• Properties should be compared for different concentrations of

dopants to find out better properties.
 ACKNOWLEDGMENT

• I am extremely fortunate and delighted to work under the guidance of

Dr.B.Kishore Babu, Assistant Professor, for his persistent interest and co-
operation in the successful completion of this Project.

• I am grateful to Prof. K. Ramji, Co-ordinator, Centre for Nanotechnology

for his support for completion of this work.

• I express my deep sense of gratitude to Mr. K. Mohan, Mr. M.S.N.A Prasad

(Research Scholars-Dept. of Engineering Chemistry).
 ACKNOWLEDGMENT

• I take immense pleasure to express my deep sense of gratitude to

Dr.A.M.Umabala, Head of the Department - Department of Inorganic and
Analytical Chemistry, Andhra University for UV characterization facility.

• I am grateful to Sri K.Krishnamurthy Research Scholar - Dept. of

Engineering Chemistry IIT Hyderabad for XRD characterization.

• My sincere thanks to Mr.Rama Rao and Mr. Rajasheker (Research

Scholars) of AU for help in DC Characterization.
 ACKNOWLEDGMENT

• My deepest gratitude is to the almighty, and my Parents who have

been very caring and supportive to me all the time in all ways.

• I wish to expresses my sincere thanks to my classmates

Mr.A.Manikanta, Mr.B.Venkat, Mr.B.Lokesh, Ms.M.Sowmya Sree,
friends and persons who helped me directly and indirectly without
whom this project work would not have been completed successfully.
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