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Morphology, Bandgap, and Grain Size Tailoring in Cu₂O Thin

Film by SILAR Method

Article  in  IEEE Transactions on Nanotechnology · January 2015

DOI: 10.1109/TNANO.2014.2369438

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108
Morphology, Bandgap, and Grain Size Tailoring
in Cu2O Thin Film by SILAR Method
A. T. Ravichandran, K. Dhanabalan, A. Vasuhi, R. Chandramohan, and Srinivas Mantha
Abstract—Copper Oxide thin films have been deposited onto
glass substrate with different time for 30 cycles by successive ionic
layers by adsorption and reaction method. The layers were grown
with different immersion times such as 15, 20, 25, and 30 s, respec-
tively, employing copperthiosulphate aqueous solutions. Crystal
phases were attained in all dipping levels. Copper oxide is one of
the most promising candidates for nonstoichiometric p-type trans-
parent semiconducting oxide materials. Fourier transformation
infrared spectroscopy studies confirmed the formation of copper
oxide and the characteristic vibrational mode of CuO was iden-
tified. Both the structural and surface properties of copper oxide
thin films were improved with increase in the deposition time as a
result of which the optical absorption edge of copper oxide shifts
toward longer wavelengths, the optical bandgap energy vary from
1.43 to 1.96 eV. The crystallinity of the film is high with allow
the maximum nucleation process. The room temperature photolu-
minescence spectrum has also been taken to elucidate the optical
emission properties of these thin films.
Index Terms—Copper oxide, FESEM, optical properties, SILAR
method, thin film.
I. INTRODUCTION
ETAL oxides are important from both scientific and tech-
M nological perspectives. They present interesting oppor-
tunities for research. Especially thin films offer opportunities to
pursue structure property relations using controlled microstruc-
tures. Thin film oxides are extensively used to prove very strong
electronic correlations. Copper oxide is one of the metal ox-
ides in photovoltaic devices such as light emitting diodes [1]
Recently, researchers are very much interested in Cu2 O and
CuO [2] Cu2 O possess a simple cubic structure and the direct
band gap is approximately 2.17 eV [3], it’s a p-type semicon-
ductor with p-n heterojunction with different kinds of n-type
materials [4]. Among p-type semiconducting oxide materials,
the Cu2 O is one of the parent components like CuXO2 delafos-
ites (X = Al, Cr, B, In, Ga, Zn, KCL, etc.) [3]. Existing and
developing such a system in thin film form without any exter-
Manuscript received April 20, 2014; accepted October 31, 2014. Date of
publication November 11, 2014; date of current version January 6, 2015. The
review of this paper was arranged by Associate Editor Prof. G. Ramanath.
A. T. Ravichandran is with the PG and Research Department of Physics,
National College, Tiruchirappalli 620001, India.
K. Dhanabalan is with the Department of Physics, J. J College of Arts and
Science, Pudukkottai 622404, India.
A. Vasuhi is with the Department of Physics, H. H. The Rajah’s College,
Pudukkottai 622001, India.
R. Chandramohan is with the Department of Physics, Sree Sevugan Anna-
malai College, Devakottai 630005, India.
S. Mantha is with the Department of Electronics and Communication Engi-
neering, SASTRA University, Thanjavur 613401, India.
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TNANO.2014.2369438
1536-125X © 2014 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications standards/publications/rights/index.html for more information.
IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 14, NO. 1, JANUARY 2015
nal help and naturally occurring the mineral form of Cu2 O as
the starting material for the active layers in solar cells [4], and
devices operating in visible light regions [1]. Recently it has
been found that the efficiency of Cu2 O/ZnO heterojunction is
better than 2% [2] over in solar energy conversion average and
hence offers many potential applications in energy conserva-
tions [2]. Cu2 O thin film preparation uses different technique
like water splitting [5]–[8], energy conservation for solar energy
[9], [10] lithium ion batteries [11] and photocatalyst [12] with
kind of applications for various fields. The development of p-
type semiconductors is especially used to p-n junctions for solar
cells. Copper oxide (Cu2 O) is one of the most promising candi-
dates for non-stoichiometric p-type transparent semiconducting
oxide materials. The preparation technique varies depend upon
the applications. The SILAR technique is also known as mod-
ified chemical bath deposition (M-CBD) technique, it is very
useful to prepare nanostructure thin films at low cost and low
temperatures. All the films are investigated for their structural,
morphological and electrical properties based on the deposition
time.
II. EXPERIMENTAL PROCEDURE
Substrate cleaning is one of the important factors in the depo-
sition of thin films. Glass slides of 26 mm × 76 mm × 1 mm di-
mensions were used as substrates. These substrates were boiled
in concentrated chromic acid for 2 h, then cleaned with double
distilled water and finally rinsed in acetone before use in the
deposition of the films.
To prepare Cu2 O thin films onto glass substrates a SILAR
method was used. For the preparation of Cu2 O thin films cop-
per sulphate pentahyrate (CuSO4 .5H2 O), sodium thiosulfate
(Na2 S2 O3 .5H2 O) and sodium hydroxide (NaOH) were used
in an aqueous medium. 1.0 M NaOH solution as prepared in
the beaker and heated to 70 °C. A colorless solution of copper
thiosulphate was prepared by adding 0.1 M Na2 S2 O3 and 0.1 M
CuSO4 after constant stirring for 30 min. Formation of colorless
solution could be represented by the equation,
−
2 ↔ 2[Cu(S2 O3 )] + [S4 O6 ] .
2Cu2+ + 4S2 O3−
2−
The slide was immersed in NaOH solution at 70 °C by holding
the slide vertically using sample holder for 15 s. As a result OH−
ions from NaOH solution adhered to the surface of the substrate.
Second immersion of the substrate was performed in the copper
ion complex solution for 15 s. In the solution of thiosulfate
cuprite, the Cu (I) ions formed by dissociation equilibrium,
[Cu(S2 O3 )] ↔ Cu+ + S2 O2−
3 .
RAVICHANDRAN et al.: MORPHOLOGY, BANDGAP, AND GRAIN SIZE TAILORING IN CU2 O THIN FILM BY SILAR METHOD 109

Fig. 2. Variation of Particle size with increases of deposition time.

Fig. 1. (a) XRD studies of copper oxide thin films for different deposition
time on glass substrate.

They adhere to the substrate and react with (OH− ) ions present
on the surface to form Cu2 O by the reaction is
2Cu+ + 2OH− → Cu2 O + H2 O.
Again the substrates were immersed in double distilled water
for durations of 10 s, for the purpose of removing the unre- Fig. 3. FTIR spectra of copper oxide thin films on glass substrate for different
acted Cu+ and OH− ions that remove loosely bounded parti- deposition time.
cles from the substrates. This completes one cycle of the ion TABLE I
layer adsorption and reaction process. Successive cycles led to THE FTIR ASSIGNMENTS OF CU2 O THIN FILMS FOR VARIOUS DIPPING TIME
thin film deposition at the end of three immersions silvery in
reflection. Increasing the number of immersions will increase Sample Immersion FTIR Peaks Group Assignments
the thickness of films. Repeated immersions up to 30 cycles Time cm−1 and Class and Remarks
were employed. Similarly the deposition time is varied as 20, (Seconds)

25 and 30 s for 30 cycles. The resulting thickness of the films A 15 484 Napththalenes Out-of-plane ring
increases from 0.44 to 1.6 μm with increases of deposition bending
B 20 511 C–O–C in ethers C–O–C bend
time. The films were washed with double distilled water and C 25 499 C–N–C in amines C–N–C bend
air dried. D 30 711 OH in phenols OH out of Plane
deformation

III. CHARACTERIZATION TECHNIQUES

A. Structural Analysis TABLE II
XRD AND OPTICAL STUDIES OF COPPER OXIDE THIN FILMS FOR DIFFERENT
Fig. 1 shows the X-ray diffraction (XRD) patterns of copper IMMERSION TIMES
oxide thin films as-deposited on glass substrate for different
deposition times. The broad peaks of low intensity reveal that Sample Immersion JCPDS Particle Energy Band
time (seconds) size D (nm) gap (eV)
the films consist of coarsely fine grains that are nanocrystalline
in nature. The diffraction peaks at 2θ values equal to 35.57° A 15 77–0199 7.980 1.72
and 42.32° corresponding to (1 1 1) and (2 0 0) planes for B 20 30.96 1.43
C 25 58.01 1.96
cubic system (Standard data Card: JCPDS: 77-0199) and all D 30 08.40 1.83
other immersion times are given in Table II. The intensity of
the peaks enhanced and gradually the peaks shifted toward the
higher 2θ values with increases of the immersion time. This
result can be attributed to the improvement in crystallinity of cycles. Fig. 2 shows the variation of particle size with increases
the copper oxide thin films with increases of immersion time. of deposition time in seconds.
The mean crystalline size (D) of the films was calculated using
Scherrer’s formula and neglecting the peak broadening due to B. Fourier Transformation Infrared (FTIR) Analysis
residual stresses in thin films [13], The formation of copper oxide was further confirmed by FTIR
D = kλ/ß cos θ Spectroscopy (Model: Spectrum RXI, Make: Perkin Elmer).
The FTIR spectrum show relates in Fig. 3, the copper ox-
where “K” is the shape factor (K = 0.9 for near spherical ide nanocrystalline thin films for different immersion period.
grains), “λ” is the wavelength of the X-rays, “θ” is the Bragg’s The peaks 484, 511, 499 and 711 cm−1 which corresponds to
diffraction angle, and “β” is the full width at half- maximum of the characteristic stretching vibrations of Cu–O bond and the
the diffraction peaks(in radians). The mean crystalline size was corresponding assignments are in Table I. The regions below
found to be 26.3 nm that increase with the number of immersion 1500 cm−1 are caused by bending vibrations and the bonds
110
Fig. 4. PL spectrum of copper oxide thin films for various deposition time.
Fig. 5. UV-vis Pattern spectrum of Transmittance for varying deposition time
of copper oxide thin films.
resulting from the stretching vibrations of C–C, C–O and C–N.
In a spectrum, the number of bonding vibrations is usually more
than the number of the stretching vibrations.
The regions are usually, finger prints of the materials [14],
[15] The band at ࣈ1909 cm−1 corresponds to the stretching and
bending modes of hydroxyls of adsorbed water.
C. Photoluminescence (PL) Spectrum
Fig. 4 shows the room temperature PL spectra
(JobinYvon_Flurolog-FL 3-11) of Cu2 O thin films prepared
after 30 cycles with different immersion times. With increase in
the deposition time the PL peak position shifts towards higher
wavelengths. It can be attributed to the variations in the optical
band gap of the materials [16] All the films exhibit violet emis-
sion at 372 nm, blue emission at 431 nm and green emission
peak at 542 nm. The intensity of the peaks decreases (film-20 s)
and increases (film-25 and 30 s) with increase of immersion
time, which may be attributed to improvements in crystalline of
the film.
D. Optical Studies
The optical transmittance of the thin films was studied us-
ing UV visible spectrophotometer (model: Lambda 35, make—
perkin Elmer) wavelength range from 450–1100 nm, Fig. 5
shows a typical transmittance versus wavelength in nanometers.
The transmittance data can also be used to calculate band gap
and refractive index of the thin films, the highly varying trans-
mittance increases with increases of immersion time. From the
transmittance, copper oxide thin films is highly obey the solar
cells [17].
The absorption co-efficient “α” can be calculated with the
transmittance data [18] by,
A(λ) = −1/d ln (T /T o).
IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 14, NO. 1, JANUARY 2015
Fig. 6. A typical curve for computing band gap of copper oxide thin films for
various deposition time. The straight indicates that the band gap of thin films.
Fig. 7. Reflectance of copper oxide thin films for varying immersion time.
Here (T /To ) is the transmittance and d is the thickness of the
films. In order to calculate the optical band gap of the thin films,
we use the Tauc’s relationship as follows [19], [20],
Ahν = A(hν − Eg)υ .
Here hν is the photon energy and A is constant. The absorption
co-efficient is computed according to the above equations.
The calculated data fit to the curve shown in Fig. 6. The
straight line indicates the band gap of thin films 1.43 to 1.96 eV
with respective films as shown in Table II. Fig. 7 shows the
reflectance spectra of Cu2 O films and synthesize thermal oxida-
tion of copper. The reflectance spectra may be influenced by the
surface roughness of the films. In this case, all films are coated
under the same conditions and best for maximum immersion
time level. In thin film devices, the optical reflectance plays
a key role in energy conversion efficiency. Typically, the high
band gap Cu2 O layer can be employed in the top layers Cu–O
bottom layers on solar cells [21] From the result, the reflectance
spectra of Cu2 O thin films can be considered as a key parameter
in feasibility investigations of Cu2 O films for optical material
applications.
E. Refractive Index
It is necessary to give attention to the refractive index, when
the optical properties and the optical behavior of materials were
treated. The refractive index of the films was calculated using
the equation [22],

n = 4R/(R − 1)2 − k 2 − (R − 1)/(R − 1)
where R is the reflectance and K is the extinction co-efficient
defined as
K = αλ/4π
where λ is the wavelength and α is the absorption co-efficient.
RAVICHANDRAN et al.: MORPHOLOGY, BANDGAP, AND GRAIN SIZE TAILORING IN CU2 O THIN FILM BY SILAR METHOD
Fig. 8. UV refractive index spectrsdsum of copper oxide thin films for various
deposition time.
Fig. 9. FESEM Images of copper oxide thin film for with respective seconds
of (a) 15, (b) 20, (c) 25 and (d) 30 for immersion time.
The variation of refractive index with of the copper oxide
thin film with immersion time duration levels is shown in Fig. 8.
From the figure, it is seen that the refractive index of films is
very much related to the immersion time. The refractive index
of all films gradually decreased.
F. Morphological Studies
Fig. 9 shows the field emission scanning electron microscope
(FESEM) of Cu2 O thin films deposited on glass substance by
varying immersion time (like 15,20, 25 and 30 s) for 30-cycles.
The surface of the minimum immersion [15 s, Fig. 9(a)] film
revealed that the surface is made of homogeneous grains with
uniform spherical shape and with different radii. The size of the
spherical grain vary from 83 to 500 nm. When the immersion
time increases [20 s, Fig. 9(b)], the films surface is found to
be made of the spherical grains with less range of grain size
variation (130 to 26 nm) that gradually disappear and begin to
have needle shaped grains (length is 26 to 52 nm) that appeared
with increase in further dipping time. Again increases of the
immersion time [25 s, Fig. 9(c)] the nanorods appeared distinctly
separated and along with some agglomerated spherical grains.
The nanorods(width of the rod from 40 to 100 nm) are clearly
visible in the FESEM image. In the case of 30 s immersion
time [maximum, Fig 9(d)] the surface of the film is found to
be made of nano rods width decreases and increases of length
with the formation of dentrite–like structure typical of Cu2 O
111
architecture appeared. The width of the nano rods vary from 40
to 100 nm. However, the surface morphology of nanostructure
can be varied by varying the nucleation time of the precursor
solution. The nucleation rate is high and the crystallinity of
the film is high. From the FESEM result it is evident that,
the crystalline property of the film surface are increased with
increases of immersion time. This result is correlated with the
XRD studies.
IV. CONCLUSION
In this report, a good quality of copper oxide thin film was
successively deposited onto glass substrate using SILAR tech-
nique. FTIR revealed and confirm, the films Cu-O vibrated in
the range of 484 , 499, 511 cm−1 . From XRD, the crystallinity
of the films were increases with increases nucleation process
of the precursor solution (immersion of the film). FESEM, the
surface of the film initially found to be of spherical grains. The
spherical grains gradually disappear and appear as nanorods
with dentrite-structure of the film. It is attributed to the increase
of crystalline nature of the film with increase of immersion time.
The results indicate that the copper oxide film improved its crys-
tallinity with increase of immersion (nucleation processes) or
deposition time.
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