Ceramics International 44 (2018) 2478–2484

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Structural, vibrational and electronic properties of CuO nanoparticles T

synthesized via exploding wire technique
⁎
Anshuman Sahaia,c, Navendu Goswamia, , Monu Mishrab, Govind Guptab
a
Department of Physics and Materials Science and Engineering, Jaypee Institute of Information Technology, A-10, Sector-62, Noida 201307, India
b
CSIR-National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi 110012, India
c
Department of Physics, Faculty of Applied Sciences (FAS), Manav Rachna University, Sector-43, Aravalli Hills, Delhi-Surajkund Road, Faridabad 121004, Haryana,
India

A R T I C L E I N F O A B S T R A C T

Keywords: The study of mixed phase Cu/Cu2O/CuO nanoparticles synthesized by Exploding Wire Technique has been
Nanoscale materials and structures: fabrication recently reported by us. Aiming to achieve single phase CuO nanoparticles, the mixed phase Cu/Cu2O/CuO
and characterization nanoparticles were subjected to annealing at different temperature and time durations in oxygen environment.
Infrared and Raman spectra In this article, we discussed two samples; two phase Cu2O/CuO and single phase pure CuO nanoparticles ob-
Photoemission and photoelectron spectra
tained by annealing at 500 °C and 900 °C for 10 h. Rietveld refinement and Williamson-Hall analyses revealed
X-ray diffraction
formation of pure phase of CuO at 900 °C with an average crsytallite size of 27.6 nm. Irregular shape of na-
Transmission electron microscopy (TEM)
noparticles with average size of ~8 nm was observed by Transmission Electron Microscopy. Selected Area
Electron Diffraction pattern matches with standard interplanar distance of CuO. Fourier Transform Infrared and
Micro-Raman (µR) spectra exhibit broadening of vibrational modes; indicative of pure phase CuO at 900 °C.
Extensive X-ray Photoelectron Spectroscopy analysis revealed that the percentage contributions of Cu1+ and
oxygen vacancy (VO) decreases whereas; Cu2+ and interstitial oxygen (Oi) enhances on increasing the annealing
temperature from 500 °C to 900 °C and thus, resulting the pure phase formation of CuO nanoparticles. Notably,
through our analyses we propose an electronic band structure diagram on the basis of valance band maximum, as
obtained by XPS and the band gap energy as estimated via UV–visible spectroscopy for mixed phase of Cu2O/
CuO (1.6 ± 0.02 eV) and pure phase of CuO (1.3 ± 0.02 eV) nanoparticles.

1. Introduction related to electron-phonon interaction [5,6]. Earlier several researches

Among transition metal oxide nanomaterials, copper oxide (also
known as cupric oxide, CuO) nanostructured material has drawn great
interest of wide group of researchers [1,2]. Since, CuO is a p-type
semiconductor with a narrow band gap of 1.2 eV, it is widely reported
for gas sensing, interconnection of microelectronic, biologically com-
patible processes involving DNA complexes, solar cell fabrication, high
Tc superconductors, magnetic storage devices, magneto-resistance,
catalysis, photothermal, photoconductive and electrode material for
battery applications [2–4]. CuO also acts as a field emitter and as a
cathodic material in dye-sensitized solar cells (DSSCs) [2]. The com-
parable work function of CuO (5.3 eV) and Pt (5.65 eV), arrays of CuO
nanorods were cheaper substitute to replace Pt in DSSCs [4]. CuO also
attracted much interest because of being the basis of several high-Tc
superconductors [5]. Previously, Raman scattering experiments have
been carried out to investigate the lattice dynamics in CuO powder and
single crystal because Raman intensity was considered to be directly
were performed to study the reactions of copper atoms with dioxygen
because of their important role in corrosion of materials and catalytic
oxidation to oxygen transport in biological systems [7]. Further, the
basic nature to weakly bound complex of Cu + O2 was not very clear
for which different infrared absorption spectroscopies assigned several
groups like cyclic Cu(O2) (C2v) and bent CuOO (Cs), but clear agreement
is still debatable [7]. It was earlier known that phases of Cu/Cu2O and
CuO nanophases coexisted with a slight variation in temperature and
ambient environment which was very important to understand the
oxidation states, electronic and optical properties of copper oxide as
these properties vastly influence the performance of many devices
[1,3].
On the basic of above mentioned promising applications as well as
challenges encountered to achieve single phase CuO nanoparticles via
facile and cost effective synthesis process, we attempt to achieve the
pure CuO nanoparticles by Exploding Wire Technique (EWT).
Advancing ahead from our previous published report, here we report

⁎
Corresponding author.
E-mail address: navendugoswami@gmail.com (N. Goswami).

http://dx.doi.org/10.1016/j.ceramint.2017.10.224
Received 15 April 2017; Received in revised form 30 October 2017; Accepted 30 October 2017
Available online 31 October 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Sahai et al.
the synthesis of pure CuO nanoparticles employing the EWT followed
by systematic annealing in presence of oxygen rich environment [1].
The samples thus obtained were studied through an assortment of
characterization techniques. Hereby, this study explains the synthesis
mechanism as well as transformation of mixed phases CuO/Cu2O na-
noparticles into pure single phase CuO nanoparticles and corresponding
alterations in various structural, vibrational and electronic properties of
the nanosystem.
2. Materials and methods
We adopted Exploding Wire Technique (EWT) to obtain copper
oxide nanoparticles [8]. The details for obtaining the mixed phase of
Cu/Cu2O/CuO nanoparticles have been already reported by some of us
[1]. Advancing on this work, Cu/Cu2O/CuO nanoparticles, initially
collected in the powder form through previous approach, were now
subjected to annealing in quartz tube at different temperatures ranges
(from 100 to 1100 °C) for different time duration (1–10 h), respectively
in the absence and/or presence of O2 rich supply. The powder annealed
for 10 h was grinded to obtain fine nanopowder which was investigated
by various characterization techniques.
3. Characterizations
The XRD data of all samples was acquired using X-ray Diffractometer
(XRD) 6000 Shimadzu Analytical, Japan having incident Cu Kα radiation
wavelength of 1.54 Å. Transmission electron micrographs (TEM) of
nanoparticles were captured employing a Tecnai G20-Stwin, High-re-
solution Transmission electron microscope (HRTEM), operating at the
principal maximum acceleration voltage 200 kV. Utilizing the same
instrument, Energy Dispersive X-rays Spectroscopy (EDS) analysis and
Selected Area Electron Diffraction (SAED) data of CuO nanoparticles
was also collected. The vibrational modes of prepared nanosamples
were probed through Perkin-Elmer BXII FTIR spectrophotometer,
Germany. FTIR spectra of the prepared nanoparticles suspended in the
KBr matrix, were recorded at room temperature in the low energy range
of 440–660 cm−1. Raman scattering processes in prepared nano-
particles were examined through an InVia Raman microscope, Renishaw
UK system consisting of an Ar+ ion laser. The electronic absorptions in
prepared nanoparticles were investigated employing Perkin Elmer
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Ceramics International 44 (2018) 2478–2484
Fig. 1. (a) XRD spectrum of CuO/Cu2O nanoparticles
annealed at 500 °C for 10 h phases of Cu2O, CuO are
shown respectively by ‘#’, ‘Δ’, (b) Rietveld refined
spectrum of pure CuO nanoparticles obtained
through annealing at 900 °C for 10 h. The dots, solid
line, and vertical ticks respectively represent the
observed data, calculated profile, and Bragg posi-
tions for CuO phase. The difference pattern (Yobs-
Ycalc) is given below the vertical tics. (c) W-H plot of
CuO nanoparticles annealed at 900 °C. (d) Crystal
structure of the refined CuO unit cell.
Lambda 35 UV–visible spectrophotometer, Germany. The absorption
spectra of nanoparticles dispersed in DI water were collected. X-ray
Photoemission spectroscopic (XPS) experiments were performed using
an Ultra-high vacuum (UHV) based system, OMICRON Multiprobe Surface
Analysis System operating at a base pressure of 5 × 10−11 Torr. Samples
were mounted on molybdenum plates using conductive tape to avoid
charging. The XPS measurements were carried out by using Mg Kα
(1253.6 eV) radiation source. The core level profile fitting was per-
formed using a Shirley background and Voigt (mixed
Lorentzian–Gaussian) line shape calibrated against the C (1 s) binding
energy of 284.8 eV. The VB maximum (VBM) position was determined
by extrapolating a linear fit to the leading edge of the valence band
photoemission to the baseline [9,10].
4. Result and discussions
4.1. X-ray diffraction (XRD) analysis
Based on the low temperature oxidation kinetics of copper and its
dependence on thickness of oxide layer, a diffusion model was proposed
earlier [11]. As per the previous reports, films of copper oxide show the
formation of CuO through conversion of Cu2O at the surface due to
oxygen abundance in the oxide-air interface along with the instability
of Cu2O in the temperature region of 750–950 °C [12]. Also, it was
reported earlier that unstable phase of Cu2O reacts with oxygen at
1020 °C to form more stable phase of CuO [13–15]. In view of aforesaid
reports, the powder of mixed phase Cu/Cu2O/CuO nanoparticles ob-
tained through EWT method was subjected to annealing at different
temperatures ranges (100–1100 °C) for different time duration
(1–10 h), in the absence and presence of O2 rich supply, respectively. In
order to identify the phase formation, all samples were subjected to
XRD characterization. The XRD spectra of material obtained through
above mentioned annealing conditions are presented in the supple-
mentary file.
It is indicated in the XRD spectrum of the sample, annealed at
500 °C in presence of oxygen (Fig. 1(a)) that incomplete oxidation of
Cu/Cu2O/CuO nanoparticles results in partial formation of CuO phase
(marked by ‘Δ’) concurring with formation of minor Cu2O phase
(marked by ‘#’). This experimental evidence encouraged the in-
vestigators to further anneal the sample at 900 °C in presence of
A. Sahai et al.
Table 1
Rietveld refinement parameters used for atomic positions in FullProf Suite Program (ver.
2.05).
Element X Y Z Occ
Atom #1 Cu 0.25 0.25 0 1.085
Atom #2 O 0 0.414 0.25
oxygen, the XRD data of the same has been presented in Fig. 1(b).
Moreover, Williamson-Hall analysis (shown in Fig. 1(c)) was also per-
formed to estimate the crystallite sizes and strain in the prepared na-
noparticles.
In Fig. 1(b), Rietveld refinement, profile matching and integrated
intensity refinement of X-ray data was performed by using FullProf Suite
Program ver. 2.05. The pseudo-voigt function was used to refine CuO x-
ray data applying C1c1 space group and monoclinic symmetry with Lau
class 2 /m. The parameters thus obtained for the atomic positions of Cu
and O element are presented in Table 1.
Other parameters for example, full width at half maximum
(FWHM), shape parameters, linear interpolations etc. were refined
iteratively. All the diffraction peaks could be suitably indexed to the
CuO teronite phase [13–15]. Refinement results reveal a monoclinic
lattice structure (JCPDS 141–0254), having lattice constants a =
4.68 Å, b = 3.42 Å and c = 5.13 Å alongwith α = γ = 90°, and β =
99.471°. The Rp (profile fitting R-value), Rwp (weighted profile R-
value) and χ2 (quality factor for goodness-of-fit) parameters obtained
after iterative refinement cycles are 18.6, 12.8 and 3.97, respectively.
The crystallite size calculated from W-H plot (as shown in Fig. 1(c))
found to be 27.6 nm whereas, strain (ε) and unit cell volume (V) are
found to be 0.00119 and 81.15 Å3, respectively. The refined crystal
structure of CuO nanoparticles is illustrated through Fig. 1(d). Here, the
crystallographic information file, as obtained by Rietveld refinement,
was used in the Visualization for Electronic and Structure Analysis
(VESTA) software, Version 3.3.2 to visualize the refined structure of
CuO in our case. In usual CuO crystal, Cu atom is coordinated by four
coplanar O atoms, forming an rectangular parallelogram while, O co-
ordination polyhedron has four Cu atoms at the corners of a distorted
tetrahedron [16]. Similar to previous report on CuO structure, it could
be illustrated through Fig. 1(d), that while sharing the opposite edges,
−
two ribbons of parallelograms run in [110] and [110] directions which
can easily differentiate between two types of –Cu-O-Cu- chains along
− annealing at 500 °C and 900 °C are shown in Fig. 4.
the [101] and [101] directions [16]. The energies of these surfaces were
reportedly determined via density functional theory calculations and
{001} facets found to be most active crystal planes that provide highly
reactive sites, leading to enhanced performance for technological ap-
plications [16]. Therefore, CuO nanoparticles prepared by our approach
could possibly be ideal for gas sensing and enhancing the efficiency of
Li-ion batteries [16].
Having determined the basic lattice parameters, we now perform
electron microscopy of single phase CuO sample to directly determine
the real space lattice structure and purity of prepared nanoparticles.
4.2. Transmission electron microscopy (TEM), selected area electron
diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS) analysis
TEM image of CuO nanoparticles annealed at 900 °C is shown in
Fig. 2(a). Here, irregular shape CuO nanoparticles with average size of
8 nm are observed. The agglomeration of smaller nanoparticles is also
indicative through appearance of larger nanostructures in Fig. 2(a).
The interplanar distances (d) estimated through diffraction profile
fitting in Fig. 2(b) were found to be 2.75, 2.54, 2.35, 1.95, 1.84, 1.66,
and 1.55 Å. These values are in excellent match with the ones obtained
earlier by Rietveld refinement respectively as, 2.75 Å (110), 2.53 Å
− −
(002), 2.32 Å (111), 1.96 (1 12), 1.86 Å (2 02), 1.62 Å (021) and 1.58 Å
(202). EDS spectrum (Fig. 2(c)) confirms that the sample obtained at
Ceramics International 44 (2018) 2478–2484
900 °C is free from any impurity. The presence of carbon and Ni peaks
in the data however, is basically due to utilization of carbon coated Ni
grid for the experiment. Thus, collectively from TEM, SAED and EDS
analyses, it is ensured that the prepared sample is of CuO nanoparticles
without any extraneous impurity.
1.086
4.3. Fourier transform infrared (FTIR) spectroscopy analysis
To detect the bondings and interactions through examination of
vibrational modes in the prepared nanomaterials, we performed FTIR
spectroscopy. The FTIR data was recorded in the range of
400–4000 cm−1. However, for better clarity and in view of region of
interest FTIR spectra are shown in a selective range of 400–650 cm−1 in
Fig. 3.
As per theoretical report, a set of six IR active bands exist for CuO at
147 (Bu), 161 (Au), 321 (Au), 478 (Au), 530(Bu) and 590 (Bu) cm−1
[14]. In Fig. 3, we too observe the Au vibrational mode at 478 cm−1, a
Bu Cu-O stretching mode along [101] direction at 533 cm−1 and an-
−
other Bu Cu-O stretching mode along [101] at 581 cm−1 for both the
nanoparticle samples [14]. Interestingly, the modes broaden for the
sample annealed at 900 °C (Fig. 3(a)) as compared to the sample an-
nealed at 500 °C (Fig. 3(b)). The broadening of the peaks suggest that
when the sample was annealed at high temperature, formation of pure
phase CuO nanoparticles give rise to enhancement of intensity for Cu-O
−
stretching mode along [101] and [101] directions. As indirect evidence
for reassuring the purity of the prepared nanomaterials the IR mode at
610 cm−1 is absent now which was previously attributed for the
stretching mode of Cu2-O [14]. This finding further endorses that the
annealing of the samples assist in achieving the pure materials.
4.4. Micro Raman spectroscopy (µRS) analysis
The vibrational properties, micro-structural changes and possible
defect states in prepared nanoparticles could be investigated through
µRaman spectroscopy [5,6]. Copper (II) oxide (CuO) belongs to the C26h
space group with two molecules per primitive cell [5,6]. There are nine
zone-centre optical phonon modes with symmetries 4Au + 5Bu + Ag
+ 2Bg; only three Ag + 2Bg modes are Raman active [5]. In a previous
report, the change in grain size was found to largely shift and broaden
the Raman peaks [5]. The µRaman spectra of nanoparticles obtained by
In Fig. 4, three Raman peaks at 294, 341 and 629 cm−1 are ob-
served for the nanomaterials annealed at 900 °C. Here, second mode (at
341 cm−1) is more intense whereas, third mode (at 629 cm−1) is more
broadened as compared to the respective nanoparticles at 500 °C. In
comparison to the vibrational spectrum of CuO nanocrystals, the peak
at 294 cm−1 can be assigned to Ag mode and the peaks at 341 and
629 cm-1 for the Bg modes [5]. Earlier, the Bg mode was attributed to
the stretching vibration in the x2-y2 plane [6]. Here we notice that these
wavenumbers observed in our study are lower than the reported lit-
erature values (i.e. at 298, 354 and 632 cm-1) and hence indicative of
the size reduction effect in CuO nanoparticles [5]. Earlier, three Raman
modes in CuO (as aforesaid three modes in our case too) were believed
to originate from the vibrations of oxygen atoms only and it was ex-
perimentally shown later that any shift in Raman modes appears due to
grain size [5].
Further as seen in Fig. 4(a) and (b), one can observe that by in-
creasing the annealing temperature, the modes of sample annealed at
900 °C get intense and broadened as compared to those at 500 °C. These
distinct changes demonstrate that the pure CuO phase formation at
900 °C as compared to CuO/Cu2O phase formed at 500 °C.
However, more concrete and direct evidences of alterations in
oxygen vacancies or defects so as to establish the transition of two
phase CuO/Cu2O (at 500 °C) towards single phase CuO (at 900 °C)
could be suitably addressed through x-ray photoelectron spectroscopy
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Fig. 2. (a) Transmission electron micrograph

showing ~ 8 nm average size nanoparticles, (b)
SAED pattern demonstrating the interplanar distance
d for CuO planes and (c) EDS spectrum of nano-
particles obtained by annealing at 900 °C.

(XPS) analysis. Assuming this, we performed the detailed XPS analysis

of nanoparticles annealed at 500 °C and 900 °C.

4.5. X-ray photoelectron spectroscopy (XPS) analysis

The XPS spectra for the Cu (2p) and O (1s) core levels for the na-
noparticles annealed at 500 °C and 900 °C are shown in Fig. 5.
In Fig. 5(a) and (b), the Cu (2p3/2) peaks of both the samples were
deconvoluted into two major components corresponding to Cu1+ and
Cu2+ species along with their satellites [13,14,17,18]. Similarly, in
Fig. 5(c) and (d), the O (1s) spectra were deconvoluted into four peaks
corresponding to O2- and adsorbed oxygen with some chemisorbed
hydroxyl species [13,14,17–21]. The percentage contributions of var-
ious emissions for Cu (2p3/2) and O (1s) are tabulated in Table 2.
Fig. 3. FTIR spectra of nanoparticles obtained after annealing at (a) 500 °C and (b) One can directly infer from Table 2 that with the increase in an-
900 °C. nealing temperature, the percentage of Cu2+ increases from 42.4% to
65.2%. Also, a decrease in Cu1+ phase was observed from 25.3% to
10.2%. Together, these findings confirm that Cu2O nanoparticles at
500 °C are oxidised completely to transform into CuO nanoparticles and
hence, Cu2+ enhances at the expense of decrement of Cu1+. The neg-
ligible presence of Cu1+ phase in samples annealed at 900 °C, was at-
tributed to the naturally oxidised Cu nano-crystalline layer [22].
As observed from Fig. 5(c, d) and Table 2, an asymmetric O (1s) XPS
core level peaks could be deconvoluted adopting Voigt fitting into four
components i.e. lattice oxygen of CuO and Cu2O (OL(Cu2+) and
OL(Cu1+)), oxygen vacancy (VO), interstitial oxygen (Oi) and adsorbed
oxygen (OC). The OC component of high binding energy (> 532.9 eV) is
usually attributed to chemisorbed and dissociated oxygen species (O2-,
O2- or O-) and OH- [21]. The total contribution of lattice oxygen (O2-)
and chemisorbed and dissociated oxygen species (O2-, O2- or O-) and
OH- remained almost same in both the samples. No significant change
Fig. 4. Raman spectra of prepared nanoparticles annealed at (a) 500 °C and (b) 900 °C for in the percentage contribution of lattice oxygen (O2-) is observed al-
10 h. though, oxygen vacancy (VO) decreased and interstitial oxygen (Oi)
increased with annealing at 900 °C in oxygen rich environment. This
observation is complementary to above findings of enhancement of
Cu2+ state with annealing. Jointly, the changes of Cu1+ into Cu2+ and
decrease of VO to enhance Oi absolutely establish the oxidation of Cu2O
nanoparticles to form CuO nanoparticles at 900 °C.

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Fig. 5. Deconvoluted XPS peaks for the nano-

particles annealed at 500 °C (a and c) and 900 °C (b
and d).

Table 2 photoelectric cross-section and the density of states of the valance band
Position and percentage contribution of various peaks occurring in Cu (2p3/2) and O (1 s) of the crystal [23]. Moreover, it will be interesting to note the spectral
core level spectra of samples annealed at 500 °C and 900 °C.
width of VBM spectra of the samples annealed at 500 and 900 °C
Sample CuO/Cu2O @500 °C CuO @900 °C Attribution
(Fig. 6(a) and (b), respectively). The broader plateau observed in
name Fig. 6(a) could be ascribed to overlapping of two density of states for
Peak Position % Position (eV) % the valence band of CuO/Cu2O nanoparticles. Hence, it is in line with
(eV) coexisting two phases of Cu2O/CuO nanoparticles at 500 °C. However,
1 932.9 25.3 932.7 10.2 Cu1+
contrary to broader hump of Fig. 6(a), the peak is quiet sharp in
2 935.0 42.4 934.6 65.2 Cu2+ Fig. 6(b) and hence, vividly establishes the single phase formation of
3 941.0 11.8 940.8 4.2 Cu2+(Satellite Peak) CuO nanoparticles.
4 943.4 20.5 943.3 20.4 Cu2+(Satellite Peak) Understanding the coexistence of Cu2O, albeit in little quantity,
5 530.0 20 530.2 21.7 OL(O2-)
along with the dominating phase at 500 °C and its transformation into
6 531.7 33.2 531.7 29.3 VO (Oxygen vacancy)
7 533.0 26.8 532.9 31 Oi (Interstitial CuO at 900 °C, has been of great significance. In view of this, we further
oxygen) propose the schematics of energy band diagrams of both types of na-
8 534.3 20 534.3 18 OC (OH-/adsorbed noparticles systems illustrated through Fig. 7.
moisture) Before elucidating aforesaid proposed schematics, the prerequisite
brief background of the electronic band structure of semiconductor is as
follows. The electronic structure of semiconductor is usually signified
The study of valance band structure of graphite states that X-ray
through its band gap (Eg), which is basically an energy gap with few
photoemission spectrum of valance band is related with density of
electronic states (of low density of states) between valence band and
states [23]. To analyse the electronic structure and semiconducting
conduction band (which have high density of states) [25]. The electrons
behaviour of nanoparticles (p- or n- type), the valence bands of both the
undergo a transfer from the highest occupied molecular orbital
samples were probed (shown in Fig. 6). We attempted to examine the
(HOMO) known as valence band maximum (VBM) with energy EV,
valence band spectra of prepared nanoparticle employing XPS. The
which is also a measure of the ionization potential I, of the bulk ma-
valence band maximum (VBM) to Fermi level (EFi) separation are il-
terial [25]. The lowest unoccupied molecular orbital (LUMO) in most
lustrated through Fig. 6(a) and (b), as obtained for the two samples
semiconductors coincides with the bottom of the conduction band (CB),
CuO/Cu2O (at 500 °C) and pure CuO (at 900 °C) nanoparticles, re-
having band energy EC, where EC is a measure of the electron affinity
spectively.
(EA) of the compound [25]. The Fermi level energy (EF) represents the
The VBM positions were found to be 0.13 and 0.5 eV, respectively
chemical potential of electrons in a semiconductor [25]. In essence, the
for the sample obtained via annealing at 500 °C and 900 °C. As per
Fermi level is the absolute electronegativity –χ, of a pristine semi-
literature, both Cu2O and CuO are p-type semiconductors with direct
conductor, a value that corresponds to the energy halfway between the
band gap of 2.2 and 3.39 eV, respectively [2–4,12–14,17,24]. Other
conduction and valence band edges [25]. The relationship between
investigations report the band gap of bulk CuO to be about 1.2 eV [24].
band edge energies and electronegativity can therefore be expressed as:
From UV–visible spectroscopy, we had already estimated the values of
absorption energies from the band edge. The samples annealed at EC = −EA = −χ + 0.5Eg (1)
500 °C and 900 °C, absorption energy values were found to be
1.6 ± 0.02 eV and 1.3 ± 0.02 eV, respectively (data not shown). The EV = −I = −χ – 0.5Eg (2)
low value of VBM also indicates the p-type nature of the prepared na- Incorporation of impurities in the structure of a semiconductor leads
nomaterial [24]. It has been reported earlier that the intensity of the to the presence of electron acceptor state levels and/or donor state le-
photoemission spectrum is directly proportional to average vels within the band gap [25]. The presence of donor or acceptor state

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A. Sahai et al.
levels changes the position of EF so that EF lies just above EV for p-type
semiconductors (presence of acceptor states) and EF lies just below EC
for n-type semiconductors (presence of donor states) [25].
In our case, as estimated from valence band analysis of CuO/Cu2O
nanoparticles (Fig. 7(a)), the EFi lies at 0.13 eV above the VBM while for
CuO nanoparticles (Fig. 7(b)), the EFi lies at 0.5 eV above the VBM. This
demonstrates that the Fermi level lies closer to VBM for the sample
containing mixed phase of CuO/Cu2O as compared to that of pure
single phase of CuO nanoparticles. Thus, pure CuO nanoparticles as
well as two phase Cu2O/CuO nanoparticles prepared by us maintain
their p-type behaviour [2–4,12–14,17,21]. Finally, our analysis also
reveals that the sample obtained at 900 °C is pure single phase CuO
nanoparticles as the close gap of 0.13 eV from VBM in case of CuO/
Cu2O nanoparticles only (Fig. 7(a)), is suggestive of the existence of
degenerate p++-type semiconducting behaviour of mixed CuO/Cu2O
nanoparticle which is absent for CuO nanoparticles as here EFi is not
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Ceramics International 44 (2018) 2478–2484
Fig. 6. Valence band spectra of nanoparticles an-
nealed at (a) 500 °C and (b) 900 °C.
close to VBM. Thus, this analysis unravelled the intricate depiction of
electronic structure of the nanoparticles obtained by our novel process.
5. Conclusions
We establish that the facile synthesis method of EWT, capable of
synthesizing Cu/Cu2O/CuO nanoparticles, can further be advanced to
achieve pure single phase CuO nanoparticles. We developed and opti-
mized the process to obtain pure phase CuO nanoparticles by annealing
the mixed phase nanomaterials to 900 °C in oxygen rich environment.
Irregular shapes of CuO nanoparticles with average diameter ~ 8 nm
are vividly seen. The FTIR and Raman spectroscopy studies revealed the
fundamental modes of copper oxide and endorsed the XRD interpreta-
tions. Although above analyses could only partially implicate towards
the transformation of Cu2O into CuO with the increasing rate of an-
nealing, yet the finer details of the oxygen – annealing driven
Fig. 7. Schematic energy band diagrams for samples
annealed at (a) 500 °C consisting of CuO/Cu2O na-
noparticles and (b) 900 °C consisting of pure CuO
nanoparticles. Symbols E0, EFi, Eg, EA and φ corre-
sponds to Fermi level, intrinsic Fermi level, electron
affinity and work function, respectively.
A. Sahai et al.
conversion of Cu2O/CuO nanoparticles into CuO nanoparticles can be
substantially elucidated through our detailed XPS analyses. By XPS
analysis, not only the quantitative determination of enhanced Cu2+
phase was demonstrated but more notably the degenerate p++ type and
simple p type behaviour, for CuO/Cu2O and CuO samples, respectively
was proposed on the basis of VBM spectra based schematics.
Acknowledgements
We are grateful to Dr. P.K. Siwach, NPL, New Delhi, for providing
annealing resources and XRD facility and Prof. B.R. Mehta, IIT Delhi for
providing crucial TEM characterization. Author (AS) acknowledges
Department of Science and Technology (DST), New Delhi for INSPIRE
Fellowship [IF#120042].
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.ceramint.2017.10.224.
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