Facile synthesis and characterization

of cupric oxide (CuO) nanoparticles:

Inexpensive and abundant candidate for
light harvesting
Cite as: AIP Conference Proceedings 2093, 020047 (2019); https://doi.org/10.1063/1.5097116
Published Online: 15 April 2019

Ayana Bhaduri, and Kajal

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AIP Conference Proceedings 2093, 020047 (2019); https://doi.org/10.1063/1.5097116 2093, 020047

© 2019 Author(s).
 Facile Synthesis and Characterization of Cupric Oxide
(CuO) Nanoparticles: Inexpensive and Abundant Candidate
for Light Harvesting
Ayana Bhaduri 1a) and Kajal 2, b)

1
Department of Applied Physics, Amity University Gurgaon, Gurgaon 122413 INDIA
2
Department of Applied Chemistry, Amity University Gurgaon, Gurgaon122413 INDIA
a)
Corresponding author: ayana.bhaduri@gmail.com, b)kajaldu399@gmail.com

Abstract. Cupric Oxide (CuO), is an inexpensive and non-toxic p-type semiconductor material with a monoclinic crystal
structure having indirect band gap (Eg) 1.2 eV -1.9 eV. In this study, co-precipitation method has been employed to
synthesize CuO nanoparticles. The samples were calcinated at 200 0C or 4000C for decomposition of hydroxides to oxide.
The XRD pattern of the CuO nanoparticles annealed at 400°C exhibited well defined peaks and are consistent with the
standard values showing monoclinic structure of CuO with particle size in the range around 10 nm -12 nm and 14 nm-17
nm for slighty different precursor materials both samples annealed at 200°C. The nanoparticles size got aggregated when
they are annealed at 400°C . This may be attributed to the agglomeration of the particles at high temperature. Hereby we
are emphasizing the fact that the interest on old semiconductor like copper oxide still remains at a time when many new
semiconductors such as the perovskites and organic semiconductors are being studied for PV applications is mainly due
to sustainability. Both copper and oxygen are abundant elements like silicon and thus there can be no supply concern in
the long run.
INTRODUCTION
Cupric Oxide (CuO), is a inexpensive and non-toxic P-type semiconductor material [1] with a monoclinic crystal
structure having indirect band gap (Eg) 1.2 eV -1.9 eV [2]. The first photovoltaic cells observed by Becquerel in
1839 was copper oxide coated metal electrodes immersed in an electrolyte solution. CuO have interesting. With
excellent thermal stability, good electrical and optical, photovoltaic, electrochemical and catalytic properties [3] it
found many practical applications such as an antimicrobial [4] photothermal and photoconductive [5], chemical and
biological sensing [6], catalysis [7] application in lithium ion batteries [8] solar cell [9], dye-sensitized solar cells
[10], field emission emitters [11] etc. Hereby we are emphasizing the fact that the interest on old semiconductor like
copper oxide still remains at a time when many new semiconductors such as the perovskite and organic
semiconductors are being studied for PV applications is due to sustainability. Both copper and oxygen are abundant
elements like silicon and thus there can be no supply concern in the long run [12]. This is one of the basic
requirements for a semiconductor to be usable for large scale PV power generation [13]. A careful sustainability
analysis of a large number of semiconductor materials showed that Cu2O and CuO are sustainable PV materials
[14,15]. In addition, all oxides of copper are non-toxic and can be deposited as thin films relatively simply at low
cost. The alternative p-type binary oxides such as tin monoxide (SnO) and nickel oxide (NiO), have energy band
gaps of 2.5 eV and 3.6–4.0 eV, respectively, are too wide for PV applications [16].

EXPERIMENTAL
Synthesis of CuO Nanoparticles
In this study, co-precipitation method has been employed to synthesize CuO nanoparticles. This technique has
drawn much attention as it provides high surface stability and also has significant influence on the morphology and
optical properties of CuO nanoparticles [17]. Employing three slightly different route, we have synthesized, copper
oxide nano particles. 1st method, CuO nanoparticles are synthesized using copper chloride dehydrated and sodium
Hydroxide pellets as precursors in aqueous media [18]. In 2nd method, potassium hydroxide is used for the synthesis.
In the 3rd process, copper chloride dehydrated dissolved in ethanol at room temperature. To this, sodium hydroxide
dissolved in ethanol was added drop wise. The solutions were stirred continuously at room temperature to carry out
the reaction. The color of the solution gradually changes from green to black precipitation of copper hydroxide.

Proceedings of the National Conference on Recent Advances in Condensed Matter Physics

AIP Conf. Proc. 2093, 020047-1–020047-4; https://doi.org/10.1063/1.5097116
Published by AIP Publishing. 978-0-7354-1823-3/$30.00

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Take for one hour to complete the precipitation reaction. For all the methods, these precipitates were centrifuged and
washed to remove nonreactive contents. Obtained precipitates were dried in oven at 60 0C for 4 hours and kept
overnight to get dried samples.These were calcinated at 2000C, 4000C for decomposition of hydroxides to oxide.
During, the synthesis of copper oxide nanoparticles, hydroxide ion plays an important role. Firstly, it is combined
with cupric ion to form cupric hydroxide and this is decomposed to cupric oxide on heating. Sodium and potassium
hydroxides are strong electrolytes, as a result they may neutralize the surface charges of the CuO nanoparticles,
preventing them from possible crystalline aggregation. Apart from these, the use of high concentrated hydroxides
helps in formation of diffusion layers on certain surfaces of CuO nanoparticles, and this may create an additional
growth anisotropy allowing only energetically favorable crystallographic planes to grow [19,20].

Characterization of CuO Nanoparticles

Blackish CuO nanopowder was collected and characterized. Structural analysis was done by FESEM imaging and
Powder XRD. The optical band gap of the prepared material was measured by UV-VIS absorption spectra, which
were records with the help of 2401 PC Shimadzu Spectrophotometer.

RESULTS & DISCUSSION

Structural Characterization by XRD
The X-rays diffraction pattern of CuO nanoparticles calcined at 2000C and 4000C. All diffraction peaks are well
indexed to the single phase of CuO monoclinic crystals structure (JCPDS-410254). The well-defined peaks in the
XRD spectrum of CuO nanoparticles show high crystalline nature. The broadening of the peaks indicates the
formation of Nano metrics particle size. In this case, the Scherer’s equation (1):
୩஛
‫ܦ‬ൌ ሺͳሻ
௖௢௦௾ఉ೓ೖ೗
Where D is the crystalline size (nm), k is a constant equal to the 0.94, λ is the wavelength of X-rays radiation
(1.5418 A0) and ߚ௛௞௟ is the broadening of the peak at half maxima (FWHM).

FIGURE 1 XRD pattern for CuO nanoparticles

The XRD pattern of the CuO nanoparticles annealed at 400°C exhibited well defined peaks and are consistent with
the standard values showing monoclinic structure of CuO [Fig 1].
The sharp and intense peaks in the XRD pattern of the product indicate good crystallinity of CuO nanoparticles.The
mean crystalline size is calculated from the full-width at half-maximum (FWHM) of XRD lines by using the Debye-
Scherrer relation. The average crystallite diameter of the CuO nanoparticles is around 10 nm -12 nm for the 3 rd
method with annealed at 200°C, 14 nm-16 nm for 2 nd method with annealed at 200°C. It was found that an increase
in particle size with the increase in annealing temperature. The nanoparticles size got aggregated when they are
annealed at 400°C . This may be attributed to the agglomeration of the particles at high temperature. The sharp and
intense peaks in the XRD pattern of the product indicate good crystallinity of CuO nanoparticles.
Morphology Analysis by SEM
Morphology of the produced powder was analyzed with field emission scanning electron microscopy (FE-SEM),
ZEISS. The accelerating voltage for FE-SEM examination was 5 kV. SEM images (fig 2) revealed that the

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nanoparticles are with cubical, oblong or rice like shape, but not spherical and the agglomeration to form a cluster is
also being observed. The nanoparticles observed are in the range ~40-50 nm.

FIGURE 2 (a) & (b)SEM Micrograph for CuO nanoparticles (3rd Route)

Optical Analysis by UV-VIS Absorption

UV-VIS spectra of CuO nanoparticles in ethanol medium were recorded to study the optical properties of the
material. The absorption coefficient (α) was estimated from the absorption data using the relation (equation 2)
ͳ ͳ
ߙ ൌ ൬ ൰ Ž ൬ ൰ሺʹሻ
݀ ܶ
Where d is the width of Quartz taken as 10-2 m and T transmittance estimated using Beer –Lambert’s equation
considering reflectivity as zero. Using Tauc’s equation (αhυ)2=C(hυ-Eg); the band gap (direct) of all the samples are
2.75- 2.9 eV. The direct band gap (~2.8eV) is higher as compared to bulk values (2.4eV), this blue shift in the direct
band gap is due to the quantum confinement effect [21]. This quantum confinement effect, which enhances the the
band gap with decreasing particle size, follows the relations [22]
݄ߨ ͳ ͳ ͳǤͺ݁ ଶ
‫ܧ‬௚ ൌ ‫ܧ‬௚ ሺλሻ ൅  ଶ ൬ ൅ ൰െ ሺ͵ሻ
ʹܴ ݉௘ ݉௛ ߝܴ
where Eg is the effective band gap, Eg (∞) the bulk band gap, me and mh the effect mass, h Planck’s constant, R
radius of particles and ε the dielectric constant.
Current –Voltage (I-V) Characteristics
If a Metal/semiconductor contact with a thin interfacial layer is considered, it is assumed that the forward bias
current of the device is due to thermionic emission current, and it may be expressed as [22]

“ “
 ൌ ଴ ‡š’ ൬ ൰ ൤ͳ െ ‡š’ ൬െ ൰൨ሺͶሻ
 
௤ః
Where ଴ ൌ ‫ ܶ כܣܣ‬ଶ ‡š’ ቀെ ್ǡబቁis the saturation current density, ߔ௕ǡ଴ is the barrier height atzero bias, A* is
௞்
the effective Richardson constant and equals to 32 A/cm2 K2 for p-Si and 112A/ cm2 K2 n-Si, A is the diode area, n
is an ideality factor and is a measure of conformity of the diode to pure thermionic emission and it is determined
from the slope of the straight line region of the forward bias ln I–V characteristics according to Eq. (4).
Fig. 3 shows the semi-logarithmic plot of forward and reverse current-voltage characteristics of the CuO/Al (MS)
structures. I-V characteristics of the device have rectifying behavior with a potential barrier at the interface. The
diode rectification ratio (RR) of fabricated diode can be determined at a certain applied voltage on the diode as the
ratio between the passage current when diode connect in the forward bias to the passage current in reverse bias
(IF/IR) The rectification ratio (RR) of Au:CuO nanocomposite/ porous silicon is 15.5 at ±0.5 V. The ideality factors
of the MS structures is 1.82 (dark) & 1.39 ( under illumination).

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 FIGURE 3: Forward and reverse bias current vs. voltage characteristics of the Metal Semiconductor structure

CONCLUSION
In this study, we make a summary on the influences of different factors of synthesis process, some unique
properties and some promising applications of CuO nano particles. The present study demonstrates that the co-
precipitation method is one of the successful and facile routes for obtaining good quality CuO nanoparticles. In co-
precipitation technique, both sodium hydroxide (Method1) and potassium hydroxide (Method 2) as electrolyte are
efficient in aqua medium. The structural analysis clearly indicated the single crystalline nature of CuO monoclinic
phase with a size range 12-14nm (3rd Method, ethanol medium with NaOH electrolyte) and 14-16 nm (1st & 2nd
Method) when the samples are annealed at 200°C and a round 25-30nm crystallite size when annealed at annealed
at 400°C. The SEM morphology of the product revealed that the CuO nanoparticles of cubic, rice like shapes grown
under moderate conditions. The quantum confinement effect exerted by such nanocrystals found to bring a
significant blue-shift in the band gap energy (2.78eV).However, the diode characteristics only appeared in the
samples synthesized by 3rd Method. It was found from the electrical characterizations, that the ideality factor is lying
between 1 and 2. CuO nanoparticles synthesized by facile co-precipitation method may offer some exciting
opportunities for potential applications as absorbing material in solar cells.
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