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Copper oxide based nanostructures for improved solar cell efficiency

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 Thin Solid Films 572 (2014) 126–133

Contents lists available at ScienceDirect

Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Copper oxide based nanostructures for improved solar cell efficiency

A. Bhaumik a, A. Haque a, P. Karnati a, M.F.N. Taufique a, R. Patel b, K. Ghosh a,⁎
a
Department of Physics, Astronomy and Materials Science, Missouri State University, Springfield, MO 65897, USA
b
Centre for Applied Science and Engineering, Missouri State University, Springfield, MO 65897, USA

a r t i c l e i n f o a b s t r a c t

Available online 7 October 2014 Resurgence of copper oxide based thin film solar cells demands exclusive methods of integrating various layers
with superior constituents for increased solar-electric conversion efficiency. Exceedingly optically active nano-
Keywords: structured phase mixture of copper oxides was synthesized by an energy efficient hydrothermal process. Com-
Solar cell prehensive structural and optical studies of these nanostructured copper oxides reveal its efficacy as a unique
Nanostructures solar cell material. Excellent solar cell characteristics have been observed when these nanopowders are integrat-
Nanotechnology
ed with ZnO/CuO based thin films. X-ray diffraction, Raman micro-scattering, scanning electron microscopy, en-
Photovoltaics
ergy dispersive X-ray spectroscopy, UV–vis spectroscopy, atomic force microscopy, and optoelectronic
measurements were employed to characterize these unified electronic devices. Solar cell measurements indicate
a considerable increase in short circuit current density (Jsc) and open circuit voltage (Voc) in the fabricated nano-
structure powder-thin film hybrid solar cell devices. The solar cell efficiency of these nanopowder-thin film de-
vices is found to be 2.88%. The physics behind this enrichment of solar cell properties has also been elucidated in
the study. Exhaustive Raman spectroscopic and photoluminescence studies prove that multi-phonon scattering
may play a major role for this enhancement. This integration of nanostructures with thin film solar cells can
evolve to a new direction in photovoltaic technology.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction Copper oxide based semi-conductors are widely studied as photo-

Developing high-end solar cell devices by implementing inexpen-
sive nanostructured materials and unique processing techniques is ur-
gently required to sustain the ever demanding energy need. Copious
new concepts for solar-electric energy conversion have been reported
which challenge traditional photovoltaic (PV) devices based on the
physics of semiconductor p–n junction diode [1]. Semiconductor mate-
rials used in solar cell technology are predominantly governed by their
energy band gap, optical properties, and charge carrier diffusion length
[2,3]. Highly efficient solar cell design necessitates optically active pho-
tovoltaic layers to enable nearly complete light absorption thereby in-
creasing the rate of electron–hole pair generation. Considerable efforts
have been made to develop state-of-the art nanostructured materials
that absorb better at long wavelengths, so far with little success [4,5].
An option to increase the absorption of visible solar spectrum is by in-
creasing the film thickness to improve the optical density. However,
this leads to detrimental effects of exceeding the electron diffusion
length through the nanoparticle network [6]. The ever demanding in-
creased solar cell efficiency and reduced material consumption urgently
require a decrease in active cell region thickness while preserving high
optical absorption.
voltaic materials [7], owing to its abundance and suitable optical prop-
erties for solar cell applications. These materials provide a unique
possibility to tune the optical and electronic properties from insulating
to metallic conduction, from band gap energies of 2.1 eV to the infrared
at 1.4 eV, i.e. right into the middle of the maximum efficiency for solar-
cell applications. Cupric oxide (CuO) and cuprous oxide (Cu2O) are
being widely used as a p-type semiconductor for designing solar cells
[8,9]. There are innumerous examples of copper oxide based PV devices
reported in literature, often prepared by using low-cost, solution-based
methods [10–12]. Predominantly, all of these devices are either bulk or
thin-film bilayer cells, and these types of cells suffer from the fact that
the optimal material length scales for optical absorption and carrier
extraction are contrary to one another. The use of nanomaterials repre-
sents a general approach to reduce both cost and size thereby improving
efficiency in photovoltaic cells [13,14]. The physical mechanism under-
lying high external quantum efficiencies for photoluminescence in low
dimensional materials is mainly due to the quantum confinement of ex-
citons in a nanometer-scale crystalline structure [15,16]. As photons are
absorbed by the material and charge carriers are produced, the average
diffusion time (τd) from the bulk of the material to the surface has been
shown to follow Eq. (1):

2
⁎ Corresponding author. r
τd ¼ ð1Þ
E-mail address: kartikghosh@missouristate.edu (K. Ghosh). Dπ2

http://dx.doi.org/10.1016/j.tsf.2014.09.056
0040-6090/© 2014 Elsevier B.V. All rights reserved.
 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133
where r is the grain radius and D is the diffusion coefficient of the mate-
rial [2]. A decrease of grain radius reduces the average diffusion time for
the charge carriers thereby reducing recombinations, which forms the
backbone of an efficient solar cell. Several device structures have been
proposed, including nanopillar arrays with axial and radial junctions
[17–19], and nanopillar collectors embedded in absorbing thin films
[20]. Stringent control over the morphology of the nanomaterial itself
has been shown to change the optical properties of a material [21,22].
The morphology associated with both the particle network and the
inter particle contact area also dictates solar activities [23,24]. Band
gap engineering for better optical properties is being widely used for
metal oxides by the process of doping [25], and mixed oxide synthesis
[26]. The constant effort to synthesize nanostructures with well-
defined geometrical shapes and organizing them as 2- and 3-
dimensional assemblies have further expanded the possibility of devel-
oping new strategies for light energy conversion [27,28]. Recently, we
have reported a considerable change in the optical properties with the
change in phase percentage, morphology and size of room temperature
stable copper oxides [29].
The relative band alignment of two materials is important to under-
stand the charge transport at the interface. For an effective charge sep-
aration there should be a type II or type III band alignment [30]. For
better comprehension of the charge transport in thin films the p-type
material should have both valence and conduction bands higher than
the n-type material. The charge separation for an increased solar cell ef-
ficiency demands faster diffusion time of the charge carriers [31]. As-
suming radiative recombination at the interface and proper alignment
of the valence band of p-type material with the conduction band of n-
type material gives the theoretical value of the open circuit voltage
(Voc) [32,33]. Integration of zinc oxide with copper oxide forms a type
II band alignment which favors a perfect solar cell assembly [34]. Sur-
face textures of a thin film as well as the morphology of nanoparticles
play a major role in charge transport. Structural distortion in thin
films could impede solar cell efficiency. In this paper we report a unique
way of fabricating copper oxide based solar cells by integrating the thin
films grown by pulsed laser deposition (PLD) and nanomaterials
through drop-casting. The incorporation of nanostructured copper
oxide powder with high optical absorption onto glass/ITO/ZnO/CuO
thin film stack enhances the performance of solar cells. Subsequent an-
nealing of the device at low temperature boosts the solar cell
characteristics.
2. Experimental details
All chemicals were analytic grade reagents and used without further
purification. The experimental details were as follows: (0.15 M)
CuSO4·5H2O (GFS Chemicals — Assay 98.0–102.0%) was dissolved in
(20 ml) deionized HPLC water (GFS Chemicals — Resistivity at 25 °C is
18.0 M ohm cm) under constant stirring. 45% (w/w) of KOH (GFS
Chemicals — Assay 45%) was added to the resulting aqueous solution
until the pH reached 13. The solution was transferred into a Teflon
lined stainless steel autoclaves, sealed and maintained at 80 °C for
15 h. In order to investigate the growth mechanism of copper oxides,
10 ml ethylene glycol (GFS chemicals — 99% pure) was added to the
aqueous solution before the hydrothermal process was started. After
the completion of the hydrothermal process, the solid products were
centrifuged (LW Scientific centrifuge — Model E8) at a rotation speed
of 1800 rpm for 30 min, washed three times with distilled water and
ethyl alcohol (Fisher Scientific, anhydrous and denatured), respectively,
to remove the ions possibly remaining in the final product, and finally
dried at 100 °C in air. Thin films of ZnO and CuO were deposited on
glass/ITO substrates by pulsed laser deposition (Excel Instrument,
PLD-STD-18) using a ZnO and CuO target. A KrF excimer laser (Lambda
Physik, COMPEX 201) with energy density of 2 J cm−2, λ = 248 nm,
pulsed duration of 20 ns, was used at a pulse rate of 10 Hz for the depo-
sition. Thin films were grown at a growth temperature of 300 °C and
127
oxygen pressure of 1 × 10−5 mbar in the chamber. The base pressure
of the deposition chamber was 1.2 × 10− 9 bar. The thicker ZnO PLD
grown film deposition was followed by a thinner PLD grown CuO film.
Typical film thicknesses were approximately 100 nm and 50 nm for
ZnO and CuO respectively, measured ex-situ by a profilometer (Veeco,
Dektak 150). The nanostructured phase mixture of copper oxide was
dissolved in toluene and sonicated for 5 min. The solution is then
drop-casted and annealed at 130 °C in O2 on the glass\ITO\ZnO\CuO
heterostructures. The sample was annealed for different annealing
times (1 h and 2 h). Low temperature annealing was performed to
retain the structural integrity of the nanostructured phase mixture
of copper oxide. The temperature of 130 °C in O 2 was sufficient
enough for physisorption of the copper oxide nanostructures onto
glass\ITO\ZnO\CuO thin film. The drop-casted film thickness was
tracked via optical absorption, and the process was repeated to obtain
films of the desired thickness. DC sputtering technique was used to
grow high quality top silver electrodes (500 μm diameter). The devices
were characterized using X-ray diffraction (Bruker, D8 Discover) θ–2θ
scan with CuKα (λ = 1.5405 Å); Rietveld analysis was done using
Diffrac plus Topas software. The morphology of as-prepared samples
were characterized by scanning electron microscopy (FEI Quanta
200S) and atomic force microscope (Digital Instruments, DI 3100).
The vibrational phonon modes and photoluminescence studies of the
samples were determined by Raman spectroscopy using a 532 nm
green laser, and 325 nm UV laser (Horiba Labram Raman-PL). Absorp-
tion characteristics spectra were measured by Ocean Optics HR 4000
spectrometer in conjunction with Ocean Optics Spectra suite software.
Solar measurements were done using AM 1.5 solar light source
(Newport, 69907 light source) coupled with Labview 2012 software
programming. The variable voltage across the solar cell device was ap-
plied using a voltage source (Keithley, 230 programmable voltage
source), and the current was measured by an electrometer (Keithley,
617 programmable electrometer).
3. Results and discussion
3.1. Copper oxide nanostructures
Hydrothermally synthesized copper oxide nanostructure was char-
acterized to determine its optical superiority as compared to other syn-
thesized nanopowders. Fig. 1 elucidates the optical effectiveness of the
as synthesized copper oxide nanostructures, and its dependency on
structural (X-ray diffraction) and molecular vibrational modes (Raman
spectroscopy). The observed XRD pattern (black line) along with that
of calculated (red line) using Rietveld analysis and difference (blue
line) profile for the powder sample are shown in Fig. 1(a). XRD data in-
dicate that the mixture of copper oxides formed crystallizes in space
group symmetry of C12/c1 (monoclinic) and Pn—3 m Z (cubic) for
CuO and Cu2O, respectively. The crystal structure was extracted by
Rietveld analysis and is represented in the inset of Fig. 1(a). The calcu-
lated bond angles (a, b) and the bond length (c) of the copper oxide
nanostructures are 95.74°, 78.93°, and 1.961 Å, respectively. The calcu-
lated goodness of fit is 1.07. The calculations indicate a least deviation
from the standard bond angles and bond length [29]. A larger deviation
in bond angles and bond lengths from the pure CuO results in weak or
strained bonds. The energy of the weak bonds is higher and these
bonds can easily break to form defects in the atomic network [35].
Band tail states represent the energy states of electrons that form the
strained bonds in the crystal network [36]. Increase in disorder and
strained bonds increases the width of the tail states. The wave functions
of the tail and defect states are localized within the structure and there-
fore these states are also referred to as localized states [37]. The mobility
of the charge carriers are least in those localized states [36,37]. Incorpo-
ration of these nanostructures for fabricating a solar cell can actually be
useful due to minimal density of the above-mentioned tail states.
128 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133

(c)

500 nm

Fig. 1. (a) Rietveld analyzed XRD plot of the copper nanostructure synthesized by hydrothermal process. The inset figures depict the CuO monoclinic crystal structure. The bond angles and
the bond lengths are calculated from the cif files generated by Rietveld refinement. Figure (b) represents the Raman spectra of the nanopowder copper oxide, and the inset figures portray
the vibrational modes in copper oxides. The blue balls represent Cu and the green ones O. SEM image showing the lassie nanostructures formed is shown in Figure (c). Figure (d) represents
the superior optical coefficient value of the nanostructured copper oxide when compared with standard Si [43] and commercially available CuO [42] in the visible solar range.

Fig. 1(b) pictorially represents the molecular vibrational modes
along with the Raman spectra of the hydrothermally synthesized cop-
per oxide nanopowder. CuO belongs to the C62h space group with two
molecules per primitive cell. There are nine zone-center optical phonon
modes with symmetries 4Au + 5Bu + Ag + 2Bg; only three modes (1Ag +
2Bg) are Raman active [38,39]. The optical vibrational Raman active
modes present in pure CuO are at 290 cm− 1 (Ag), 340 cm− 1 (B1g),
and 620 cm−1 (B2g) [40,41]. The Raman spectra of the sample shows
three optical vibrational modes of CuO (279.0 cm−1, 322.4 cm−1, and
611.0 cm−1), namely Ag, B1g, and B2g. The shift of these peaks towards
lesser wavenumbers (red shift) and increased value of FWHM ascer-
tains the nanostructured CuO. In addition to CuO peaks, a Cu2O peak
was also seen at 485.2 cm− 1 which corresponds to 2Eu vibrational
mode and is assigned to multi-phonon scattering, which involves vibra-
tions of both Cu and O atoms [36]. The synthesized sample shows a sta-
ble structure, as the Raman peaks shift towards lower wavenumbers
and thus can be an admirable material for solar cell applications.
A SEM image of the synthesized copper oxide sample is shown in
Fig. 1(c). The sample has a unique one dimensional lassie nanostructure
measuring less than 50 nm. This morphology and size of the prepared
copper oxide nanostructures can act as light trapping centers, which
thereby increase the rate of electron–hole pair generation. It's interest-
ing to note that after absorption, and optical band gap calculations for
this nanostructured phase mixture of copper oxide can absorb better
than commercially available copper oxide [42] and Si [43]. An optical
absorption coefficient of 7.05E+5 cm−1 at 525 nm was observed and
represented in Fig. 1(d) in that particular nanostructured phase mixture
of copper oxides, which is appreciably larger than commercially pure
CuO (1.19E+5 cm− 1) and Si (1.72E+5 cm−1). Detailed calculations
can be found elsewhere [29]. This optically superior phase mixture of
copper oxide nanopowder was deposited onto glass/ITO/ZnO/CuO thin
film by drop-casting at low temperatures to fabricate solar cells.
3.2. Solar cell device (glass/ITO/ZnO/CuO/copper oxide nanostructures)
3.2.1. X-ray diffraction
Fig. 2(a) shows the logarithmic XRD plot of the fabricated hybrid
solar cell device. The peaks at (222), (431), and (440) represent in
the plot belong to that of ITO [44]. Five diffraction peaks ( 1010 ),
(0002), (1120), (2020), and (0004) corresponding to the hexagonal
wurtzite structure of ZnO [45] can be clearly identified from the XRD
plot. The ZnO film grown by PLD has shown a diffraction peak at
(0002) having the highest intensity. This preferential orientation is
due to its highest surface energy theoretically calculated using the den-
sity functional studies [46]. The intense (0002) peak also indicates the
crystalline nature of the ZnO film grown and it grows perpendicular to
the substrate [47]. Chen et al. [48] explained the orientations of the pre-
ferred planes (111) and (111) of the CuO phase grown by PLD technique
as the crystalline nature of the CuO thin film. Fig. 2(a) shows the pres-
ence of the peaks (111) and (111) which belong to CuO present in the
device. Reports have shown that CuO thin film deposited on the ZnO
thin film by PLD process have peaks corresponding to (111), (111),
and ( 202 ) which also conforms with our XRD results [49]. Drop-
casting of the hydrothermally prepared nanostructured phase mixture
of copper oxide has been done on the CuO thin films. According to
Scherrer formula, the broadness of the copper oxide peaks confirms
the smaller particle size [50]. In addition, the presence of the Cu2O
peak (111) indicates successfully drop-casting of the nanoparticles
onto the thin film. The logarithmic XRD plot also proves the absence
of any secondary crystalline phases in the device.
 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133
Fig. 2. (a) XRD, (b) Raman spectra, and (c) photoluminescence of the fabricated hybrid
solar cell. The inset figures in (b) correspond to the different Raman active vibrational
modes of ZnO. The red balls represent Zn, and the green ones represent O.
3.2.2. Raman spectroscopy
Fig. 2(b) represents the Raman spectra of fabricated nanopowder-
thin film solar cell device. The inset pictures portray the Raman active
optical vibrational modes of ZnO. The Raman data were analyzed
129
using Voigt peak fittings in Labspec 5 software. The stable crystal struc-
ture of ZnO at room temperature is hexagonal, having the space group
symmetry of C46v which consists of four atoms in the primitive unit
cell (two ZnO molecular unit) [51]. Polar A1 (574 cm−1) mode repre-
sents the vibration of Zn and O atoms in its crystal lattice along the c
axis. On the other hand, the E2 vibrational modes indicate the vibration
of O atom and are perpendicular to the c axis. E2 (low) (99 cm−1) and E2
(high) (438 cm−1) modes are non-polar on the account of mutual can-
cellation of the displacement vectors [51]. The peak positions in Raman
spectra of thin films are useful for extracting valuable information re-
garding the predominant optical vibrational modes. The main mecha-
nisms of the optical phonon shifts of ZnO nanostructure are due to the
spatial confinement within the dot boundaries, internal stress (strain),
localized defects (oxygen vacancies), and excess amount of Zn atoms
in the crystal structure [52]. The change of Huang–Rhys parameter,
which depends on the ionic nature of semiconductors and the separa-
tion of the Fourier transformed charged distribution, the number of
multiple phonon scattering processes observed in semiconductor pho-
tovoltaic devices varies monotonically [53]. It has been theoretically
proven that crystalline ZnO have a large value of Huang–Rhys parame-
ter [53], and therefore multi-phonon scattering is predominantly
observed in this case. Optical excitation of ZnO generates mobile
charges carriers, which when collectively oscillate is referred to as
plasma oscillation [51].
The Raman spectra of the fabricated solar cell device shows peak
shift of ZnO with respect to their bulk counterparts. This can be due to
the presence of internal lattice stress originating from the lattice mis-
match of ZnO and the substrate [54]. From Fig. 2(b) it is seen that the
peak at 431.5 cm− 1 which corresponds to the E2 high mode, is red
shifted. The peak at 572.2 cm−1 corresponds to the A1 (LO) vibration
which is more prominent than the E2 high mode of ZnO. This can be
due to the presence of heavier oxygen moieties vibrating along the c
axis. The A1 (LO) peak shows asymmetricity, and the possible reason
can be due to the presence of plasmon phonon mixed states. These
states are visible in the range between 499.5 cm− 1 and 572.2 cm− 1
[51]. The peak at 1115.1 cm−1 indicates the second order Raman scat-
tering of A1 (LO) mode of ZnO. The presence of multiple phonon scatter-
ing Raman peaks indicates optical superiority of the fabricated hybrid
solar cell device [55]. The peaks at 290.7 cm−1, 338.7 cm−1 and
623.3 cm−1 correspond to Raman active vibrations of Ag, B1g and B2g
of CuO nanostructures of the solar cell device. These three optical
vibrational modes indicate the vibrations of oxygen atoms [56]. The
peak at 499.5 cm−1 corresponds to the T2g vibrational mode of Cu2O
nanopowder. The red shift and broader FWHM of this optical phonon
mode are indicative of copper oxide nanostructures. The shoulder
peaks in the range between 431.5 cm− 1 and 499.5 cm− 1 are due to
the multi-phonon scattering of Cu2O [57]. Multi-phonon scattering
plays an important role in generating multiple charge carriers from a
single photon. This increases the cumulative number of charge carriers
taking part in light-electric energy conversion. The presence of distinc-
tive Raman spectra of ZnO, CuO, and Cu2O is an indicative of an exciting
hybrid structure existing in the device.
3.2.3. Photoluminescence (PL) spectroscopy
Fig. 2(c) represents PL spectra of the hybrid nanopowder-thin film
device. The room temperature 325 nm laser excitation PL data were an-
alyzed using Voigt peak fittings in Labspec 5 software. The emission
peaks are observed at 3.2 eV (382.8 nm—violet), 2.3 eV (528.6 nm—
green), 2.2 eV (576.1 nm—yellow), 1.9 eV (663.1 nm—red) and 1.6 eV
(763.7 nm—red). The emission peak at 3.2 eV indicates the direct
band gap of ZnO. The sharp emission peak at 1.6 eV indicates the second
order electronic transition of ZnO. Interesting peak features arise after
deconvolution of the broader peak region between 1.8 eV and 2.5 eV.
In that region three peaks are observed. The origin of this broader
zone is due to the superimposition of the defects attributed by oxygen
vacancies or Zn interstitials, the band to band transition in copper
130 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133

oxides, and other defects like copper ion vacancies in the nanostructure (a)
[58–60]. Fortunately, increasing this region assists better visible solar
absorption, which forms the backbone of an efficient solar cell. The
emission peak at 2.3 eV may correspond to the copper oxide
nanopowder. The peaks at 2.2 eV and 1.9 eV appeared due to the tran-
sition of electrons from conduction band to acceptor level and the tran-
sition of electrons from donor level to valance band or acceptor level in
copper oxide [60]. It is visible from the PL spectra that the fabricated 1µm
solar cell device can absorb better in the visible region which is an im-
portant criterion for a photonic device.

3.2.4. Microscopy
Fig. 3 depicts high definition images taken for the fabricated hy-
brid solar device. The cross-sectional SEM image as shown in
Fig. 3(a) indicates the copper oxide nanostructures drop-casted
onto the glass/ITO/ZnO/CuO thin film. The inset picture in 10µm
Fig. 3(a) shows a single nanostructure of copper oxide which re-
mains structurally intact after annealing. The SEM image also proves
better contact between the nanostructures and the thin film, which is (b)
mandatory for an efficient solar cell. The EDX is also done to demon-
strate the spatial distribution of zinc oxide and copper oxide in the de-
vice. The coloring sequence as represented in Fig. 3(b) is an indicative
of adherence between the copper oxide nanostructures and ZnO thin
film. The “interlocking” phenomenon for better solar cell efficiency is
clearly demonstrated in the AFM image in Fig. 3(c). The nanopores are
visible on the ZnO/CuO thin film deposited by PLD technique. The cop-
per oxide nanostructures are embedded onto the thin film device by the
process of annealing. Fig. 3(c) is also useful in demonstrating the verti-
cal locking of copper oxide nanostructures, which forms a better contact
with the underlying ZnO thin film. The porous thin film also facilitates
better anchoring the nanostructures on annealing. The zoomed in 6µm
view of the surface topography is shown as inset in Fig. 3(c).

3.2.5. Electrical characteristics

Fig. 4 represents solar characteristic curves of (a) glass/ITO/ZnO/CuO
thin film (sample 1), (b) glass/ITO/ZnO/CuO/commercially available
copper oxide micro-powder (sample 2), and (c) glass/ITO/ZnO/CuO/
hydrothermally prepared copper oxide nanostructures (samples 3A,
Oxygen Copper Zinc
3B, and 3C). The inset graphs are zoomed in view near the origin
depicting the increase in Voc and Jsc with the incorporation of the hydro-
thermally prepared copper oxide nanostructures onto ITO/ZnO/CuO
thin film. The actual solar cell device on which the electrical measure-
ments were taken is also drawn as an inset picture. Fig. 4(c) indicates
a considerable increase in solar performance of the hybrid device with
the increase of annealing time from 1 h (sample 3A) to 2 h (sample 3B
& sample 3C). The increased solar cell efficiency in all the samples was
tested repeatedly to ascertain the improvement in the short circuit cur- (c)
rent and open circuit voltage. The preparation of sample 3B is identical
to that of sample 3C. The identical solar characteristic curve for samples
3B and 3C proves the reliability of sample preparation. The photovoltaic
effects of all the devices were investigated at room temperature using
AM 1.5 sun illumination source. All the samples show a nonlinear cur-
rent density (J) vs bias voltage (V) curve without illumination which re-
sembles to conventional p–n junctions. The thin film of ZnO shows n-
type semiconducting properties while copper oxide grows as a p-type
semiconductor, thereby creating a space charge region at the p–n junc-
tion [61]. During the illumination through the ITO-glass substrate, the Fig. 3. (a) SEM imaging indicating drop-casted nanostructure of copper oxide on ITO/ZnO/
CuO thin film, (b) EDX showing distribution of CuO and ZnO on the device, and (c) AFM
photovoltaic characteristic of the heterostructure solar cells was also in- indicating nanopores on ZnO/CuO thin film which facilitates “interlocking” of the nano-
vestigated. The corresponding J–V curves of all the devices imply con- structures. The inset figure in (c) explicitly shows a zoomed in portion of the thin film.
ventional solar cell characteristics.
As illustrated in Fig. 4(a), the measured value of Jsc is 0.29 mA cm−2
which can be an implication of higher number of micro/nanovoids and the reduction of the textural defects as well as thicker active absorbing
smaller grain size of the constituents present in the thin film. With the layer. After annealing, the hydrothermally prepared nanostructures for
introduction of commercially available micro-powder of copper oxide 1 h onto the thin film show improvement in solar properties. The best
onto the thin film, the measured Jsc increased by an order of magnitude solar cell characteristics were achieved with the increase of the anneal-
to 4.22 mA cm−2. The possible reason for this increment may be due to ing time to 2 h. Annealing treatment helps remove the surface ligands
 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133 131

Fig. 4. Solar characteristic curves of (a) glass/ITO/ZnO/CuO thin film (sample 1), (b) glass/ITO/ZnO/CuO/commercially available copper oxide micro-powder (sample 2), and (c) glass/ITO/
ZnO/CuO/hydrothermally prepared copper oxide nanostructures (samples 3A, 3B, and 3C). Figure (c) shows J–V characteristic curves of sample 3A (annealed for 1 h), sample 3B (annealed
for 2 h), and sample 3C (annealed for 2 h). Figure (c) indicates an increase in solar cell efficiency with increasing annealing time. The inset figures are zoomed in view near the origin
depicting Voc and Jsc. The solar cell devices are also drawn as an inset picture. The violet color represents glass substrate, green represents ITO layer, gray represents ZnO thin film, dark
yellow represents CuO thin film, blue represents top Ag electrodes, spheres of dark gray indicates commercially available copper oxide micro-powder, and lassie structures of dark
gray represents hydrothermally synthesized nanostructured copper oxide.

which sinter the nanoparticles into a more continuous thin film to where ℏ is the reduced plank's constant, μ is the refractive index, m is
achieve better mobility [62]. The sample A consisting of nanoparticles the electron mass, me is the electron effective mass, mh is the hole effec-
indicates a Jsc of 7.56 mA cm−2, which is almost 80% larger as compared tive mass, q is the charge of an electron, K is the Boltzmann constant, T is
to the micro-powder device. With the addition of nanopowders, the in- the absolute temperature, and c is the speed of light. For a constant μ, the
creased optical absorption increases the number of charge carriers. Im- value of B increases with the square of Eg. Therefore to achieve the max-
proved surface textures on annealing assist better diffusion of these imum possible value of τm, a trade-off between the phase percentages of
electron–hole pairs to the external circuit. With the increase in anneal- copper oxide is desired to find the optimum level of B and NA. This has
ing time to 2 h, more amount of nanoparticles adheres onto the thin film been proven from the electrical measurements of our fabricated solar
which tremendously increases the Jsc to almost 3 times than sample A. devices, containing greater phase percentage of cupric oxide.
The Jsc was found to be 20.90 mA cm−2. This proves that annealing The introduction of the nanostructure with high absorption coeffi-
time also plays an important role in determining the solar cell efficiency. cient also helps separate electron–hole pairs resulting higher Jsc which
The minority carrier lifetime (τm) is given by Eq. (2): can be explained using Eq. (1). So, the smaller particle size helps the
charge carriers reach the surface before recombination because τd is
shorter than τm. In the case of the thin film device the measured Voc is
1
τm ¼ ð2Þ 0.30 V which normally depends on the band alignment of p and n-
B NA
type semiconductors [67]. Similarly, in the devices of Fig. 4(c), the mea-
sured Voc also increased successively from 0.35 V to 0.40 V which refer
where B is the radiative recombination coefficient and NA is the concen- to better band alignment (introduction of nanostructures). For low-
tration of the dopant in p-type semi-conductor. It is widely known that, level carrier injection, assuming constant minority carrier concentration
CuO is inherently having high NA compared to that of Cu2O, which can throughout the p type layer with thickness w, the open circuit voltage
help achieve higher carrier lifetime [63]. Nevertheless B is dependent can be expressed by the following Eq. (4) [66]:
on optical band gap (Eg) by the following Eq. (3) [64–66]: !
Eg KT qwBNc Nv
V oc ¼ − ln ð4Þ
q q J ph
3
3
 2
ð2πÞ2 ℏq2 m 2 m m Eg
B¼ μ 1þ þ 3  ð3Þ where Nc and Nv are effective density of states at conduction and va-
3 m2 c2 me þ mh me mh ðKT Þ2 mc2 2
lance band respectively, and Jph is the photogenerated current density.
132 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133
In our thin film device the possible reason of moderate value of Voc may
be due to higher Nc and Nv. It can be inferred from previously studied
electron effective mass and band gap calculations that Nc is related to
Eg by the following Eq. (5) [68,69]:
3
Nc ∝ E2g :
Therefore, the change in Eg using different phase percentage of cop-
per oxide nanoparticles introduces a change in the second term of the
Eq. (4) which thereby proves the non-linear variation of Voc.
Fig. 5 depicts the J–V and power density vs voltage plot of sample 3A
and sample 3B. The overall low power conversion efficiency in our de-
vices can be due to large recombination, large series resistance (Rs),
and low shunt resistance (Rsh). This can also be observed in Fig. 5.
Using the Eq. (6) the fill factor (FF) for all the devices were calculated
and represented in Table 1.
V m Im
FF ¼
V oc Isc
where Im and Vm are the current and voltage respectively, at the maxi-
mum power point of the I–V curve [69], which is calculated from
Fig. 5. The overall power conversion efficiency (η) has been calculated
using the following Eq. (7):
V oc  J sc  F F
η¼
P and a distributed heterojunction, and potentially offers the advantages
where P is the illumination intensity [20]. Both Voc and Jsc follow an in-
creasing trend with incorporation of copper oxide nanostructures. The
η also increases accordingly and all calculated device parameters are
given in Table 1. Our reported power conversion efficiency values sug-
gest that a significant enhancement in solar device performance can
be achieved by nanostructuring and annealing copper oxide phase mix-
ture onto glass/ITO/ZnO/CuO thin film device.
3.3. Discussion
The response of nanoparticles to electromagnetic light wave is
caused by dipole oscillation of localized surface plasmons (LSPR)
which serve to increase the material extinction coefficient [70]. For bet-
ter photovoltaic conversion, plasmon resonant absorption represents an
unwanted loss process, but off-resonant enhanced scattering can yield
an increase in photon absorption and thereby increased photocurrent
generation [71]. The optical properties of nanoparticles directly depend
on the nanoparticle size and shape [72]. Proper morphological design of
the nanoparticles is indispensable to achieve higher efficient plasmonic
Fig. 5. J–V and power density vs voltage plot of sample 3A and sample 3B.
solar cell. At wavelengths below surface plasmon resonance, scattered
incident light by the nanoparticles may yield enhanced absorption in
the photovoltaic layers of a solar cell. Thereby, the interacting surface
plasmons between the nanoparticles can enhance the plasmonic scat-
tering effect. Such cells serve as a model system for investigating
ð5Þ plasmon-enhanced absorption in solar cells and enable one to develop
guiding principles for solar cell design. Another inherent advantage of
introduction of nanostructure is improvement in the fill factor for the
solar devices, indicating the reduction in the surface sheet resistance.
This effect can be expected in all solar cells that form better contact be-
tween the nanoparticle array and the cell window layer. Improvement
in both Voc and Isc is achieved in the case of nanoparticle injection onto
the thin film solar cell. The better surface contacts might be useful for
easier electron transfer through the semi-conducting layers, thus facili-
tating better efficiency in the solar cells. The sparse nanostructured ar-
rays enable the reduction in the loss of incident light resulting from
either absorption or backscattering by the nanoparticles near the sur-
face plasmon resonances, while the plasmonic scattering can be en-
ð6Þ hanced in the dense array cases at wavelengths below the surface
plasmon resonances. Especially the copper oxide nanoparticles signifi-
cantly enhance the photocurrent, which can be attributed to the strong
scattering by interacting surface plasmons. Our results demonstrate that
the arrangement of nanoparticles on thin film enhances the plasmonic
scattering and thus in turn increases the absorption of the incident
light. Segregation of donor towards anode and acceptor towards cath-
ode in a photovoltaic device represents a compromise between a planar
ð7Þ
of both configurations: efficient exciton dissociation as a result of the in-
timate intermixing of components, efficient charge transport, and en-
hanced electrode selectivity as a result of the segregation. This
distribution of components is expected to enhance the selectivity of
the contacts towards one type of charge carrier and to reduce charge
leakage. Another reason for photocurrent enhancement can be due to
integration of plasmonic copper oxide nanoparticles with a thin copper
oxide layer that has greater refractive index contrast relative to a low
index substrate layer (ZnO). This is an excellent approach to achieve
total internal reflection at the cell back interface and guided wave prop-
agation in the cell photovoltaic layers.
4. Conclusion
We have fabricated highly efficient solar cells in a unique way by
integrating an optically active copper oxide nanostructure with its
thin film. The use of nanostructures introduces interesting physics
of LSPR and multi-phonon scattering in a solar cell device. The intro-
duction of copper oxide nanopowders onto the thin film increases
the power conversion efficiency by 80% compared to micro-
powder-thin film solar devices. Our findings show a higher solar
cell efficiency (2.88%) in copper oxide based solar cells, and a corre-
lation of photovoltaic physics with Raman spectroscopy and PL stud-
ies was done. Multi-phonon scattering as observed from Raman
spectroscopy illustrates optical superiority of the fabricated thin
film device. The increase in the broadness of PL spectra between
1.8 eV and 2.5 eV is an indicative of better visible solar light absorp-
tion of the device. The solar cell device performance is also depen-
dent on the annealing time. The Jsc increases by 176% and Voc by
14% with increasing the annealing time from 1 h to 2 h. Annealing
the thin film with nanopowder “interlocks” the nanostructures bet-
ter, thereby creating a situation where the light induced charge car-
riers find an easy path through the external circuit, resulting an
increase in the solar cell efficiency by 180%. The use of economical,
environmentally benign, and stable oxide materials suggests better
lifetime and commercially viable solar cell devices. This inexpensive
fabrication process is one of the most elegant and versatile architec-
tures for constructing practical nanoscale solar devices.
 A. Bhaumik et al. / Thin Solid Films 572 (2014) 126–133 133

Table 1
Calculated Jsc, Voc, FF, and efficiency for all the solar cells.

Solar cell Jsc (mA cm−2) Voc (V) FF (%) Efficiency (%)

ITO/ZnO/CuO thin film 0.30 0.30 32.5 0.03

ITO/ZnO/CuO/commercially available copper oxide micro-powder 4.21 0.32 34.7 0.57
ITO/ZnO/CuO/hydrothermally prepared copper oxide nanostructures (sample A) 7.56 0.35 38.6 1.03
ITO/ZnO/CuO/hydrothermally prepared copper oxide nanostructures (sample B) 20.90 0.40 34.3 2.88

Acknowledgments [34] H. Kidowaki, T. Oku, T. Akiyama, J. Phys. 352 (2012) 012022.

[35] M. Zeman, J. Krc, Mater. Res. Soc. Symp. Proc. 989 (2007) A03.
[36] S. Kugler, J. Phys. Conf. Ser. 253 (2010) 1.
This research was funded by the National Science Foundation, grant [37] K. Nomura, H. Ohta, A. Takagi, T. Kamiya, M. Hirano, H. Hosono, Nature 432 (2004)
numbers: DMR-1126375 and DMR-0907037. 488.
[38] J. Chrzanowski, J. Irwin, Solid State Commun. 70 (2009) 11.
[39] H. Goldstein, D. Kim, P. Yu, L. Bourne, J. Chaminade, L. Nganga, Phys. Rev. B Condens.
References Matter Mater. Phys. 41 (2009) 7192.
[40] J. Nye, Physical Properties of Crystals: Their Representation by Tensors and Matrices,
[1] M. Grätzel, Nature 421 (2003) 586. Oxford University Press, London, 1957. (Chap. 5).
[2] T. Markvart, L. Castaner, Solar Cells Materials: Manufacture and Operation, Elsevier, [41] R. Loudon, Adv. Phys. 13 (1964) 423.
Oxford, 2005. (Chap. IIa). [42] T. Maruyama, Sol. Energy Mater. Sol. Cells 56 (1998) 85.
[3] S. Agarkar, V. Dhas, S. Muduli, S. Ogale, RSC Adv. 2 (2012) 11645. [43] M. Green, Sol. Energy Mater. Sol. Cells 92 (2008) 1305.
[4] A. Frank, N. Kopidakis, J.V.D. Lagemaat, Coord. Chem. Rev. 248 (2004) 1165. [44] D. Raoufi, A. Kiasatpour, H.R. Fallah, A.S.H. Rozatian, Appl. Surf. Sci. 253 (2007) 9085.
[5] M. Law, L. Greene, J. Johnson, R. Saykally, P. Yang, Nat. Mater. 4 (2005) 455. [45] V. Craciun, J. Elders, J.G.E. Gardeniers, I.W. Boyd, Appl. Phys. Lett. 65 (1994) 23.
[6] T. Oekermann, D. Zhang, T. Yoshida, H. Minoura, J. Phys. Chem. B 108 (2004) 2227. [46] B. Meyer, D. Marx, Phys. Rev. B 67 (2003) 035403.
[7] B.P. Rai, Sol. Cells 25 (1988) 265. [47] X. Teng, H. Fan, S. Pan, C. Ye, G. Li, Mater. Lett. 61 (2007) 201.
[8] A. Mittiga, E. Salza, F. Sarta, M. Tucci, R. Vasanthi, Appl. Phys. Lett. 88 (2006) 163502. [48] A. Chen, H. Long, X. Li, G. Yang, P. Lu, Vacuum 83 (2009) 929.
[9] H. Kidowaki, T. Oku, T. Akiyama, A. Suzuki, B. Jeyadevan, J. Cuya, J. Mater. Sci. Res. 1 [49] S. Mridha, D. Basak, Semicond. Sci. Technol. 21 (2006) 928.
(2012) 138. [50] C. Chen, Y. Zheng, Y. Zhan, X. Qizheng, K. Wei, Cryst. Growth Des. 8 (2008) 3549.
[10] T. Minami, T. Miyata, K. Ihara, Y. Minamino, T. Satoshi, Thin Solid Films 494 (2006) [51] H. Morkoc, Ü. Özgür, Zinc Oxide: Fundamentals, Materials and Device Technology,
47. Willey-VCH, 2009. (Chap.1).
[11] K. Akimoto, S. Ishizuka, M. Yanagita, Y. Nawa, G.K. Paul, T. Sakurai, Sol. Energy 80 [52] M. Rajalakshmi, A.K. Arora, B.S. Bendre, S. Mahamuni, J. Appl. Phys. 87 (2000) 2445.
(2006) 715. [53] J.F. Scott, T.C. Damne, W.T. Silvast, R.C.C. Leite, L.F. Cheesman, Opt. Commun. 1
[12] M. Izaki, K. Mizuno, T. Shinagawa, M. Inaba, A. Tasaka, J. Electrochem. Soc. 153 (1970) 397.
(2006) C668. [54] F.K. Shan, G.X. Liu, Z.F. Liu, W.J. Lee, G.H. Lee, I.S. Kim, B.C. Shin, Y.S. Yu, J. Korean
[13] N. Lewis, Science 315 (2007) 798. Phys. Soc. 459 (2004) 771.
[14] W. Huynh, J. Dittmer, A. Alivisatos, Science 295 (2002) 2425. [55] B. Kumar, H. Gong, Y.C. Shue, T. Sudhiranjan, H. Younan, Appl. Phys. Lett. 89 (2006)
[15] O. Bisi, S. Ossicini, L. Pavesi, Surf. Sci. Rep. 38 (2000) 1. 071922.
[16] L. Pavesi, L. Dal Negro, C. Mazzoleni, G. Franzo, F. Priolo, Nature 408 (2000) 440. [56] J.C. Irwin, T. Wei, J. Phys. Condens. Matter 3 (1991) 3.
[17] B.M. Kayes, H.A. Atwater, N.S. Lewis, J. Appl. Phys. 97 (2005) 114302. [57] J. Reydellet, M. Balkanski, D. Trivich, Phys. Status Solidi B 52 (1972) 175.
[18] J.A. Czaban, D.A. Thompson, R.R. LaPierre, Nano Lett. 9 (2009) 148. [58] K. Vanheusden, C.H. Seager, W.L. Warren, D.R. Tallant, J.A. Voiget, Appl. Phys. Lett. 68
[19] E.C. Garnett, P.D. Yang, J. Am. Chem. Soc. 130 (2008) 9224. (1996) 403.
[20] Z.Y. Fan, H. Razavi, J.W. Do, A. Moriwaki, O. Ergen, Y.L. Chueh, P.W. Leu, J.C. Ho, T. [59] K. Vanheusden, W.L. Warren, C.H. Seager, D.R. Tallant, J.A. Voigt, B.E. Gnade, J. Appl.
Takahashi, L.A. Reichertz, S. Neale, K. Yu, M. Wu, J.W. Ager, A. Javey, Nat. Mater. 8 Phys. 79 (1996) 7983.
(2009) 648. [60] B. Balamurugan, B.R. Mehta, D.K. Avasthi, F. Singh, A.K. Arora, M. Rajalakshmi, G.
[21] J. Zhang, H. Liu, Z. Wang, N. Ming, Z. Li, A. Biris, Adv. Funct. Mater. 17 (2007) 3897. Raghavan, A.K. Tyagi, S.M. Shivaprasad, J. Appl. Phys. 92 (2002) 3304.
[22] W. Yuxin, L. Xinyong, W. Ning, Q. Xie, C. Yongying, Sep. Purif. Technol. 62 (2008) [61] J. Katayama, K. Ito, M. Matsuoka, J. Tamaki, J. Appl. Electrochem. 34 (2004) 687.
727. [62] B.D. Yuhas, P. Yang, J. Am. Chem. Soc. 131 (2009) 3756.
[23] N. Kopidakis, K. Benkstein, J. van de Lagemaat, A. Frank, Q. Yuan, E. Schiff, Phys. Rev. [63] L.Y. Isseroff, E.A. Carter, Chem. Mater. 25 (2013) 253.
B Condens. Matter Mater. Phys. 73 (2006) 7. [64] R.N. Hall, Proceedings of the IEE — Part B: Electronic and Communication Engineer-
[24] K. Zhu, N. Neale, A. Miedaner, A. Frank, Nano Lett. 7 (2007) 69. ing, 106, 1959, p. 923.
[25] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science 293 (2001) 269. [65] W.V. Roosbroeck, W. Shockley, Phys. Rev. 94 (1954) 1558.
[26] B. Faughnan, R. Crandall, Appl. Phys. Lett. 31 (1977) 834. [66] J. Bardeen, F.J. Blatt, L.H. Hall, Photoconductivity Conference, Wiley, 1956, p. 146.
[27] R. Jin, Y. Cao, E. Hao, G. Metraux, G. Schatz, C. Mirkin, Nature 425 (2003) 487. [67] J. Cui, U.J. Gibson, J. Phys. Chem. C 114 (2010) 6408.
[28] Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim, H. Yan, Adv. Mater. [68] S. Adachi, GaAs and Related Materials, World Scientific, New Jersey, 1994. 232.
15 (2003) 353. [69] S.O. Kasap, Principles of Electronic Materials and Devices, Tata-McGraw-Hill Pub-
[29] A. Bhaumik, A.M. Shearin, R. Patel, K. Ghosh, Phys. Chem. Chem. Phys. 16 (2014) lishing Company Limited, New Delhi, 2006. (Chap. 5).
11054. [70] H.R. Stuart, D.G. Hall, Appl. Phys. Lett. 69 (1996) 2327.
[30] L.M. Wong, S.Y. Chiam, J.Q. Huang, S.J. Wang, J.S. Pan, W.K. Chim, J. Appl. Phys. 108 [71] D.M. Schaadt, B. Feng, E.T. Yu, Appl. Phys. Lett. 86 (2005) 063106.
(2010) 033702. [72] C.F. Bohren, D.R. Huffman, Absorption and Scattering of Light by Small Particles,
[31] V.I. Arkhipov, E.V. Emelianova, H. Bassler, Phys. Rev. Lett. 82 (1999) 1321. Wiley, New York, 1983. (Chap. 2).
[32] T. Kirchartz, J. Mattheis, U. Rau, Phys. Rev. Lett. B 78 (2008) 235320.
[33] S.C. Abhramas, A. Kvick, Acta Crystallogr. B 45 (1989) 34.

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