PJAEE, 17 (6) (2020)

INFLUENCE OF PURE AND Cd, Zn DOPED CuO THIN FILMS

USING SPRAY PYROLYSIS TECHNIQUE
1
S.J.Helen, 2R. Chandramohan
Department of Physics, Idhaya college for Women, Sarugani – 630411
1

2PG Department of Physics, Vidhyaa Giri College of Arts and Sciences, Puduvayal- 630180,
India
drhelenphysics@gmail.com

S.J.Helen, R. Chandramohan -- Influence Of Pure And Cd, Zn Doped Cuo Thin Films
Using Spray Pyrolysis Technique -- Palarch’s Journal Of Archaeology Of
Egypt/Egyptology 17(6), ISSN 1567-214x
Keywords: Spray pyrolysis, Doped Cu,; Thin Films, UV visible spectra, Optical band gap,
Hall measurement,

Abstract
Pristine (undoped) and Zinc, Cadmium doped CuO thin films are prepared using spray
pyrolysis technique over glass substrates. Influence of Zn andf Cd doping on the structural,
optical and electrical properties of CuO thin films is reported. X ray diffraction (XRD) analysis
exposes that the prepared pure and Zn & Cd doped CuO films show polycrystalline nature with
face centered cubic structure. Also, Zn& Cd doping radically increases the crystalline and
changes the crystallite size. SEM images illustrate that the surface morphology was formed by
grains which are rod shaped grains uniformly distributed. The transmittance of the prepared CuO
films recorded in the UV visible spectra show 40 to 70% in the visible region. The estimated
optical band gap values are blue shifted in Zn doped CuO thin films. Hall measurement shows
that the films are n-type semiconductor. Also, it is experiential that when the Cd doped, the
electrical resistivity is high when compared to Zn doped CuO thin films.

1. Introduction

Visible light constitutes a very small segment of the electromagnetic

spectrum that has a wavelength of 380-740 nm or energies in the range of 1.7-
3.3 eV. On irradiation with visible light, if there is no scattering or absorption
by an object, then the object can be considered as optically transparent. For
materials having a band gap larger than 3.3 eV, inter-band transitions do not
occur in the visible range of light, which allows the light to pass through

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without any difficulty to make them completely transparent. Consequently, to

achieve the desired optical transparency in a semiconductor material, the band
gap energy needs to be above 3.3 eV. In view of the fact that the energy (3.3
eV) is too large to transfer electrons into the conduction band at room
temperature, it is to be worth noting that the high optical transparency is not
matching with high electrical conductivity [1]. Thus, TCOs are considered as a
special group of materials that have both the optical transparency and high
electrical conductivity.
Copper oxides have been studied as semiconductor materials for a long
time because of their following advantages: non-toxic nature, abundance of
starting material (Cu), cheap production processing, and reasonably good
electrical and optical properties [2]. Cuprous oxide (Cu2O), a p-type
semiconductor with a direct band gap of 2.0 eV, is one of the materials feasible
for fabricating of thin film solar cells due to its high absorption coefficient in
the visible range and large hall mobility (usually > 10 cm2/Vs) . Cu2O
crystallizes in the cuprites structure, formed by a Body centred cubic (bcc)
array of oxygen atoms with metal atoms inserted between two consecutive
oxygen layers, in such a way that each oxygen atom is surrounded by a
tetrahedron of copper atoms. Different methods are employed to prepare CuO
thin film such as, sol-gel, thermal evaporation, sputtering, chemical bath
deposition, spray pyrolysis, spin coating and vacuum evaporation [3.4]. Thin
films are generally coated on materials called substrates to obtain the desired
properties. The substrates provide the mechanical support without altering its
characteristic features. Thin films of metals, semiconductors, insulators or
dielectrics are prepared by various preparative techniques along with
innovative methods to deposit materials with reproducible physical properties.
The present work reports the synthesis using spray pyrolysis and
characterization of pristine CuO and Cd & Zn doped CuO thin films.

2. Experimental details

Copper acetate was dissolved in distilled water at room temperature and

water was used as solvent to synthesize CuO thin films using the spray
pyrolysis technique. Cadmium acetate and zinc acetate were used as the source
for Cu & Zn doping and the concentration of the dopant was taken as 3-wt% of
both the compound. The glass substrate was placed at the distance of 18 cm
from the nozzle tip. For all the films, 3 ml/min flow rate and 300 °C parameter
is adopted for spraying on the substrate. The substrate was allowed to be in a
heated atmosphere to certain temperature before spraying. X-ray diffraction
analysis was performed using X ray diffractometer (Shimadzu X-600) in order
to study the crystal structure of the spray pyrolysed thin films. The surface
morphology was recorded using scanning electron microscope (SEM, JEOL 2
– JSM 6000). Optical transmission spectra of all the deposited films were
obtained using UV-VIS spectrophotometer (UV Vis NIR JASCO V-670). The
electrical studies were carried out using Hall measurement system (ECOPIA,
HMS 3000).

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3. Result and Discussion

3.1 X-ray diffraction

The x-ray diffraction patterns were recorded for the undoped and Cd &
Zn doped CuO thin films as shown in figure 1. The peaks corresponding to
planes (111) and (200) are seen on the diffractograms of the CuO films which
display the random orientation of the crystallites having the polycrystalline
nature. The CuO: Cd & Zn X- ray diffraction patterns are well matched with
JCPDS Card No: 05-0640, which represents the cubic structure. It is observed
that the intensity of the peak at 2θ ~ 33° corresponding to (200) plane
increases, with the increase in Cd and Zn dopant concentration. The slight
lower angle shift in the preferential orientation of the (200) plane may be
attributed to the imperfection in crystalline structure by the excess of Zn and
Cd incorporation into the CdO lattice structure [5].

Fig. 1. XRD patterns of undoped Cd & Zn doped CuO thin films

Table 1: Structural parameters of undoped and Metal (Cd, Zn) doped CdO thin films
Microstrain Dislocation
2θ (200) FWHM D (Scherrer)
Samples (x10-3) density
Degree (radian) (nm)
using formula (x1015)m-2
CuO 38.20 0.73 11 3.009 7.529
Cd doped
11
CuO 38.16 0.751 3.096 7.971
Zn doped
2812
CuO 38.28 0.698 2.877 6.880

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The grain size D values were determined by using the Scherrer’s formula given below

0.9 𝜆
D = 𝛽 cos 𝜃

where D is grain size, λ is the X-ray wavelength, β is the angular line width of half maximum
intensity, and θ is the Bragg’s angle[6]. Table 1 shows the values of structural parameters
deduced from XRD pattern of CdO thin films for Cd, Zn doped samples.

3.2 Morphological Studies

(a)

(b) (c)

Figure 2 SEM images of (a) undoped (b) Cd doped CuO (c) Zn doped CuO thin films

The SEM images were shown in figure 2. Pristine CuO reveals that the
surface is smooth and the spherical particle like grains are seen in equally
spread through the substrate. In Cd incorporated samples a rough surface with
flowery grains made of spherical particles are in bigger size. Zn doped CdO
films seen that the surface of the particles are not equally spread on the
substrate.

3.3 Optical Properties

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Figure 3 Optical transmittance of undoped and Cd, Zn doped CuO thin films

Optical transmittance spectra of undoped and Cd Zn doped CuO thin

films were recorded between of 300 to 1000 nm and is presented in figure 3. In
the visible region the transparency is maximum for undoped films. However, as
the metal doping level increase, the optical transparency beyond 700 nm
increases for pure CdO thin films is table and remain 70%. But with doping
this region shows on increase in transmittance. Zn doping records the highest
transparency in the region. For metal dopant the increases in the transmittance
may be accounted by the absorption of free carriers [9]. Generally the energy
bandgap value depends on crystal structure of the films and the arrangement
and distribution of atoms in the crystal lattice. The absorption coefficient and
the incident photon energy are related by the equation [9]
(αhν)1/N = A (hν-Eg)

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Figure 4 Energy bandgap of undoped Cd and Zn doped CuO thin films

Where α is absorption coefficient, A is constant, Eg is the band gap of

the material and the exponent N depends on the type of transition, N = 1/2, 2,
3/2, and 3 corresponding to allowed direct, allowed indirect, forbidden direct
and forbidden indirect respectively [7]. The determination of Eg was by
extrapolating the linear portion of the curves until they intercept the photon
energy axis [5]. The allowed direct transition bandgap values vary from 2.45 to
2.67 eV in fig 4. This suggests a band gap tailoring in the region between 2.4 to
2.7 eV by metal doping.

3.4 Electrical Studies

The electrical studies of undoped and Cu, Zn doped CdO thin films is
shown in the figure 5. Pure CuO has high conductivity. Cd doped CuO reveals
that the films show high conductivity owing to favourable morphology made of
conductive grains. Zn doped CdO has low conductivity due to high resistivity
and presence of voids in the morphology.

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Figure 5 Electrical studies of undoped and Cd & Zn doped CuO thin films

4.Conclusion

Pure, Cd and Zn doped CuO thin films are prepared using spray pyrolysis technique on
glass substrates. The prepared thin films were characterized for structural, optical and electrical
properties and the results are presented. XRD reveals that the films are polycrystalline nature
with cubic structure. SEM images show that the films have smooth surface made of spherical and
near spherical grains. Metal doping enables a flowery grain formation. Optical studies reveal that
pure CuO films have high transparency in the visible region and optical band gap has decreases
compared to undoped CuO thin films. The electrical studies reveals that Cd doped CuO has high
conductivity. The properties are correlated with structural and morphological features

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