Fabrication of p-type CuO thin films using chemical bath deposition technique and

their solar cell applications with Si nanowires

Funda Aksoy Akgul and Guvenc Akgul

Citation: AIP Conference Proceedings 1815, 110002 (2017); doi: 10.1063/1.4976471

View online: http://dx.doi.org/10.1063/1.4976471
View Table of Contents: http://aip.scitation.org/toc/apc/1815/1
Published by the American Institute of Physics
Fabrication of p-type CuO Thin Films Using Chemical Bath
Deposition Technique and Their Solar Cell Applications
with Si Nanowires
Funda Aksoy Akgul1, a) and Guvenc Akgul2, b)
1
Physics Department, Ömer Halisdemir University, Nigde 51240, Turkey
2
Bor Vocational School, Ömer Halisdemir University, Nigde 51700, Turkey
a)
Corresponding author: fundaaksoy01@gmail.com
b)
guvencakgul@gmail.com

Abstract. Recently, CuO has attracted much interest owing to its suitable material properties, inexpensive fabrication cost
and potential applications for optoelectronic devices. In this study, CuO thin films were deposited on glass substrates using
chemical bath deposition technique and post-deposition annealing effect on the properties of the prepared samples were
investigated. p-n heterojunction solar cells were then constructed by coating of p-type CuO films onto the vertically well-
aligned n-type Si nanowires synthesized through MACE method. Photovoltaic performance of the fabricated devices were
determined with current–voltage (I–V) measurements under AM 1.5 G illumination. The optimal short-circuit current
density, open-circuit voltage, fill factor and power conversion efficiency were found to be 3.2 mA/cm−2, 337 mV, 37.9 and
0.45%, respectively. The observed performance clearly indicates that the investigated device structure could be a promising
candidate for high-performance low-cost new-generation photovoltaic diodes.

INTRODUCTION
Over the past decade, photovoltaic systems have progressed enormously with the implementation of
semiconductor nanowires in solar energy harvesting applications. One-dimensional Si nanostructures in the form of
nanowires have revealed a conspicuous promise for next-generation photovoltaic applications due to their interesting
optical and electronic characteristics including high surface-to-volume ratios, direct conduction pathway for charge
transport, intrinsic antireflection effect and thus high light absorption. Up to now, several fabrication methods for the
formation of nanowires on Si substrates have been developed [1]. Among them, metal-assisted chemical etching
(MACE) of Si substrates is a very easy and powerful solution-based route. Facile and relatively cheap process
equipment, adaptability to large area applications, controlled density and length, same crystal quality and uniform
doping type with pristine Si substrate can be major advantageous of MACE over other methods.
Tremendous efforts have been made by researchers to fabricate Si nanowires-based photovoltaic devices integrated
with different materials including metal oxide semiconductors. Copper(II) oxide (CuO) has emerged as a potential
complementary candidate for solar cell applications due to its suitable properties such as p-type conductivity, narrow
optical bandgap between 1.2-1.9 eV (ideal for sunlight absorption), high absorption coefficient over a substantial
portion of the solar spectrum, direct type bandgap structure and similar electron affinity to Si. A wide range techniques
have been employed to prepare CuO thin films [1].
In this study, photovoltaic characterization of CuO thin film/Si nanowires heterojunction structure was reported.
p-type CuO thin films were deposited via chemical bath deposition. Structural, optical, and electrical properties of the
prepared thin film samples were investigated as a function of post-deposition annealing temperature. n-type Si
nanowires were synthesized through facile and cheap MACE method. Finally, Si nanowires-based solar cells were
fabricated by coating CuO films onto Si nanowire arrays, and photovoltaic properties of the constructed heterojunction
structures were investigated.

Turkish Physical Society 32nd International Physics Congress (TPS32)

AIP Conf. Proc. 1815, 110002-1–110002-4; doi: 10.1063/1.4976471
Published by AIP Publishing. 978-0-7354-1483-9/$30.00

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 EXPERIMENTAL
Fabrication of Si nanowires-based heterojunction solar cells was achieved in two steps. In the first, highly oriented
Si nanowire arrays were produced by typical MACE method, as discussed in a previous work [2]. One side polished
n-type Si (100) wafers of 1-10 Ω.cm resistivity were used. In the second fabrication step, thin CuO films were
deposited onto the as-grown Si nanowire arrays via chemical bath deposition in order to create three-dimensional p-n
heterojunctions structures. The solution for the deposition of CuO thin films was prepared by dissolving copper acetate
(Cu(CH3COO)2 . H2O, Merck, 99.98%) in ethanol. Afterwards, lactic acid (C3H6O3, 85%) and triethylamine (C6H15N,
99.95%) was added into the prepared solution. The solution was deposited directly onto the Si nanowire arrays by
chemical bath deposition. CuO thin films were also deposited onto pre-cleaned commercially available soda-lime
silicate glass slides for the characterization of the film properties. Si and glass substrates were dipped vertically into
CuO solution for 20 seconds, then dried on a hot plate at 150 °C for 3 minutes in air under ambient conditions.
Dipping/drying cycle was repeated as many times as desired in order to get sufficient film thickness. The device
fabrication was completed by the thermal evaporation of gold (Au) and silver (Ag) as ohmic front and back contacts,
respectively. Formation of ohmic-type contacts was achieved by subsequent annealing at 180 °C for 10 minutes.
X-ray diffraction (XRD) measurements were performed using a Rigaku Miniflex diffractometer with Cu Kα
radiation (λ = 0.154 nm). Optical properties of the thin film samples were analyzed using an optical setup [3]. Electrical
properties including carrier concentration and mobility were obtained from Hall Effect measurements by conventional
four-point dc Van der Pauw technique. Morphological examination of the fabricated solar cells was carried out by
Nova NanoSEM 430 model field emission scanning electron microscope (FESEM). The current-voltage (I-V)
characteristics of the fabricated solar cells were measured by LabVIEW controlled Keithley 2400 source meter and
tested with an AM 1.5G solar simulator controlled with Newport I-V test software.

RESULTS AND DISCUSSION

CuO thin film samples deposited onto glass substrates were annealed in a muffle furnace under atmospheric
conditions for 20 minutes at different temperatures varied between 200 and 600 qC to obtain films with better
properties. Structural properties of the as-deposited and post-annealed CuO films were evaluated through XRD
measurements. XRD patterns of the samples are shown in Fig 1(a).

FIGURE 1. XRD patterns of as-deposited and post-annealed CuO thin films (a) and average crystallite size and dislocation
density of CuO thin films as a function of annealing temperature (b).

As-prepared sample exhibits two distinct peaks, indicating polycrystalline structure. The first and second Bragg
diffraction peaks at an angle 2θ of 35.6q and 38.7 can be indexed to (-111) or (002) and (111) or (200) reflections,
respectively, indicating tenorite phase of CuO [4]. Sharpest XRD peaks were monitored for the thin film annealed at
600 ºC. The Rietveld method was applied to the collected diffraction data to derive structural parameters of CuO
samples. Variation of the average crystallite size and dislocation density with post-annealing temperature is
demonstrated in Fig. 1(b). The largest crystallite size of 554 Å was estimated when CuO thin film was annealed at

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600 ºC. The same thin film sample also exhibited the lowest value for the density of dislocations, as shown in Fig.
1(b). Obviously, thermal energy provided by annealing treatment leads to larger crystallite formation. The observed
increase in crystallite size could be correlated with the reduced amount of lattice imperfections in the crystalline
structure of CuO.
Spectral variation of the transmittance and reflectance of samples with the wavelength of the incident photon are
shown in Fig. 2(a) and Fig. 2(b), respectively. Highly absorbing thin films in the visible wavelength region were
obtained by applying chemical bath deposition method. In the near-infrared region, an average transmittance was
found to be 73%. Relatively similar reflectance spectra with low intensity reflectivity were measured for the as-
deposited, 200 ºC-annealed and 400 ºC-annealed thin films. However, high-temperature annealing of CuO films at
600°C caused a rise in the intermediate region of the reflectance curve. Larger crystallites formed at this temperature
could lead to enhanced light scattering and more reflection from the film surface. Tauc model was used for estimating
optical bandgap energy (Eg) of CuO thin films [5]. Eg of the as-deposited and annealed CuO films at 200 °C, 400 °C
and 600 °C was estimated to be approximately 1.77, 1.71, 1.54 and 1.45 eV, respectively. Determined bandgap
energies are consistent with the reported values of CuO thin films [6].

FIGURE 2. Transmittance (a) and reflectance (b) spectra of as-deposited and post-annealed CuO thin films.

Transport properties of CuO thin films were studied through Hall measurements. All investigated thin film samples
revealed p-type conductivity. Table 1 summarizes the obtained carrier concentration and mobility values for as-
deposited and post-annealed films. Experimental results indicate that the electrical properties of the post-annealed
CuO films are substantially improved by annealing process compared to as-deposited sample.
TABLE 1. Electrical properties of as-deposited and post-annealed CuO thin films.
Samples Carrier concentration (cm-3) Mobility (cm2 V-1s-1)
As-deposited 0.8u1013 1.42
200 ºC-annealed 1.15u1013 4.14
400 ºC-annealed 2.32u1016 10.26
600 ºC-annealed 5.13u1016 25.56

The optimal film characteristics were obtained at an annealing temperature of 600 ºC, based on the obtained results.
p-n heterojunction solar cells were constructed by coating of p-type CuO films onto the vertically aligned n-type Si
nanowires. Thereafter, fabricated devices were annealed at 600 ºC for 20 minutes. Cross-sectional SEM image of a Si
nanowires-based heterojunction device is provided in Fig. 3(a). The image evidently reveals that the deposited film
covers the surface of Si nanowires, and a continuous film forms at top of the nanowire arrays. As shown in Fig. 3(a),
thin film packing increases from the bottom towards the top, resulting in the formation of matchstick-shaped CuO/Si
nano-heterostructures. In order to determine the electrical properties and photovoltaic characteristics of the constructed
nanowires-based devices, typical current-voltage (I-V) measurements were carry out in between -1 and +1 V. The
semi-logarithmic I-V characteristics measured both in the dark and under illumination at room temperature is shown
in Fig. 3(b). Significant rectifying behaviour with a rectifying ratio of 102 at ±1 V was observed in the dark. This result
confirms the successful formation of p-n heterojunctions within the device structure. Important diode parameters
including ideality factor (n) and dark saturation current (I0) were determined using the standard Shockley-diode model

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[7] and they were calculated to be 1.95 and 8.75 u 10-6 A, respectively. The best photovoltaic cell yielded a power
conversion efficiency of 0.45%. Other solar cell parameters such as short-circuit current density, open-circuit voltage,
fill factor, series resistance and shunt resistance were found to be 3.2 mA/cm−2, 337 mV, 37.9, 460.25 : and 98.46 :,
respectively. The obtained cell efficiency may not be high for a solar cell device, but it can be enhanced by the
optimizing the fabrication process of the nanowires, plasmonic effects, refinement of the physical properties of the
deposited CuO thin films, inserting a passivation layer in the cell structure and some contact issues.

FIGURE 3. Cross-sectional FESEM image (a) and semi-logarithmic I-V characteristics (b) of the fabricated Si nanowires-based
solar cells measured in the dark and illumination conditions at room temperature.

CONCLUSION
In this work, Si nanowires-based heterojunction solar cells were fabricated by depositing of p-type CuO films onto
the MACE-grown vertically well-aligned n-type Si nanowire arrays via simple and cost-effective chemical bath
deposition technique. Constructed solar cell structures demonstrated good p-n characteristics in the dark and
illumination conditions. Diode parameters of ideality factor and rectification ratio were calculated to be 1.95 and 102,
respectively. The optimal short-circuit current density, open-circuit voltage, fill factor and power conversion
efficiency were found to be 3.2 mA/cm−2, 337 mV, 37.9 and 0.45%, respectively. The observed performance clearly
indicates that the investigated device structure could be a promising candidate for high-performance low-cost new-
generation photovoltaic diodes.

ACKNOWLEDGEMENTS
F.A.A. and G.A. would like to give thanks to Research Projects Unit of Ömer Halisdemir University (The Project
Code: FEB 2014/25-BAGEP and The Project Code: FEB 2014/26-BAGEP) for the financial support.

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