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Journal of Thin Films, Coating Science Technology and Application

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 Journal of Thin Films, Coating Science Technology and Application
ISSN: 2455-3344 (Online)
Volume 4, Issue 1
www.stmjournals.com

Effect of Spray Pyrolysis on the Properties of Chemically

Sprayed CuO: Al Thin Films
1, 1 2 3 4
S. Muthukrishnan *, Venkat Subramaniam , T. Mahalingam , S.J. Helen , P. Sumathi
1
Department of Electronics, PSG College of Arts and Science, Coimbatore, Tamil Nadu, India
1
Department of ECS, Karpagam University, Coimbatore, Tamil Nadu, India
2
Department of Physics, Alagappa University, Karaikudi, Tamil Nadu, India
3
Department of Physics, Karunya University, Coimbatore, Tamil Nadu, India
4
Department of Physics, Rathinam Institutions, Coimbatore, Tamil Nadu, India

Abstract
CuO: Al thin films were grown from 50 ml of spray solution on glass substrates by chemical
spray at Ts=400°C using solution spray doping percentages of 0, 4, 5 and 6%. Copper acetate
and aluminium chloride were used as Cu and Al sources, respectively. Independent of solution
spray rate, the crystallites in CuO: Al films grow preferentially in the (201) plane , parallel to
the substrates. The spray pyrolysis solution are using different percentages of influences in the
structural properties, surface morphology, electrical properties are studied. The carrier
concentration increases from 2.1019 to 1.1020 cm-3 when spray rate is increased from 0 to
3%, independent of film thickness, the carrier mobilities are always lower in slowly grown
films. Sprayed CuO: Al films transmit 60 –80% of the visible light while the increase and
decrease in doping carrier concentration.

Keywords: Thin film spray pyrolysis, XRD, optical properties, electrical properties

*Author for Correspondence E-mail: s.muthukrishnan@rediffmail.com

INTRODUCTION approximately 0, 4, 5 and 6% solution and

Copper oxides and aluminium chloride are
semiconductors that have been studied for
several reasons such as the natural abundance of
starting material copper and aluminium (Cu: Al);
the easiness of production by Cu: Al oxidation;
their non-toxic nature and the reasonably good
electrical and optical properties of CuO: Al.
CuO: Al has been established in a number of
applications like gas sensors [1], solar
photovoltaic [2], lithium ion electrode etc. There
are various established ways of fabricating CuO:
Al thin films like spray pyrolysis spin coating,
dip coating, and SILAR [3] to name a few.
EXPERIMENTAL
The spray pyrolysis method of solution:
chemicals used for the preparation were
copper acetate of aluminium chloride
(Al(Cl3)3.9H2O) of analytical grade from the
3
micro slides of 75×25×1 mm which were
used as substrates for copper oxide and
aluminium chloride film coating. The copper
oxide and aluminium chloride complex
solution was prepared by adding
could be represented by Eq. (1):
(1)
(CH3CuO)2CuAl3.H2O⇔CuO+CuOAl
In the solution of copper acetate and aluminium
chloride, ions present on the surface form CuO:
Al, by the reaction, complete one cycle of the ion
layer adsorption and reaction process. Successive
cycles lead to thin film deposition [4]. At the end
of four doping percentages of cycles, the thin
film appeared silvery in reflection [5]. Increasing
the number of doping percentages, coated in the
spray pyrolysis solution will increase the
thickness of the films. The films were washed
well with distilled water and dried. The films
were coated in 400°C temperatures from the
doping percentages of 0, 4, 5 and 6%. The spray
pyrolysis coating process was done in a furnace
with temperature control.
RESULTS AND DISCUSSION
XRD patterns for CuO: Al thin films synthesized
at substrate temperature of 300°C are shown in
Figure 1. The diffraction peaks observed at 2θ
values of 35.23 and 38.53° correspond to the
diffraction lines produced by

JoTCSTA (2017) 1-5 © STM Journals 2017. All Rights Reserved Page 1
Effect of Spray Pyrolysis on CuO: Al Thin Films Muthukrishnan et al.

(201) and (200) planes of the face-centered
cubic structured CuO: Al (JCPDS card No.
03-1005). Crystallite size of the prepared
CuO: Al thin film was determined from the
strongest peak of (201) for every XRD
pattern using Scherrer formula [6].
The (200) surface of CuO: Al thin film is
energetically the most stable and the
predominant monoclinic crystal face found in
polycrystalline samples. It is observed from
Figure 1 that the diffraction peak positions are
identical for all the CuO thin films, obtained at
the substrate temperature of 400°C, indicating
the formation of cubic phase CuO: Al in all the
cases. Although (201) and (200) reflections are
present, for CuO: Al,
The lattice constants of the CuO thin films are
found to be: a=1.5405 Å and b=2.4506 Å and are
in good agreement with the standard JCPDS data
for cubic structured CuO: Al. It is
observed in the XRD patterns that the intensity
of the peaks increases [7]. For peak (111), the
calculated values of the crystallite size for the
CuO: Al thin films are presented in Table 1.
It is seen in the Table 1 the crystallite size
increases when the substrate temperature is
exactly 400°C and then decreases. For CuO: Al,
there are many dangling bonds related to the
copper and/or oxygen defects at the grain
boundaries. As the result, these defects are
favourable for the merging process to form larger
CuO: Al grains while increasing substrate
temperature [8]. It implies that the crystallinity of
the CuO: Al thin films are improved at higher
substrate temperatures. This may be due to
gaining enough energy by the crystallites to
orient in prober equilibrium sites at higher
substrate temperatures, resulting in the
improvement of crystallinity and degree of
orientation of the CuO thin films [9].

Fig. 1: XRD Patterns of CuO: Al Thin Film Synthesized at Various Weight Percentages.

Table 1: Crystallite Size for the CuO Thin Films at 300°C Substrate Temperature.
Percentage D(Scherrer) Microstrain Dislocation Density Texture S tacking Fault
-3 17 -2
Doping (nm) (×10 ) (×10 ) Lines m Coefficient Probability (α)
0 3 0.217 3.242 0.032 0.1432
4 5 1.563 1.035 0.356 0.3019
5 6 3.128 7.126 4.123 0.2679
6 7 4.716 8.671 5.012 0.4211

JoTCSTA (2017) 1-5 © STM Journals 2017. All Rights Reserved Page 2
Journal of Thin Films, Coating Science Technology and Application
Volume 4, Issue 1
ISSN: 2455-3344 (Online)
Texture coefficient [TC (h k l)] is used to
quantify preferential orientation of (200)
plane in CuO thin films using the well
known relation [10]:
TC  I /I
( hkl ) o ( hkl )
hkl
N 1  (I /I
n ( hkl )
Where, I (h k l) is the measured intensity and IO
(h k l) is the standard intensity from JCPDS
data file and N is the number of diffraction
peaks. It is found that the value of the texture
coefficient is >2 for all the films which means
a well aligned crystal structure. The relation
between stacking faults probability with peak
shift Δ2θ is given by [11]:
The value α is lower for 1 and 2% Al doped
CuO thin films, which indicates that these
films have lesser faults compared with high
aluminium doped films.
Fig. 2: SEM Image of CuO: Al Thin Films
Coated at Various Weight Percentages.
Morphological Analysis
SEM images were recorded to examine the
surface morphology of the deposited CuO: Al
thin films and the images obtained are shown in
Figure 2. The deposited films have islands of
different sizes and shapes, and their distribution
on the surface is quite homogeneous. These
could be the result of the chemical reaction
during the deposition. SEM micrographs reveal
the formation of particles with different shapes
and sizes, it seems appropriate to consider that
the particles which
JoTCSTA (2017) 1-5 © STM Journals 2017. All Rights Reserved
appear in scanning electron microscopy (SEM)
images are the grains of agglomerates [12].
(2)
o (hkl )
Fig. 3: Optical Transmittance at Various
(3) Weight Percentages.
Optical Properties
Figure 3 shows the combination of optical
transmittance spectra for all the four samples
of copper oxide thin films with 3 μm
thickness, coated at indium tin oxide
substrate temperature of 400°C. The curves
testify that the film surface is smooth with
wavelength longer than 600 nm. As seen
from the figure, the curves for oxide film as
coated for 400°C are distinctly similar.
Because of the crystallinity and higher
transparency, the copper oxide and aluminium
chloride films are suitable for optical analysis,
from which the absorption coefficient and
energy band gap may be determined. The
conversion of CuO into Al can also be shown
by the determination of the optical band gap.
For this, in the fundamental absorption region,
the optical absorption coefficient (α) was
-1
evaluated using α=(lnT )/t where t is the film
thickness and T is the transmittance [4]. The
best linear relationship is obtained by plotting
2
α against hυ, based on Eq. (4) below [13].
n/2
αhν=α(hν-Eg) (4)
Where, α is absorption coefficient, hν is
constant (independent from ν) and n the
exponent that depends upon the quantum
selection rules for the particular material.
The photon energy (hυ) for y-axis can be
calculated using Eq. (5).
E=hν=hν/λ (5)
Page 3
Effect of Spray Pyrolysis on CuO: Al Thin Films
-34
Where, h is Plank’s constant (6.626x10 ), c is
8
speed of light (3x10 ) and λ is the wavelength.
Fig. 4: Optical Bandgap Energy of Various
Weight Percentages.
Figure 4 shows the band gaps of films that
were obtained at various weight percentages
at constant temperatures at 400°C and thus,
thus, have the different morphologies are
known from this figure. However, the band
gap values are in the expected range for
copper oxide thin films [5]. Optical band gap
at 2.40 eV possess similar cuprite structure
with CuO: Al phase [14].
Electrical Properties
The effects of solution 0.1 m on the electrical
properties of CuO:Al thin films are shown in
Figure 5. Carrier concentration and carrier
mobility were calculated at room temperature
using the Hall coefficient and the resistivity
data [15]. The carrier concentration is derived
from the relation n=1/ne. RH, where RH is the
Hall coefficient and e is the absolute value of
the electron charge.
Fig. 5: Various Weight Percentages of
Mobility and Carrier Concentration.
JoTCSTA (2017) 1-5 © STM Journals 2017. All Rights Reserved
Muthukrishnan et al.
The carrier mobility (μ) is determined using
the relation μ=1/neρ, where ρ is resistivity .
It is seen that the electrical resistivity of the
films decreases with the substrate temperature
the carrier concentration increases from
12 1 -3
2.0×10 to 3.5×10 cm as the molar
concentration of 300°C substrate temperature
in Figure 6[14]. On the other hand, the
mobility increased with an decrease the
solution which indicates that the resistivity,
carrier concentration and mobility of CuO thin
films were sensitive to solution temperature.
Fig. 6: Various Weight Percentages of
Resistivity and Conductivity.
The initial decrease of resistivity with increase of
solution may be due to the variation of thickness
and grains having less electrical contact with
voids. Films with minimum resistivity and
maximum mobility thus correspond to an
optimum energy window to synthesize device
quality good films [15].
CONCLUSION
The consequence of variation in the precursor
concentration on the optical and electrical
properties was discussed for CuO: Al films
o
deposited at 400 C by spray pyrolysis
technique. The average crystallite size was
found to vary from 2 to 7 nm with increasing
in concentration. The Hall effect studies
unveiled a significant decrease in mobility,
conductivity and carrier concentration of CuO:
Al films for increasing concentration; and it
confirms that the grown films are P type in
nature with the carrier concentration range of
14 3
10 /cm . The optical absorption edges of all
films were kept in the range of 350 to 600 nm.
The extinction co-efficient (k) values of the
grown films indicated that the films are
Page 4
Journal of Thin Films, Coating Science Technology and Application
Volume 4, Issue 1
ISSN: 2455-3344 (Online)
stronger absorbing medium in the lower
wavelengths.
REFERENCES
1. Mariammal RN, Ramachandrana K,
Kalaiselvan G, et al. Effect of Magnetism on
the Ethanol Sensitivity of Undoped and Mn-
Doped CuO Nanoflakes. Appl Surf Sci. 2013;
270: 545–552p.
2. Hubner M, Simion CE, Tomescu-Stanoiu A,
et al. Influence of Humidity on CuO Sensing
with p-Type CuO Sensing with p-Type CuO
Thick Film Gas Sensors. Sens Actuators B.
2011; 153: 347–353p.
3. Manish Kumar Verma T, Vinay Gupta A.
A Highly Sensitive SnO2-CuO
Multilayered Sensor Structure for
Detection of H2S Gas. Sens Actuators B.
2012; 166: 378–385p.
4. Chandrasekaran S. A Novel Single Step
Synthesis, High Efficiency and Cost
Effective Photovoltaic Applications of
Oxidized Copper Nano Particles. Solar
Energy Materials Science. 2013; 109:
220–226p.
5. Amun Amri S, Xiao Fei Duan T, Chun-
Yang Yin A, et al. Solar Absorptance of
Copper-Cobalt Oxide Thin Film
Coatings with Nano-Size, Grain-Like
Morphology, Optimization and
Synchrotron Radiation XPS Studies.
Appl Surf Sci. 2013; 275: 127–135p.
6. Morales J, Sanchez L, Martın F, et al. Use of
Low-Temperature Nanostructured CuO Thin
Films Deposited by Spray-Pyrolysis in
Lithium Cells. Thin Solid Films. 2005; 474:
133–140p.
7. Madhav Singh A, Ranga Rao, Viresh
Dutta. Effect of pH on Structural and
Morphological Properties of Spray
Deposited p-Type Transparent
Conducting Oxide CuAlO2 Thin Films.
Mater Lett. 2008; 62: 3613–3616p.
8. Nasse SA, Afify HH, El-Hakim SA, et
al. Structural and Physical Properties of
Sprayed Copper–Zinc Oxide Films. Thin
Solid Films. 1998; 315: 327–335p.
9. Iqbal Singh RK, Bedi, Studies and
JoTCSTA (2017) 1-5 © STM Journals 2017. All Rights Reserved
Correlation among the Structural, Electrical
and Gas Response Properties of Aerosol
Spray Deposited Self-Assembled
Nanocrystalline CuO. Appl Surf Sci. 2011;
257: 7592–7599p.
10. Hong Youl Bae, Gyeong Man Choi.
Electrical and Reducing Gas Sensing
Properties of ZnO and ZnO-CuO Thin Films
Fabricated by Spin Coating Method. Sens
Actuators B. 1999; 55: 47–54p.
11. Aykut Nalbant, Ozlem Ertek, Ibrahim
Okur. Producing CuO and ZnO
Composite Thin Films Using the Spin
Coating Method on Microscope Glasses.
Mater Sci Eng B. 2013; 178: 368–374p.
12. Zhang HL, Zhao GY, Xua LZ. Preparation
of the Photosensitive Copper Complex and
CuO Film Pattern. Appl Surf Sci. 2013;
274: 397–400p.
13. Gulen Y, Bayansal F, Ahin BS, et al.
Fabrication and Characterization of Mn-
Doped CuO Thin Films by the SILAR
Method. Ceramics International
Processing. 2013; 39: 6475–6480p.
14. Mageshwari K, Sathyamoorthy R.
Physical Properties of Nanocrystalline
CuO Thin Films Prepared by the SILAR
Method. Mater Sci Semicond Process.
2013; 16: 337–343p.
15. De Los Santos Valladares L, Hurtado
Salinas D, Bustamante Dominguez A, et
al. Crystallization and Electrical
Resistivity of Cu2O and CuO Obtained
by Thermal Oxidation of Cu Thin Films
on SiO2/Si Substrates. Thin Solid Films.
2012; 520: 6368–6374p.
Cite this Article
Muthukrishnan S, Venkat Subramaniam,
Mahalingam T et al. Effect of Spray
Pyrolysis on the Properties of Chemically
Sprayed CuO: Al Thin Films. Journal of
Thin Films, Coating Science Technology
and
Application. 2017; 4(1): 1–5p.
Page 5
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