Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-018-0322-4

Comparative study of effective photoabsorber CuO thin films prepared

via different precursors using chemical spray pyrolysis for solar cell
application
D. Naveena1 · T. Logu2 · R. Dhanabal1 · K. Sethuraman2 · A. Chandra Bose1

Received: 30 July 2018 / Accepted: 31 October 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Copper oxide (CuO) thin film is a promising material used as a photo-absorber layer in solar cell application due to its narrow
bandgap, low cost and high abundance. In this work, the CuO thin films have been prepared using various source materi-
als such as Cu(NO3)2·3H2O, ­CuCl2·2H2O and Cu(CH3COO)2·H2O by chemical spray pyrolysis technique. The XRD result
shows an increased crystallite size for Cu–N compared with Cu–Cl and Cu–A films. Good optical absorption in the visible
region is observed for all CuO films and Cu–N film illustrates high absorption coefficient in the order of 5.7 × 105 cm−1.
From SEM analysis, flake like morphology is observed for Cu–N and Cu–A films. The good electrical property i.e. high
conductivity (0.0611 S cm−1) and carrier concentration (2.287 × 1017 cm−3) is observed for Cu–N films. All CuO films
exhibit a single semicircle impedance nature and smaller diameter of semicircle corresponding to Cu–N film indicates low
electrical resistivity present in the sample. From I–V measurement, it is observed that the high current for Cu–N (16.6 µA)
than Cu–Cl (2.3 µA) and Cu–A (10.7 µA). All CuO films are photo-responsive under solar light exposure, which is due to
high absorption coefficient that leads to higher photocurrent (20.5 µA) for Cu–N film. The best solar cell performance is
obtained for Cu–N film which shows an efficiency of 0.31%. From the above results, we conclude that Cu–N is an optimum
precursor for fabricating CuO based thin film solar cell.

1 Introduction used as solar absorber, since it should have a suitable band-

gap and only few materials have been reported as absorber
Recently, there has been increasing interest in metal oxides layer for solar cell application. Among the metal oxide fam-
semiconductor due to its fascinating properties and wide- ily, copper oxide has drawn attention because of its nar-
spread research interests for the use of active layer in diverse row bandgap, low cost, chemically stable, non-toxic, facile
fields of nanoscale electronics, solar cells, sensors and pho- synthesis and earth abundant. Since, it is an ancient semi-
tocatalyst [1–4]. Mainly, in order to sustain the increasing conductor material still it attracts interest due to its sustain-
energy needs, low cost solar cells are fabricated based on ability. The most common stable phases of copper oxides
semiconducting metal oxide. Metal oxide semiconductor are: (a) cupric oxide or tenorite (CuO) which has mono-
occupies a most significant role in the fabrication of solar clinic crystal structure, (b) cuprous oxide or cuprite (­ Cu2O)
cells and mainly used as transparent conducting oxides which has a cubic structure with lattice constant of 4.2696 Å
(ZnO, ­TiO2), hole transporting material (NiO, M ­ oO3) and [9]. They are p-type semiconductor with the direct band-
light absorber material [5–8]. All metal oxides cannot be gap of 1.2–1.9 eV and 2–2.6 eV respectively. Particularly,
cupric oxide (CuO) has good light absorption coefficient
(> 105 cm−1) due to its narrow bandgap and superior charge
* A. Chandra Bose transport capability, so that it can be effectively utilized as
acbose@nitt.edu a photoabsorber layer in solar cell and also it can be easily
1 deposited as thin film at lower cost. In addition, due to its
Nanomaterials Laboratory, Department of Physics,
National Institute of Technology, Tiruchirappalli, exclusive properties it is used in various fields such as photo
Tamil Nadu 620 015, India transistors, photodiodes and transparent electrodes in flat-
2
School of Physics, Madurai Kamaraj University, panel displays, IR detectors anti-reflection coatings and solar
Madurai 625 021, India thermal applications [10, 11]. Numerous methods have been

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 Journal of Materials Science: Materials in Electronics

followed for the deposition of CuO thin films such as elec-

tro deposition, chemical vapour deposition, SILAR, sput-
tering, spray pyrolysis, spin coating, thermal evaporation,
etc [12–17]. Besides of various thin film deposition tech-
niques, we used chemical spray pyrolysis method because
of its advantages such as scalability of the process, facile,
reproducibility, easiness of doping, control of thickness
and opportunity of multilayer deposition. However, there
are many reports available on the deposition of CuO thin
films using chemical spray pyrolysis technique, but to our
knowledge no one had explained in detail by varying the
precursors of copper. In this manuscript, we have used three
different precursors such as copper nitrate, copper chloride
and copper acetate, without altering any physical parameters
they are successfully deposited on glass substrates using
indigenously constructed chemical spray pyrolysis tech-
nique. The structural, morphological, optical, and electrical Fig. 1  Schematic diagram of chemical spray pyrolysis setup
properties of CuO prepared using various precursors were
compared and effectively discussed in detail. In addition,
we fabricated solar cell of soda lime glass (SLG)/indium substrate which was controlled at an optimum temperature
doped tin oxide (ITO)/n-zinc oxide (n-ZnO)/p-copper oxide of 300 °C for all three different precursors. The substrate
(p-CuO)/molybdenum (Mo) configuration using three pre- temperature was maintained using a temperature control-
cursors of copper oxide as absorber layer and their efficiency ler. In each deposition the nozzle to substrate distance was
is calculated. fixed at 24 cm and 50 mL solution was sprayed at a rate
of 1 mL min−1. Compressed air was used as a carrier gas
which allows the precursor solution to pass through the
2 Experimental section nozzle. The nozzle with 0.2 mm atomizes the given pre-
cursor solution. The aerosol underwent evaporation, sol-
2.1 Chemicals ute condensation and thermal decomposition on reaching
towards the heated substrate and gets deposited [18]. The
Copper(II) nitrate trihydrate (Cu(NO3)2·3H2O), copper(II) probable mechanism that takes place on the heated surface
chloride dihydrate ­(CuCl2·2H2O), copper(II) acetate mono- for the formation of CuO thin films using different precur-
hydrate (Cu(CH3COO)2·H2O) were purchased from Merck, sors are given below Eqs. (1–3).
India. Indium tin oxide (ITO) was purchased from Sigma
(1)
( )
Aldrich. All the chemicals were of analytical grade and Cu NO3 2 ⋅ 3H2 O + H2 O → CuO + 2HNO3 + 3H2 O
used without any additional purification. Double distilled
(DD) water was used as solvents in all experiments. CuCl2 ⋅ 2H2 O + H2 O → CuO + 2HCl + 2H2 O (2)
( )
2.2 Deposition of copper oxide thin film (CuO) Cu CH3 COO 2 ⋅ H2 O + H2 O → CuO + 2CH3 COOH + H2 O
(3)
The copper oxide thin films were deposited on glass sub- From the above equations, the precursor aerosol from
strate by homemade chemical spray pyrolysis unit using the nozzle undergoes evaporation. The CuO precipitate
different precursors (Fig. 1). An aqueous solution of 0.1 M melts and vapor diffuses on the heated substrate at 300 °C
of Cu(NO3)2·3H2O, ­CuCl2·2H2O and Cu(CH3COO)2·H2O to form CuO thin films. In the middle the byproducts
is used as precursors. Each precursor was dissolved indi- ­(2HNO3, 2CH3COOH, 2HCl) that were formed during the
vidually in 50 mL of DD water with same molar concen- reaction have lower melting point. It gets evaporated with
tration of 0.1 M and allowed to stirrer for 15 min to attain the solvent before reaching the substrate. Finally, uniform
a homogenous and clear solution. Prior to film deposi- blackish CuO thin films for three different sources such
tion, the glass substrates were washed thoroughly with as Cu(NO3)2·3H2O, ­CuCl2·2H2O and Cu(CH3COO)2·H2O
soap solution and then cleaned in acetone and DD water were obtained and it was named as Cu–N, Cu–Cl and Cu–A
for 20 min in an ultrasonic cleaner and dried in air. The respectively.
precursor solution was sprayed onto a preheated glass

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Journal of Materials Science: Materials in Electronics

2.3 Fabrication of SLG/ITO/n‑ZnO/p‑CuO/Mo solar

cells

To fabricate SLG/ITO/ZnO/CuO/Mo thin film solar cells,

the ITO with size of 2.5 mm x 2.5 mm was used as front
contact. Using spray pyrolysis technique, the n type ZnO
(SLG/ITO/n-ZnO) with thickness ~ 200 nm was depos-
ited and used as window layer. Subsequently, p type CuO
(SLG/ITO/n-ZnO/p-CuO) with thickness of 600 nm was
coated on the n-ZnO and used as absorber layer. Finally,
Mo with thickness ~ 100 nm (to be used as back contact of
the solar cells) was deposited on SLG/ITO/n-ZnO/p-CuO/
Mo using Electron beam evaporation technique. Molybde-
num metal was used to deposit Mo films on the p type CuO
thin film by electron beam evaporation method (Hind High
Vacuum electron beam evaporation Unit-Model BC-300
8 KW Electron Beam Gun 270 bent beam with 4 source
EB gun power supply with 40 mA) at room temperature.
The distance between the source and substrate was main- Fig. 2  XRD patterns of CuO thin films prepared using different pre-
tained at 12 cm. The chamber pressure was retained at cursor solutions
6 × 10−6 mbar. Molybdenum metal was taken in a graphite
crucible and evaporated for 3 min at the rate of 5–6 Å s−1
which was maintained during the deposition. XRD pattern of CuO shows the polycrystalline nature with
monoclinic phase, which coincides with JCPDS No 45-0937.
2.4 Characterization The observed pattern shows two prominent peaks at 35.43°
and 38.57° which are assigned to (002) and (111) planes of
The phase identification of all the as-prepared CuO thin films CuO phase respectively. In addition, two other peaks were
was performed using Ultima III Rigaku X-ray diffractometer also observed for Cu–N precursor which is well matched with
(XRD) with scanning rate 4° min−1, step size 0.02° min−1, the JCPDS data of CuO. Also, no other impurity phases were
Cu Kα1 radiation, λ = 1.5406 Å in a 2θ range from 10° to observed in the prepared films. The average crystallite size for
80° at room temperature. The thickness of the prepared CuO, three different precursors is calculated using Scherrer formula
ZnO and Mo thin films was measured by Dektak 3030 Sty- [19] as shown in Eq. (4).
lus Profilometer. The surface morphology of the films was
investigated by scanning electron microscopy (FESEM, Nova k𝜆
D= (4)
NanoSEM 230). The optical absorption spectra of prepared 𝛽 cos 𝜃
films were measured by UV–Vis spectrophotometer (SHI-
where, D is the crystallite size; k is the shape factor (0.9); λ
MADZU UV-1800). The photoluminescence spectra were
is the wavelength used for measurement; β is the full width
recorded for the prepared thin films using a spectrofluorometer
half maximum. The calculated crystallite size is found to
(SHIMADZU-5301). The electrical properties were studied
be 22 nm for Cu–N film which is higher than the other two
using a Hall measurement set-up in the Van der Pauw configu-
precursor films. And it can be assumed that crystalline qual-
ration (Ecopia HMS-3000). The Solartron S. I 1260 Imped-
ity of Cu–N is better as it can be seen from stronger relative
ance/Gain phase analyser was used to study the frequency
intensity of the peaks, and the reduction of the FWHM with
dependent electrical properties. The photovoltaic measurement
increase in crystallite size [20]. The dislocation density and
was carried out using Keysight (B2910A precision source/
micro-strain of the films were calculated using the following
measure unit) with Oriel LCS-100 solar simulators.
equations [21, 22].
1
𝛿= (5)
3 Results and discussion D2

Figure 2 shows the XRD patterns of the as-prepared CuO 𝛽 cos 𝜃

𝜀= (6)
thin films prepared using different precursor solutions by 4
chemical spray pyrolysis technique. From the figure, all the

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 Journal of Materials Science: Materials in Electronics

where δ is the dislocation density, D is the crystallite size, The optical absorbance of CuO thin films prepared using
ε is the micro-strain and β is the full width half maximum various precursors is shown in Fig. 3. The measurement
of the prepared films. The dislocation density indicates the is carried out at room temperature in wavelength range of
presence of defect in the material. From Table 1, the Cu–N 200–1000 nm. All the films exhibit absorption edge near
film dislocation density is lower with increase in crystal- 880 nm and the majority light absorption is from the vis-
lite size and the microstrain values are also reduced, which ible region of the spectrum. The Cu–N shows high absorp-
indicates the reduction of lattice deficiency and exhibits high tion compared to other two precursors, this may be due
quality CuO films [23]. Hence, the outcome of the results to variations associated with morphology and crystalline
shows good crystallinity of CuO is achieved by Cu–N pre- nature of the prepared films. The absorption coefficient
cursor when compared to Cu–Cl and Cu–A precursors. For was also determined for the samples using the following
evaluating the degree of preferred orientation of the CuO Eq. (8) [26].
films, the texture coefficient (­ TC(hkl)) [24] was also calcu- ( )
1 1
lated using the following relation (7). ∝= (8)
t ln (T)
I(hkl)
I0(hkl) where α is the absorption coefficient, t is the thickness of
TC(hkl) = (7)
1
[
I
] the film, and T is the transmittance of the film. For Cu–N,
N
Σ I (hkl)
0(hkl)
the absorption coefficient value is 5.7 × 105 cm−1 which is
higher than the other sample. It may be due to availability
of high density of nanoflakes morphological structure in the
where I is the measured relative intensity of (hkl) plane,
Cu–N thin films. Nanoflakes structure leads to multiple light
­I0 is standard relative intensity of (hkl) plane and N is the
scattering at grain boundary, which shows higher number of
number of diffraction peaks. The TC was calculated using
photon absorption [27]. The optical energy gap E ­ g can be
(111) plane of the CuO thin films. It is observed that for
obtained from the intercept of (αhʋ)2 against photon energy
Cu–N and Cu–Cl films, the TC value is greater than unity
(hʋ), for the direct transition. The precise ­Eg value for differ-
which represents the preferential orientation along (111)
ent precursors are obtained from extrapolation of the straight
plane. The increase in preferential orientation is attributed
line portions to αhʋ = 0. The obtained ­Eg from the plot has
with increased number of crystallites along the plane [25].
slight variation with different precursors. The obtained band-
gap values are found to be 1.53, 1.44 and 1.48 eV for cop-
per nitrate, copper chloride and copper acetate respectively
which are consistent with the earlier report [28–30].
Table 1  Average crystallite size, dislocation density, microstrain and
texture coefficient value for different precursors Figure 4 represents the photoluminescence emission
spectra of CuO thinfilms taken at room temperature with
Sample Crystal- Dislocation Micro- Texture an excitation wavelength of 220 nm. The strong UV emis-
lite size (D) density (δ) strain (ε) coefficient
× 10−9 m × 1015 lines m−2 × 10−2 (111) sion peak at 363 nm is observed for all CuO precursor films
which ascribed to near-band-edge (NBE) emission and origi-
Cu–N 22.6 1.94 0.17 1.11 nates from electron–hole pair recombination in free exci-
Cu–Cl 15.3 4.23 0.22 0.96 tons [31]. It is observed that photoluminescence quenching
Cu–A 21.6 2.13 0.21 1.09 is more evident in Cu–N films and almost 60% of the PL

Fig. 3  a UV–Vis absorption

spectra of CuO thin films and
b Tauc plot for CuO thin films
prepared using different precur-
sors

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Journal of Materials Science: Materials in Electronics

clearly depicts that the morphology of the CuO thin film is

very sensitive to the different precursor solution. Figure 5a
shows the SEM image of Cu–N films. It shows flake-like
morphology with non-uniform distribution of the agglom-
erated particle over the entire surfaces that are intercon-
nected with each other. Figure 5b depicts the SEM image
of Cu–Cl film, in which homogenous spherical aggregates
with void free surface and uniform distribution of parti-
cles are observed. Figure 5c illustrates the SEM images
of Cu–A film which shows highly agglomerated particle
with flake-like morphology. This morphological differ-
ences in the prepared films may also depend upon the pH
of the precursor solution [33, 34]. However, the evolution
of byproducts like nitric acid, hydrochloric acid and ace-
tic acid (Fig. 6) formed during the growth of CuO films
lead to variation in the pH value of the prepared solution.
Hence, it is evident from XRD results the high crystal-
lite size is observed for Cu–N and Cu–A films due to its
Fig. 4  Photoluminescence spectra of CuO thin films prepared from flake-like morphology and it can absorb large number of
various precursors incident photons which enhances the absorbtion ability of
CuO thin films.
The Hall measurements were carried out for CuO thin
intensity is reduced when compared with Cu–Cl film. Hence, films using Van der pauw configuration. The variation of
the PL emission is directly related to the recombination of mobility, carrier concentration, conductivity and resistivity
photogenerated electrons and holes. So the low PL intensity as a function of precursor is shown in Fig. 7 and tabulated
for Cu–N precursor is due to the delay in recombination rate. in Table 2. The positive sign of the hall coefficient indi-
Thus for Cu–Cl, the intensity of the peak is higher which cates that all CuO precursor films show p-type conductiv-
indicates the recombination of electron–hole pairs and their ity which may be due to the presence of copper vacancies
lifetime of the photogenerated electrons is short. For Cu–N, [35]. Figure 7a shows the carrier concentration of CuO
it shows a lower intensity which suggests the annihilation of films prepared from different precursor, it evidently shows
electron–hole pairs recombination and improves the separa- that Cu–N film has higher (2.29 × 1017 cm−3) charge car-
tion efficiency and lifetime of photogenerated electrons and riers compared with other films [36]. The mobility of the
holes [32]. majority charge carriers is decreased for the films prepared
Figure 5 shows the SEM images of the CuO thin film from Cu–N and Cu–Cl precursor (Fig. 7b). This could be
prepared using various precursor solutions. The image ascribed to an increase of impurity scattering due to large

Fig. 5  SEM image of CuO film prepared from a Cu–N, b Cu–Cl and c Cu–A

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 Journal of Materials Science: Materials in Electronics

Fig. 6  Schematic representa-

tion of morphological evolution
under different source materials

Fig. 7  Variation of a carrier concentration, b mobility, c conductivity and d resistivity as a function of different precursors

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Journal of Materials Science: Materials in Electronics

Table 2  Electrical properties Sample Carrier concentra- Mobility Conductivity Resistivity Current Bandgap (eV)
and bandgap for various tion × 1017 ­(cm−3) ­(cm2 V−1s−1) (S cm−1) (Ω cm) × 10−6 (A)
precursors of CuO thin films
Cu–N 2.29 1.67 0.0611 16.37 16.6 1.53
Cu–Cl 1.94 0.32 0.0098 101.7 2.3 1.44
Cu–A 0.34 6.63 0.0358 27.88 10.7 1.48

number of charge carriers in the prepared films. For an effi- region (10 kHz–1 MHz), the value of Z′ corresponding to
cient usage of CuO thin film in device, the prepared film Cu–Cl and Cu–A is decreased and started to merge with Z′
should posses low resistivity and high conductivity. In our of Cu–N. This decreasing nature of Z′ value explains the
case CuO thin film prepared from Cu–N source shows high possible release of space charge in the film. Figure 8c shows
conductivity and low resistivity (Fig. 7c, d). The decrease the variation of imaginary part of impedance (Z″) as a func-
in resistivity (Fig. 7d) of CuO film from Cu–N source may tion of frequency. All the films show maximum Z″ (Z″ max)
be due to high crystalline nature as well as large number of value in the frequency region from 1 to 10 kHz. The Cu–Cl
charge carrier (2.29 × 1017 cm−3) in the prepared film. Car- film shows Z″ max at frequency 1 kHz, while Cu–A and
rier concentration, mobility, conductivity and resistivity of Cu–N show maximum peak at 10 kHz. This observed peak
the prepared film with different deposition techniques by shifting towards higher frequency region corresponds to the
different researchers [25, 36, 37] are given in Table 3. The presence of electrical relaxation process in the CuO thin
Cu–N based CuO thin film showed better electrical proper- films [40].
ties when compared to other deposition techniques. Finally Figure 9 shows the typical I–V characteristics of CuO
we conclude that high charge carriers, optimum mobility, thin films prepared using various precursor solutions. The
low resistivity and high conductivity nature of the CuO film electrical contacts were made using silver paste on both ends
prepared from Cu–N source will act as an effective absorber of the CuO film to act as contact electrodes. The DC input
layer for solid state solar cells in near future. was increased from − 5 to + 5 V in steps and subsequent
The charge transfer characteristics and frequency currents were measured. The observed linear I–V curve
dependant electrical properties were studied using imped- indicates the ohmic behaviour of the CuO films and the Ag
ance spectroscopy analysis. Figure 8a shows the complex electrodes. The measured current values for Cu–N, Cu–Cl
impedance spectra (cole–cole plot) of CuO thin films and Cu–A films at 4 V are 16.6 µA, 2.3 µA and 10.7 µA
measured at room temperature. It shows that single semi- respectively. Thus, Cu–N film has a higher current value at
circle is observed for all CuO thin films. Among them, the a given voltage when compared with other two films, this
observed semicircle with lower diameter for Cu–N film may be due to high conductivity which is analyzed from both
compared to Cu–A and Cu–Cl films indicates lower elec- Hall measurement and impedance spectra.
trical resistivity of the sample. In addition, the existence Figure 10 shows the photo-response behaviour of the
of single semicircle in the CuO thin films demonstrates CuO films investigated under illumination condition. Fig-
the presence of single polarization and it occurs due to an ure 10a shows the schematic representation of deposited
effective contribution of the grain interior [38]. The CuO films with 0.5 cm spacing of silver paste as electrical con-
film shows the dramatic variation in real part of imped- tacts and connected in series with a DC power supply. The
ance (Z′) with frequency as shown in Fig. 8b. The CuO difference between dark and illuminated current clearly
film prepared by Cu–N exhibits relatively lower Z′ value showed that the CuO thin film has good positive photo
in low frequency region (1 Hz–10 kHz) than Cu–Cl and response behaviour [41]. It is due to the absorption of pho-
Cu–A. This lowered Z′ value represents a possibility of tons which leads to the creation of free charge carriers
increase in the a.c conductivity [39]. At high frequency in the conduction band and/or in the valence band. Here,

Table 3  Comparison of carrier Materials Carrier Mobility Conduc- Resis- Method References
concentration, mobility, concentration ­(cm2 V−1s− 1) tivity tivity
conductivity and resistivity ­(cm−3) (S cm−1) (Ω cm)
of CuO thin films reported by
various works CuO 11.10 × 1017 0.38 0.007 14.91 DC sputtering [36]
CuO 13.53 × 1015 1 0.002 461 Nebulizer spray pyrolysis [25]
CuO 12.56 × 1015 0.60 – 821 Nebulizer spray pyrolysis [37]
CuO 2.29 × 1017 1.67 0.0611 16.37 Spray pyrolysis Present work

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 Journal of Materials Science: Materials in Electronics

Fig. 8  Electrical properties of a complex impedance spectra of CuO thin films and b variation of real part of impedance (Z′) c variation of imag-
inary part of impedance (Z″) with frequency

the photoconduction takes place by one of the subsequent (iv) deep level (located in the valence band) to conduction
mechanisms. (i) Band-to-band transitions, (ii) impurity lev- band transitions [42]. Compared with Cu–A and Cu–Cl
els to band edge transitions, (iii) ionization of donors, and (Fig. 10c, d), the higher photo response was observed for

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Journal of Materials Science: Materials in Electronics

Cu–N film (Fig. 10b). This result is caused by the Cu–N

film, exciting more number of photoelectrons under illu-
mination. It experiences the higher absorbance coefficient
(5.7 × 105), due to nanoflakes like morphology and good
electrical properties of the Cu–N films stimulate the good
photo-response.
The performances of fabricated solar cells using dif-
ferent precursors were investigated and also presented in
the Fig. 11. From the J–V characteristics, the observed
photovoltaic parameters such as open-circuit voltage
­(VOC), short circuit current density ­(JSC), fill factor (FF)
and power conversion efficiency (η) are shown in Table 4.
It is noted that for Cu–N solar cell, the observed V ­ OC,
­J SC and FF values are 0.319 V, 1.49 mA cm −2 and 66%
respectively which results η of 0.31%. However, in the
case of Cu–Cl, the observed ­VOC, ­JSC, FF and η values are
0.311 V, 0.99 mA cm−2, 64% and 0.22%, while 0.312 V,
Fig. 9  Typical I–V characteristics of CuO thin films prepared using 1.26 mA cm−2, 65% and 0.26% of ­VOC, ­JSC, FF and η are
various precursor solutions observed for Cu–A respectively. From these results, it is

Fig. 10  Schematic of the photoconductivity measurement and I–V characteristic curve in the dark and under the presence of light for CuO thin
films

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 Journal of Materials Science: Materials in Electronics

factor and efficiency when compared to other reports.

However, the conversion efficiency is much lower com-
pared to other conventional solar cell. It may be attrib-
uted to the defects states induced by the lattice param-
eters at the heterojunction, charge carriers recombination,
shorter minority carrier diffusion length. Therefore, fur-
ther improvement can be attained by removing lattice-
mismatch defects, introducing buffer layer between the
CuO and ZnO interface reduces the recombination losses
[46, 47].

4 Conclusion

CuO thin films were successfully deposited on glass sub-

strate using different precursors by chemical spray pyroly-
sis technique. The influence of various precursors of CuO
Fig. 11  J–V characteristics curves of CuO solar cell thin films on their structural, optical, morphological and
electrical properties was investigated deeply. The XRD pat-
Table 4  Photovoltaic parameters obtained from J–V characteristics of tern confirms that all films exhibit polycrystalline nature
CuO solar cell and higher crystallite size is observed for Cu–N film. The
Sample Jsc (mA cm−2) Voc (V) FF (%) η (%) optical absorption coefficient is higher for Cu–N compared
with Cu–Cl and Cu–A film. The bandgap values are cal-
Cu–N 1.49 0.319 66 0.31
culated to be 1.53, 1.44 and 1.48 eV for Cu–N, Cu–Cl and
Cu–Cl 0.99 0.311 64 0.22
Cu–A respectively. The Cu–N film efficiently lower the
Cu–A 1.26 0.312 65 0.26
recombination rate and raise the lifetime of photogenerated
charge carriers. The nanoflake like morphology increases
the absorption efficiency of the incident photons. Higher
concluded that performances of Cu–N solar cell is obvi- carrier concentration (2.287 × 1017 cm−3) with low electrical
ously higher than that of Cu–Cl and Cu–A. The observed resistivity and higher photocurrent (20.5 µA) is observed for
improvement in the J­ SC value of Cu–N could be due to Cu–N precursor film. The fabricated cell configuration of
its high electrical property (conductivity, carrier concen- Cu–N shows higher PCE of 0.31%. By considering all the
tration). In addition the flake like surface morphology factors, we conclude that Cu–N precursor is the judicious
allows the absorption of large number of incoming pho- choice for use as an effective photoabsorber layer in CuO
tons. Solar cell parameters like ­VOC, ­JSC, fill factor and based solar cell.
efficiency of prepared solar cell are compared with the
earlier reports [43–46] and are given in the Table 5. The
Cu–N based CuO thin film demonstrated enhanced fill

Table 5  Comparison of Junction formation Jsc (mA cm−2) Voc (V) FF (%) η (%) References
photovoltaic parameters of the
prepared solar cell with earlier CuO/ZnO 1.9 0.0028 0.25 0.0001 [43]
reports
CuO/ZnO 0.63 0.37 36.9 0.1 [44]
CuO/ZnO 0.40 0.19 0.23 0.02 [45]
Cu2O/ZnO 2.08 0.19 0.295 0.117 [46]
CuO/ZnO 1.49 0.319 66 0.31 Present work

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Journal of Materials Science: Materials in Electronics

Acknowledgements The authors are thankful to The Director, National 17. Y.F. Lim, C.S. Chua, C.J.J. Lee, D. Chi, Sol–gel deposited ­Cu2O
Institute of Technology, Tiruchirappalli, Tamil Nadu for providing and CuO thin films for photocatalytic water splitting. Phys. Chem.
Instrument facilities. Chem. Phys. 16, 25928–25934 (2014)
18. T. Logu, K. Sankarasubramanian, P. Soundarrajan, K. Rama-
murthi, K. Sethuraman, Materials design of n-type ­CuInS2 thin
films with reduction of Cu–Au. Phase using C ­ d2+ ions. J. Anal.
References Appl. Pyrol. 114, 293–301 (2015)
19. V. Gupta, A. Mansingh, Influence of post deposition annealing on
1. X. Duan, Y. Huang, Y. Cui, J. Wang, C.M. Lieber, Indium phos- the structural and optical properties of sputtered zinc oxide film.
phide nanowires as building blocks for nanoscale electronic and J. Appl. Phys. 80, 1063–1073 (1996)
optoelectronic devices. Nature 409, 66–69 (2001) 20. J.G. Quiñones-Galván, I.M. Sandoval-Jiménez, H. Tototzintle-
2. C.T. Chen, F.C. Hsu, Y.M. Sung, H.C. Liao, W.C. Yen, W.F. Su, Huitle, L.A. Hernández-Hernández, F. de Moure-Flores, A.
Y.F. Chen, Effects of metal-free conjugated oligomer as a surface Hernández-Hernández, E. Campos-González, A. Guillén-Cer-
modifier in hybrid polymer/ZnO solar cells. Sol. Energy Mater. vantes, O. Zelaya-Angel, J.J. Araiza-Ibarra, Effect of precursor
Sol. Cells 107, 69–74 (2012) solution and annealing temperature on the physical properties
3. M.E. Mazhar, G. Faglia, E. Comini, D. Zappa, C. Baratto, G. of sol–gel-deposited ZnO thin films. Results Phys. 3, 248–253
Sberveglieri, Kelvin probe as an effective tool to develop sensi- (2013)
tive p-type CuO gas sensors. Sens. Actuators B 222, 1257–1263 21. G.K. Williamson, R.E. Smallman, Dislocation densities in some
(2015) annealed and cold-worked metals from measurements on the
4. D. Shingai, Y. Ide, W.Y. Sohn, K. Katayama, Photoexcited charge X-ray Debye–Scherrer spectrum. Philos. Mag. 1, 34–46 (1956)
carrier dynamics of interconnected T ­ iO2 nanoparticles: evidence 22. K.V. Khot, S.S. Mali, N.B. Pawar, R.R. Kharade, R.M. Mane,
of enhancement of charge separation at anatase-rutile particle V.V. Kondalkar, P.B. Patil, P.S. Patil, C.K. Hong, J.H. Kim, J.
interfaces. Phys. Chem. Chem. Phys. 20, 3484–3489 (2018) Heo, Development of nanocoral-like Cd (SSe) thin films using
5. D.H. Kim, J.H. Park, T.I. Lee, J.M. Myoung, Superhydrophobic an arrested precipitation technique and their application. ‎New J.
Al-doped ZnO nanorods-based electrically conductive and self- Chem. 38, 5964–5974 (2014)
cleanable antireflecting window layer for thin film solar cell. Sol. 23. F.A. Akgul, G. Akgul, N. Yildirim, H.E. Unalan, R. Turan, Influ-
Energy Mater. Sol. Cells 150, 65–70 (2016) ence of thermal annealing on microstructural, morphological,
6. A. Bhaumik, A. Haque, P. Karnati, M.F.N. Taufique, R. Patel, K. optical properties and surface electronic structure of copper oxide
Ghosh, Copper oxide based nanostructures for improved solar cell thin films. Mater. Chem. Phys. 147, 987–995 (2014)
efficiency. Thin Solid Films 572, 126–133 (2014) 24. Y. Caglar, Sol-gel derived nanostructure undoped and cobalt
7. D.S. Ginley, C. Bright, Transparent conducting oxides. MRS Bull. doped ZnO: structural, optical and electrical studies. J. Alloys
25, 15–18 (2000) Compd. 560, 181–188 (2013)
8. W. Yu, L. Shen, S. Ruan, F. Meng, J. Wang, E. Zhang, W. Chen, 25. R.D. Prabu, S. Valanarasu, V. Ganesh, M. Shkir, S. Alfaify, A.
Performance improvement of inverted polymer solar cells ther- Kathalingam, S.R. Srikumar, R. Chandramohan, An effect of tem-
mally evaporating nickel oxide as an anode buffer layer. Sol. perature on structural, optical, photoluminescence and electrical
Energy Mater. Sol. Cells 98, 212–215 (2012) properties of copper oxide thin films deposited by nebulizer spray
9. A.S. Zoolfakar, R.A. Rani, A.J. Morfa, A.P. O’Mullane, K. pyrolysis technique. Mater. Sci. Semicond. Process. 74, 129–135
Kalantar-Zadeh, Nanostructured copper oxide semiconductors: a (2018)
perspective on materials, synthesis methods and applications. J. 26. A. Bhaumik, A.M. Shearin, R. Patel, K. Ghosh, Significant
Mater. Chem. C 2, 5247–5270 (2014) enhancement of optical absorption through nano-structuring of
10. S.B. Wang, C.H. Hsiao, S.J. Chang, K.T. Lam, K.H. Wen, S.C. copper based oxide semiconductors: possible future materials for
Hung, S.J. Young, B.R. Huang, A CuO nanowire infrared pho- solar energy applications. Phys. Chem. Chem. Phys. 16, 11054–
todetector. Sens. Actuators A 171, 207–211 (2011) 11066 (2014)
11. S. Muthukrishnan, V. Subramaniam, T. Mahalingam, S.J. 27. K.P. Ganesan, N. Anandhan, V. Dharuman, P. Sami, R. Pannersel-
Helen, P. Sumathi, Improved properties of spray pyrolysed CuO vam, T. Marimuthu, Electrochemically modified crystal orienta-
nanocrystalline thin films. J. Mater. Sci. Mater. Electron. 28, tion, surface morphology and optical properties using CTAB on
4211–4218 (2017) ­Cu2O thin films. Results Phys. 7, 82–86 (2017)
12. A. Mahmood, F. Tezcan, G. Kardaş, Photoelectrochemical char- 28. V. Saravanan, P. Shankar, G.K. Mani, J.B.B. Rayappan, Growth
acteristics of CuO films with different electrodeposition time. and characterization of spray pyrolysis deposited copper oxide
Int. J. Hydrog. Energy 42, 23268–23275 (2017) thin films: influence of substrate and annealing temperatures. J.
13. P. Markworth, X. Liu, J. Dai, W. Fan, T. Marks, R. Chang, Anal. Appl. Pyrol. 111, 272–277 (2015)
Coherent island formation of C ­ u2O films grown by chemical 29. S. Ghosh, D.K. Avasthi, P. Shah, V. Ganesan, A. Gupta, D.
vapor deposition on MgO (110). J. Mater. Res. 16, 2408–2414 Sarangi, R. Bhattacharya,. W. Assmann, Deposition of thin films
(2001) of different oxides of copper by RF reactive sputtering and their
14. K. Mageshwari, R. Sathyamoorthy, Physical properties of characterization. Vacuum 57, 377–385 (2000)
nanocrystalline CuO thin films prepared by the SILAR method. 30. M. Zhao, Y. Jiang, J. Lv, Y. Sun, L. Cao, G. He, M. Zhang, Z. Sun,
Mater. Sci. Semicond. Process. 16, 337–343 (2013) Microstructure, morphology and sunlight response of cuprous
15. S. Korkmaz, B. Geçici, S.D. Korkmaz, R. Mohammadighare- oxide thin films. J. Mater. Sci. Mater. Electron. 27, 1799–1804
hbagh, S. Pat, S. Özen, V. Şenay, H.H. Yudar, Morphology, com- (2016)
position, structure and optical properties of CuO/Cu2O thin films 31. Y.C. Chang, J.Y. Guo, C.M. Chen, H.W. Di, C.C. Hsu, Construc-
prepared by RF sputtering method. Vacuum 131, 142–146 (2016) tion of CuO/In2S3/ZnO heterostructure arrays for enhanced pho-
16. J. Morales, L. Sanchez, F. Martin, J. Ramos-Barrado, M. Sanchez, tocatalytic efficiency. Nanoscale 9, 13235–13244 (2017)
Use of low temperature nanostructured CuO thin films deposited 32. X. Zhao, P. Wang, Z. Yan, N. Ren, Room temperature photolu-
by spray-pyrolysis in lithium cells. Thin Solid Films 474, 133–140 minescence properties of CuO nanowire arrays. Opt. Mater. 42,
(2005) 544–547 (2015)

13
 Journal of Materials Science: Materials in Electronics

33. D. Perednis, L.J. Gauckler, Thin film deposition using spray 0.5Bi0.5Na0.5TiO30.5CaCu3Ti4O12 nano-composite synthesized
pyrolysis. J. Electroceram. 14, 103–111 (2005) by a modified solid state method. Mater. Sci. Semicond. Process.
34. A.V. Nikam, A. Arulkashmir, K. Krishnamoorthy, A.A. Kulkarni, 31, 386–396 (2015)
B.L.V. Prasad, pH-dependent single-step rapid synthesis of CuO 41. T. Logu, R. Raliya, S. Kavadiya, S. Palanivel, K. Sethuraman,
and ­Cu2O nanoparticles from the same precursor. Cryst. Growth P. Biswas, Hierarchical architecture of ­CuInS2 microsphere thin
Des. 14, 4329–4334 (2014) films: altering laterally aligned crystallographic plane growth by
35. S. Karle, D. Rogalla, A. Ludwig, H.W. Becker, A.D. Wieck, M. Cd and V doping. CrystEngComm 19, 6602–6611 (2017)
Grafen, A. Ostendorf, A. Devi, Synthesis and evaluation of new 42. N.V. Joshi, Photoconductivity: Art: Science & Technology, (Mar-
copper ketoiminate precursors for a facile and additive-free solu- cel Dekker, New York, 1990)
tion-based approach to nanoscale copper oxide thin films. Dalton 43. H. Kidowaki, T. Oku, T. Akiyama, Fabrication and characteri-
Trans. 46, 2670–2679 (2017) zation of CuO/ZnO solar cells. J. Phys. Conf. Ser. 352, 012022
36. A. Tombak, M. Benhaliliba, Y.S. Ocak, T. Kiliçoglu, The novel (2012)
transparent sputtered p-type CuO thin films and Ag/p-CuO/n-Si 44. P. Wang, X. Zhao, B. Li, ZnO-coated CuO nanowire arrays: fabri-
Schottky diode applications. Results Phys. 5, 314–321 (2015) cations, optoelectronic properties, and photovoltaic applications.
37. R.D. Prabu, S. Valanarasu, I. Kulandaisamy, V. Ganesh, M. Shkir, ‎Opt. Express 19, 11271–11279 (2011)
A. Kathalingam, Studies on copper oxide thin films prepared by 45. S. Hussain, C. Cao, G. Nabi, W.S. Khan, M. Tahir, M. Tanveer, I.
simple nebulizer spray technique. J. Mater. Sci. Mater. Electron. Aslam, Optical and electrical characterization of ZnO/CuO het-
28, 6754–6762 (2017) erojunction solar cells. Optik 130, 372–377 (2017)
38. A. Chithambararaj, N. Rajeswari Yogamalar, A. Chandra Bose, 46. J. Katayama, K. Ito, M. Matsuoka, J. Tamaki, Performance of
Hydrothermally synthesized h-MoO3 and α-MoO3 nanocrystals: ­Cu2O/ZnO solar cell prepared by two-step electrodeposition. J.
new findings on crystal-structure-dependent charge transport. Appl. Electrochem. 34, 687–692 (2004)
Cryst. Growth Des. 16, 1984–1995 (2016) 47. M.A. Hossain, M. Wang, K.L. Choy, Ecofriendly and nonvacuum
39. R. Dhanabal, A. Chithambararaj, S. Velmathi, A. Chandra Bose, electrostatic spray-assisted vapor deposition of Cu(In,Ga)(S,Se)2
Visible light driven degradation of methylene blue dye using thin film solar cells. ACS Appl. Mater. Interfaces 7, 22497–22503
­Ag3PO4. J. Environ. Chem. Eng. 3, 1872–1881 (2015) (2015)
40. L. Singh, I.W. Kim, B.C. Sin, A. Ullah, S.K. Woo, Y. Lee,
Study of dielectric, AC-impedance, modulus properties of

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