Journal of Materials Chemistry C

Nanostructured Copper Oxide Semiconductors: a

Perspective on Materials, Synthesis methods and
Applications

Journal: Journal of Materials Chemistry C

Manuscript ID: TC-FEA-02-2014-000345.R1

Article Type: Feature Article

Date Submitted by the Author: 23-Apr-2014

Complete List of Authors: Zoolfakar, Ahmad; RMIT University, School of Electrical and Computer
Engineering; Universiti Teknologi MARA, Fakulti Kejuruteraan Elektrik
Abdul Rani, Rozina; RMIT University, School of Electrical and Computer
Engineering
Morfa, Anthony J.; Freie Universität Berlin, Fachbereich Physik
O'Mullane, Anthony; Queensland University of Technology, School of
Chemistry, Physics and Mechanical Engineering
Kalantar-Zadeh, Kourosh; RMIT University, School of Electrical and
Computer Engineering
Page 1 of 34 Journal of Materials Chemistry C

Journal of Materials Chemistry C RSCPublishing

REVIEW

Nanostructured Copper Oxide Semiconductors: a

Cite this: DOI: 10.1039/x0xx00000x
Perspective on Materials, Synthesis methods and
Applications

Received 00th January 2012,

Accepted 00th January 2012 Ahmad Sabirin Zoolfakar,*,a,b Rozina Abdul Rania, Anthony J. Morfac, Anthony
DOI: 10.1039/x0xx00000x
P. O’Mullaned and Kourosh Kalantar-zadeh*,a

www.rsc.org/

The oxides of copper (Cu x O) are fascinating materials due to their remarkable optical,
electrical, thermal and magnetic properties. Nanostructuring of CuxO can further enhance the
performance of this important functional material and provides it with unique properties that
do not exist in its bulk form. Three distinctly different phases of CuxO, mainly CuO, Cu2 O
and Cu 4O 3 can be prepared by numerous synthesis techniques including, vapour deposition
and liquid phase chemical methods. In this article, we present a review of nanostructured
Cux O focusing on their material properties, methods of synthesis and an overview of various
applications that have been associated with nanostructured Cux O.

1. INTRODUCTION In this feature article, we present a general, yet complete,

review of nanostructured CuxO. The present review is
distinguishable from other reviews1, 17, which have a focus on
Lately, there has been a great deal of interest in nanostructured one type of CuxO (generally CuO or Cu2O), while this review
copper oxide (CuxO) semiconductors. This interest in endeavor to thoroughly discuss three types of CuxO, including
nanostructured CuxO is fuelled due to their remarkable physical CuO, Cu2O and Cu4O3. The organization of this review is as
and chemical properties as well as exciting prospects for a follows: firstly, we discuss the fundamental chemical and
variety of applications.1, 2 physical properties of nanostructured CuxO and then we
Nanostructured Copper oxides are relatively abundant in summarize the different methods of synthesis that have been
nature3, and a wide range of information is now available for reported. Finally we present a selection of interesting
their synthesis. Nanostructured CuxO can be grown using applications that exploit CuxO and illustrate the enhancements
different synthesis techniques, including vapour and liquid made possible by using the nanostructured form of this
phase deposition processes, in which a variety of nano material.
morphologies can be obtained.
Nanostructured Copper oxides are exceptionally versatile
and offer unique characteristics in many applications. CuxO 2. FUNDAMENTAL PROPERTIES
nanomaterials have been used as colouring agents for the
production of Roman mosaic glasses and antique ceramics for In this section, the fundamental properties such as crystal
thousands of years.4, 5 Nanosized CuxO has been widely structures, electronic band structures, optical and electrical as
utilized as a fungicids6, 7 and in anti–fouling paints8, 9 due to its well as transport properties of nanostructured CuxO are
biocide capability. With the advent of nanotechnology, CuxO discussed. This section also describes the effect of doping or
has shown great impact in numerous research fields including the presence of impurities on the properties of nanostructured
optics, sensors, tribology, superconductor, electrochemistry and CuxO.
electronics.10-14
The most common crystal phases of CuxO are: (a) CuO also 2.1 Crystal Structure
known as copper (II) oxide or cupric oxide where the mineral is
known as tenorite, (b) Cu2O also known as copper (I) oxide or
CuO which has a black colour and crystallizes in monoclinic
cuprous oxide with the mineral name of cuprite, and (c) Cu4O3
centered Bravais lattice in the space group of C2/c. The
with the mineral name of paramelaconite.1, 2, 15, 16

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crystallographic properties of CuO are tabulated in Table 1.2, 15, 2

16, 18 different values of Eg were due to different models ( (αE ) or
The copper atom is coordinated to four coplanar oxygen
1
atoms situated at the corners of a rectangular parallelogram,
which form chains by sharing edges. The oxygen atom is (αE ) 2 ) being used to determine the band gap value. The other
coordinated to four copper atoms situated at the corners of a significant factor that contributes to the variation of band gap
distorted tetrahedron. The chains traverse the structure in the values of CuO films is related to the heat treatment. 29, 30 Izaki
[110] and [ 1 10] directions. The two types of chains alternate in et al. demonstrated that annealing electrodeposited CuO films
the [001] direction and each type is stacked in the [010] altered the Eg value.29 They reported a reduction of 7.5% in Eg
direction with a separation between the chains of about after annealing the as-deposited CuO at 773 K. They suggested
2.7 Å.16, 18, 19. Figure 1a demonstrates the crystal structure of that the changes in the composition, grain size and lattice
CuO. constant were induced by the annealing process, altering the
Cu2O is the second stable phase of copper-oxide CuO band gap.29
compounds which is reddish in colour. Cu2O belongs to the In nanostructured CuO, the band gap generally increases
with reducing crystallite dimensions.1, 33 Experimentally, this is
cubic structure (space group, Oh4 or Pn 3 m) with a lattice often observed as a blue shift of the optical absorption band-
constant of 4.2696 Å. Each Cu atom in the unit cell is edge when the nanostructure dimensions are reduced. The blue
coordinated by two oxygen atoms.19 The crystallographic shift can be attributed to the quantum confinement (QC)
properties of CuO are tabulated in table 1. 2, 15, 16, 18 Figure 1b effect.1, 34, 35 The strong QC effect occurs when the size of the
demonstrates the crystal structure of Cu2O. crystal is reduced to much smaller than Bohr radius for the
The third stable phase of copper-oxide with an atomic ratio material (≈6.6 nm for CuO).1 This causes direct changes to the
of 1.33 is Cu4O3.20 Cu4O3 is a mixed of Cu(I)/Cu(II) oxide. The electron wavefunctions and hence significantly alters the Eg.
local coordination environments of Cu(I) and Cu(II) are similar The weak QC effect occurs when the crystal size is larger than
to the ones found in Cu2O and CuO.21 This less studied the Bohr radius. This causes indirect perturbation of the
compound of the CuxO family was first discovered in 1870 as a electron wavefunction due to Coulomb effects and results in
mineral in the Copper Queen mine (Arizona, US).2 Cu4O3 more subtle changes in the band gap energy. 34, 35 In a recent
belongs to the tetragonal structure (space group, I41/amd) with study conducted by Rehman et al., different scales of CuO
a lattice constant of a = 5.837 Å and c = 9.932 Å.21 Figure 1c nanoparticles, where the crystallite dimension is controlled by
demonstrates the crystal structure of Cu4O3. From the crystal the annealing.33 The crystallite dimensions obtained ranged
structure, one can observe that there are two types of copper from 11 nm (T = 250 °C) to 20 nm (T = 600 °C). They reported
ion which are Cu+ and Cu2+. The Cu+ has two oxygen atoms a reduction of 7% in direct Eg with an increase of crystallite
nearest neighbours forming collinear bonds of length 1.87 Å dimensions.33 In addition, it has been reported that the band
which is similar to cuprite (Cu2O ~ 1.85 Å). Similarly, the Cu2+ gap values of the nanostructured CuO can be tuned via
is surrounded by four oxygen atoms with bond lengths and engineering the morphology36-38 as well as doping39-42.
angles being very close to those observed in tenorite (CuO).18, Cu2O is also a p-type semiconductor material due to the
19, 21
The crystallographic properties of Cu4O3 are tabulated in presence of copper vacancies.2, 43 It is a direct band gap
table 1.2, 21, 22 material with Eg > 2.1 eV. However the band gap can be tuned
via engineering the grains dimensions. 24, 28, 30, 44, 45 This
observation is widely attributed to the quantum confinement
2.2 Electronic Band Structure effect in smaller grains, causing a blue shift in the band gap.34,
35, 46
In a recent study conducted by Poulopoulos et al.,46 on
The reported band gap (Eg) values for CuO, which is a p-type Cu2O thin films with thicknesses ranging from 0.75 to 5.4 nm
semiconductor, are generally in the range of 1.2 to 2.16 eV.1, 23- the Eg value increased significantly from ~ 2.6 eV (5.4 nm film
27
This wide range is attributed to several factors, including thickness) to ~ 3.8 eV (0.75 nm film thickness) due to quantum
interpretation of the nature of the gap (i.e. direct or indirect), confinement effects. In addition, Balamurugan et al 45 and
annealing treatment, grains dimensions, morphology and Chang Y et al.44 also reported on the observation of quantum
doping.1, 25, 28-30 According to the Tauc relationship, for photon confinement effects in Cu2O. They further studied the effect of
energies (E) greater than the band gap energy, the light temperature45 and annealing duration44 on manipulating the
absorption can be approximated using:31 crystallite sizes and hence altering the band gap of Cu2O.
Similar to CuO, the optical band gap of Cu4O3 has also
been reported with a wide range of values from 1.34 to 2.47 eV
(
αE = α o E − E g )η (1)
which can also be attributed to the interpretation of the type of
band gap and whether direct or indirect transitions are
where α is the absorption coefficient, α o is a constant, E g is allowed.20, 32, 47, 48
A good comparison between the electronic properties of the
the band gap energy and η is an exponent that depends on the three types of CuxO is presented via the band structure density
1 functional theory (DFT) calculations by Heinemann et al.
type of transition involved. The value of η is or 2 for direct (Figure 2i).19 Figure 2ii illustrates the Brillouin zones with
2
or indirect transitions, respectively. Rakhshani et al. have special high symmetry k points of the three copper oxide
reported detailed studies of band gap determination of RF compounds, which were used for the band structures DFT
sputtered CuO films.23 They found that their CuO films calculations.19
exhibited an indirect transition with a band gap of 1.21 eV. In
contrast, Pierson et al. while reporting the same deposition
technique (RF sputtering), determined their CuO films
exhibited a direct band gap with a value of 1.71 eV.32 The

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2.3 Optical Properties phonon interaction and the negative thermal expansion (NTE)
in CuxO. These methods also provided information about spin–
phonon interaction and size dependent electron phonon
The optical behaviours of CuxO films have been experimentally scattering.61 Debbichi et al. reported an extensive study of
studied, in particular the complex dielectric function vibrational properties of CuxO via Raman spectroscopy where
( ε (E ) = ε 1 (E ) + iε 2 (E ) ) was determined via spectroscopic they clearly distinguished the different types of vibrational
ellipsometry.2, 49, 50 For comparison, the imaginary part ( ε 2 ) of modes either by Raman and IR spectroscopy.61 Recently, Shih
et al. have reported studies on the size effects of spin-phonon
the dielectric function for CuO, Cu2O and Cu4O3 are shown in
coupling in in-plane CuO nanowires.62 They employed low-
Figure 3a,b with Gaussians fitting marked with numbers 1 to 7.
temperature Raman spectroscopy for probing the local atomic
For Cu2O the peaks originate from the various band gaps
vibrations of nanowires. They found that the spin-phonon mode
corresponding to 2.59 eV (1), 2.71 eV (2),…and 5.24 eV (7).2
varies with the size of the CuO nanowires due to the increase in
The difference in energy between these two first peaks is
the strength of spin-phonon coupling.62
attributed to the spin–orbit–splitting energy of ~0.12 eV for
The IR spectroscopy modes are associated with the relative
Cu2O.49 The absence of any sharp peaks for the CuO ( ε 2 )
motion of both copper and oxygen atoms which consist of
spectrum is due to low symmetry of this crystal. Similarly no asymmetric Cu–O stretching and asymmetric O–Cu–O bending
sharp peak is seen for Cu4O3 for energies of less than 3.7 eV. modes. In contrast, Raman active modes only involve the
There are many reports regarding the absorption coefficient relative motion of oxygen atoms.63 Figure 4 shows Raman
α (E ) and normal–incidence reflectivity R(E ) of CuxO films in spectra of CuxO with calculated frequencies of Raman active
optical ranges.2, 49-51 Cu2O is expected to have an essentially vibrational modes.61 The symmetries of the zone–center modes
full Cu 3d shell with a direct forbidden band gap of 2.17 eV in are given by the following representations:2, 61
bulk, which can only absorb light up to the visible region. In
contrast, CuO has an open 3d shell with a direct band gap (1.2 Γ Cu 2 O = A 2u + E u + 3T1u + T2u + T2g (2)
eV in bulk) of charge-transfer type, which can absorb light up
to the near infrared (IR) region.1, 15, 27 A detailed analysis of the Γ CuO = A g + 2Bg + 4A u + 5B u (3)
absorption coefficient obtained on bulk and thin film Cu2O can Γ Cu 4O3 = 3E g + A1g + 2B1g + 9E u + 6A 2u + 5B 2u + 2B1u + 2A1u (4)
be found in the report by Marleba et al.51 Additionally,
Rehman et al. and Borgohain et al. reported the optical
absorption properties of CuO and Cu2O nanoparticles of
different sizes, respectively.33, 52 A comparative study of optical 2.5 Electrical Properties
absorption between nanoparticles and near-monodisperse
nanospheres of Cu2O has been reported by Zhang et al.53 They The electrical conductivity and hole density of p–type Cu2O
found that the nanospheres of Cu2O have a wide absorption films vary with copper vacancy density, which act as shallow
peak at 520 nm while Cu2O nanoparticles have an absorption acceptors.2 Similarly in CuO, copper deficiencies account for
edge at 550 nm.53 the intrinsic p–type semiconducting behaviour.64 Suda et al.
Mayer et al. have reported that CuO is nonluminescent.2 and Young et al. have studied the effect of temperature on
This is despite a few reports demonstrating the electrical conductivity of CuO and Cu2O films, respectively
photoluminescence (PL) of CuO films, however the purity of (Figure 5 a,b).65, 66 They have shown that an increase in
such films is questionable (the presence of Cu2O is a temperature increases the conductivity of CuO and Cu2O due to
possibility). Nevertheless, Zhang et al. reported a detailed an increase in hole concentration.65 Similar findings were also
analysis of the PL properties of CuO nanostructures. They reported by Gopalakrishna et al.67 using Hall effect studies.
found that the PL properties of nanostructured CuO can be They revealed a significant increase in conductivity, mobility
controlled via altering their shape, dimension and morphology.1 and carrier concentration of nanocrystalline CuO after
The QC effect and specific surface effect are the two most annealing.67 Apart from temperature, electrical properties of
reported mechanism which can result in the blue shift and red CuxO are also relied on grain dimensions, grain boundary, film
shift of the PL peak, respectively.1, 54 On the other hand, Cu2O thickness, specific phase and dopants.1-3, 68-72 Shao et al.
shows a weak PL effect due to the fact that optical transitions reported an electrical conductivity of individual single CuO
require parity change, which does not exist between the nanowires grown by thermal oxidation.69 The electrical
energetically highest valence band and lowest conduction band transport measurement has shown that the CuO nanowire has a
of the Cu2O direct transition band.2 In bulk Cu2O, there are conductivity of 7.8 × 10−4 (Ω cm)−1.69 Additionally, Liao et al.
three peaks or shoulders that can be assigned to doubly charged reported an individual Cu2O nanowires has a high mobility of
2+
oxygen vacancies ( VO ) at 1.72 eV (720 nm), singly charged > 95 cm2 V−1s−1.70 It is possible to tune the electrical properties
1+ (resistivity, carrier concentration and mobility) of CuxO by
oxygen vacancies ( VO ) at 1.53 eV (810 nm) and copper
changing the stoichiometry and crystallinity of the CuxO films
vacancies ( VCu ) at 1.35 eV (920 nm).2 In nanostructured Cu2O, during the deposition process. Deposition parameters, such as
these peaks and shoulders can be tuned via shape, dimension pH of the solution in electrodeposition and hydrothermal
and morphology alterations as observed by Shi et al.55, 56 methods and ion pressure and concentration in RF sputtering
techniques, significantly contribute to changes in stoichiometry
2.4 Vibrational Properties and crystallinity.73-75.

The lattice dynamics of CuxO materials have been studied

using IR, Raman and photoluminescence spectroscopy.57-61
These studies provided insight into the nature of the electron

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2.6 Thermal Properties is due to oxygen vacancies at the surface/or interface of the
nanoparticles.1, 105
A neutron diffraction study revealed that Cu4O3 undergoes a
A limited number of studies have been carried out on the magnetic phase transition below 42.3 K leading to a pyrochlore
thermal properties of pristine copper oxides films. However, lattice.95, 96 The amplitude of the magnetic moment carried by
great interest has been shown for the development of Cu2+ is ~0.46 µ β which indicates the strong covalent character
nanoparticles of CuxO suspensions in fluids (nanofluids) due to
the significant enhancement of thermal conductivity that they of the Cu–O bonds and the presence of strong fluctuations even
grant to the fluid in which they are suspended.76-79 The at low temperatures.95
relatively high thermal conductivity of the CuO (76.5 Compounds made of Cu and O are the base of a famous
W/mK)78, makes it an excellent candidate for enhancing the class of high–Tc superconductors.94 Superconductivity in these
efficiency and reliability of refrigeration and air conditioning materials is observed when they are strongly doped away from
systems.80, 81 In contrast, Cu2O has a rather low thermal their ideal stoichiometry. It has been shown that spatial
conductivity of the order of 4.5 W/mK.82, 83 It has been shown changes in carrier density and superconducting gap produce
that the thermal conductivity enhancement of both CuO and local inhomogeneity, which strongly affects their
Cu2O nanofluids correspond to an increased particle volume superconductivity.106
fraction and temperature.84-87 High–Tc was first discovered by Bednorz and Müller in
The variations in the Seebeck coefficient (S) of CuO and 1986 using Cu and O compounds such as La2CuO4 doped with
Cu2O as a function of temperature are shown in Figure 5a,c for Ba.107 A few months later it was found that doping the same
which both oxides show decreasing trends. It has been shown material with Sr raised the superconducting critical temperature
that at 500 K, CuO and Cu2O exhibit a maximum value of 200 to nearly 40 K.107 Recently, the performance of high-Tc copper
µV/K and 1050 µV/K, respectively.65, 66 and oxygen based materials were further enhanced with the
The presence of a wide gap in the phonon spectra between inclusion of extra oxygen atoms as mobile “holes” into the
low frequency (due to acoustic and optical phonon modes that copper oxide planes as illustrated in the Bi2Sr2CaCu2O8+x and
involve the motion of Cu atoms) and high frequency (due to the YBa2Cu3O6+x systems.106, 108 Apart from providing charge
optical modes of oxygen vibrations) bands are reflected in the carriers, the role of oxygen dopants is still debatable and being
temperature dependence of heat capacity.88 The calculated and investigated.106, 108-110
experimental heat capacities (Cp) of CuO and Cu2O as a
function of temperature are shown in Figure 5d,e.88-93 As seen
from the Figure, the shape of Cp vs temperature curves for both 2.8 Doping
CuO (for temperatures below 800 K) and Cu2O (for
temperatures below 500 K) are accurately accounted for by the
calculations that employ the quasi–harmonic approximation.88 It is possible to modify the chemical and physical properties of
CuxO through doping. It has been shown that doping has the
capability to alter the conduction type of Cu2O (from p to n).
Based on the valence of Cu and O, which are +1 and –2 in
2.7 Magnetic Properties and Superconductivity
Cu2O, some n–type dopants including group VII elements such
as halogens (O sites) (and possibly group II elements (Cu
The copper–oxygen covalent bond is the prominent factor sites)) allow this transition to occur.111 The typical reported
governing the properties of high transition temperature (High- halogen dopants include flourine (F), chlorine (Cl) and bromine
Tc) superconducting CuxO compounds.94 Both CuO and Cu4O3 (Br) which can be intercalated into the structure of Cu2O
have an antiferromagnetic ground state. For CuO the during the synthesis process.111-114 Theoretically, F is the best
antiferromagnetic unit cell has twice the size of the primitive match for O given the similarity in size; however, CuF is
unit cell of the crystal.19 In the case of Cu4O3, it was suggested soluble in water.111 Recently, Scanlon et al. have demonstrated
that the antiferromagnetic unit cell doubles the crystallographic that intrinsic n-type defects or defects complexes in Cu2O
unit cell in all three special directions.19, 95-97 Bulk CuO is created during an electrodeposition process cannot be the
antiferromagnetic with Néel temperatures from 213 K to 230 source of any n-type behaviour.75 They have suggested that the
K.1, 98, 99 The CuO antiferromagnetic transition takes place in n-type conduction is due to an inversion layer which was
two stages: near 230 K it leads to incommensurate attributed to a shallow donor level being formed during the
antiferromagnetic order and near 213 K by a first order electrodeposition process or due to external impurities
transition to a commensurate antiferromagnetic order.94 As (dopants).75
mentioned in section 2.1, the copper atom of CuO is Generally, the hole density of native p–type CuxO films are
surrounded by four coplanar oxygen atoms, resulting in two poor, uncontrollable and sensitive to the preparation methods
sets of one dimensional Cu–O chains. The magnetic interaction and experimental conditions. It has been reported that nitrogen
due to super exchange leads to antiferromagnetic order in the (N) and silicon (Si) doped Cu2O via a RF sputtering process
can significantly reduce such instabilities.115-118 These dopants
Cu–O–Cu chains along the [10 1 ] direction with a bond angle were found to act as acceptors, which are incorporated into the
of 146°.94 Magnetic properties of nanostructured CuO oxygen lattice without converting the conduction type of
significantly rely on their grain dimensions, morphology as Cu2O.117, 118 To further stabilize the films Ishizuka et al. and
well as anisotropy of the nanostructures.1 A diameter of 10 nm Okamoto et al. investigated the effect of passivation using
is a critical size for CuO nanoparticles to show a ferromagnetic hydrogen (H) and crown–ether cyanide of the N doped Cu2O
behaviour.1, 100-102 Interestingly, there are reports regarding films.115, 119 The improvement after the treatment indicates that
room-temperature ferromagnetism of pure CuO hole traps are passivated by the cyanide or protons. These holes
nanostructures.1, 103-105 The room-temperature ferromagnetism traps are generally due to oxygen vacancies or dangling bonds
of Cu.115

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For solar cells applications, the intrinsic photoconductivity 10−3 to 1.8 × 10−3 Torr. This indicated that the higher the
of Cu2O can be limited by minority charge carrier oxygen partial pressure, the smaller the crystallite size in the
recombination caused by native defects acting as trap states. nano-crystalline Cu2O thin films.120 In contrast, Elfadill et al.
Isseroff et al. used first principles DFT calculations to study reported the crystallite size of CuO increased from 12 to 24 nm
these trap states and demonstrated that substitutional cation as the oxygen pressure increased.125
doping reduces the recombination effect.43 They found that Generally in an oxygen rich sputtering chamber, at
split vacancies are the source of trap states that inhibit the relatively low sputtering powers, only a small number of Cu
minority carrier diffusion in Cu2O. Dopants such as lithium atoms are sputtered, which effectively react with oxygen in the
(Li), magnesium (Mg), manganese (Mn), and zinc (Zn) prevent plasma, resulting in the deposition of films with high oxygen
the formation of the split vacancies for a single cation vacancy content such as CuO films. Conversely, Cu2O films are formed
which resulted in an electronic structure that exhibited no trap at high sputtering powers, due to a large number of sputtered
states within the band gap.43 Cu atoms.122, 126 However, relatively high sputtering powers
can also adversely affect the stoichiometry of the films,
resulting in presence of unreacted metallic copper and
undesirable stoichiometric ratios between copper and
3.0 NANOSTRUCTURED CuxO SYNTHESIS oxygen.122
Although Cu4O3 was discovered during the late 1870s, the
synthesis of single phase Cu4O3 thin films has rarely been
Many different approaches for the synthesis of nanostructured
reported. Pierson et al. and Richthofen et al. have successfully
CuxO have been implemented using both vapour and liquid-
demonstrated the synthesis of single CuO, Cu2O and Cu4O3
phase-based methods. In this section, we present the most
phases by varying the oxygen flow rate using a reactive
common synthesis methods and describe how they can be
magnetron sputtering technique.32, 128 They used a Cu target
employed for engineering and tuning the morphologies and
with the RF power maintained at 600 W. It was suggested that
properties of CuxO.
conductive Cu−rich copper oxide (Cu4O3) thin films tended to
form with an oxygen flow rate R(O2) < 30%, whereas insulator
3.1 Vapour phase Synthesis O−rich copper oxide (CuO) thin films tended to form at R(O2)
≥ 30%.129 This is in contrast to the work of Blobaum et al.
Vapour phase synthesis methods can be divided into two whom also successfully synthesized Cu4O3 films via the
different categories: (i) physical vapour deposition (PVD) and sputtering, but with a CuO target and at a lower sputtering
(ii) chemical vapour deposition (CVD). The main difference power of 200 W.127
between them is the process they employ, in which PVD uses
physical forces to deposit films, while CVD uses chemical 3.1.1.2 Thermal Evaporation
processes.
Deposition of CuxO films using thermal evaporation is
3.1.1 PVD methods achieved by vaporizing a source material of Cu or CuxO (in
either powder or condensed form) using heat either in a
Many of the common PVD synthesis techniques such as RF vacuum or in a controlled gaseous environment at a low
sputtering, direct current (DC) sputtering, thermal evaporation, pressure.25, 45, 130-133 The vaporized Cu or CuxO that emanates
thermal oxidation, molecular beam epitaxy (MBE), pulse from the material source interacts with the gas molecules in the
vapour deposition (PLD) and electron beam epitaxy (EBE) environment of the deposition chamber before condensing onto
have been used for the deposition of nanostructured CuxO. A a substrate. Processing parameters such as evaporation
PVD process is purely physical, starting with either CuxO or temperature, substrate temperature, substrate type, gas
Cu as the source material in the form of a solid target or environment and pressure all play important roles in achieving
powder, which is evaporated or sputtered with the application the desirable CuxO thin films.25, 131, 134 It has been reported that
of ion bombardment, thermal heating, electron beam the as-synthesized CuxO films from these methods are usually
impingement or laser irradiation. compact thin films, which are textured by nanocrystallites (25
− 30 nm).25, 45, 132, 133
3.1.1.1 Sputtering
3.1.1.3 Thermal Oxidation
Amongst the PVD techniques, sputtering has, thus far been the
most common technique to synthesize thin films CuxO, due to Thermal oxidation techniques offer a simple, convenient and
the ease of control over the deposition parameters. The as- fast method to synthesize nanostructured CuxO with various
synthesized films usually exhibit nanometer-sized tightly morphologies including nanowires, nanoribbons and
packed columnar structure.120-125. Sputtering is a process in nanorods.135-139 In this method nanostructured CuxO is directly
which atoms are ejected from a solid target material by grown on the surface of a Cu substrate.137, 138, 140 Thermal
bombarding it with energetic particles. It offers a high degree oxidation is performed by simply heating a Cu substrate to a
of control over a film’s crystallinity and stoichiometry. The high temperature (typically between 200 and 800 °C) in an
crystallinity, grains dimension and stoichiometry of the copper oxygen rich environment.135, 137, 138, 141-143 Generally, the
oxides films can be controlled by varying the sputtering morphology and stoichiometry of the CuxO can be controlled
parameters such as applied power, oxygen flow rate, oxygen by tuning the deposition parameters. For instance, the diameter
partial pressure and concentration as well as annealing and density of CuxO nanowires can be altered by changing the
temperature.32, 120-122, 124-128 For example, Chu et al. reported oxidation temperature.144 However, very high oxidation
crystallite sizes of Cu2O thin films changed from 16.8 to temperatures (> 900º C) are not suitable for nanowire
8.8 nm when oxygen partial pressures increased from 1.1 × formation as CuxO nanostructures can be fused together, as

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observed by Huang et al.145 Valladares et al. have studied the aging phenomena.169 Therefore, a second generation of adducts
effect of oxidation temperature in altering the stoichiometry of of the type M(hfa)2• tetramethylethylenediamine(TMEDA) (M
the CuxO films. They have observed that pure Cu2O films are = Cu(I) or Cu(II)) have been successfully adopted as alternative
obtained at 200 °C, whereas CuO films are obtained above precursors.169 They have favourable properties in terms of
300 °C.143 improved long–term stability and volatility with respect to
Unfortunately, mechanical adhesion between the as- conventional β–diketonate.13, 169 Barreca et al. were the first
deposited nanostructured CuxO and the substrates synthesized group to successfully demonstrate the deposition of
by the thermal oxidation method is very weak.143, 146-149 nanostructured CuO and Cu2O using Cu(hfa)2 adduct with
Cracking and flaking of the CuxO films or even exfoliation TMEDA via CVD.169 They successfully demonstrated
from the substrates posed a big challenge which severely morphological evolution from continuous films to 1D
affects the properties and practical applications of the hyperbranched nanostructures.169
nanostructured CuxO. Several methods have been proposed to Spray pyrolysis is a typical aerosol-assisted chemical
alleviate the cracking and flaking problem including pre- vapour deposition, which is utilized in the glass industry and in
deposition of a ZnO layer on copper foil150, synthesis of CuO solar cell production to deliver film coatings of various
nanowires on other foreign substrates such as silicon147, 151 or thicknesses.34 This method has the benefit of forming large-
glass152 and synthesis of CuO nanowires on porous substrates scale thin films by using a simple apparatus that can lead to
such as porous copper substrate149 or nickel foam148 as shown increase productivity. Moreover, the film thickness and
in Figure 6. Zhang et al. have successfully demonstrated non stoichiometry are easy to control and the resulting films are
cracked and flaked CuO nanowires synthesized on porous generally dense.165, 166 During film deposition, the precursor’s
copper substrates. The porous substrates managed to reduce solution is pumped to an atomizer, and then sprayed onto
thermal stress during the oxidation process and as a result heated substrates. Subsequently the droplets undergo
eliminate cracking and flaking issues.149 evaporation, solute condensation and thermal decomposition,
which results in film formation.34 The composition of these
3.1.1.4 Other PVD methods thin films is highly dependent on the solvent, morphology of
the substrate as well as the deposition temperatures.164, 170
CuxO films generated by the spray pyrolysis method are
Apart from the aforementioned vapour phase methods, PLD153-
157 generally produced from copper acetate or copper nitrate as
and EBE158-161 deposition techniques are the other
precursors dissolved in alcohol based solutions such as ethanol,
alternatives available for synthesizing CuxO films. It has been
propanol or methanol.164, 166, 170, 171 Alcohols are used to
reported that the as-synthesized CuxO from these methods are
increase the wettability of the sprayed solution on the substrate
usually compact thin films, which are textured by
and to improve the homogeneity of the deposited films.165 It
nanocrystallites (10−800 nm). The dimensions of the
has been reported that CuxO nanostructures form with the
crystallites are significantly affected by the oxygen pressure
addition of glucose or sucrose to the solution.165, 167 These
and substrate temperature which were identified as being the
sugars are used as reducing agents in the precipitation of the
two most important parameters.154, 155
CuxO nanostructures.165 Waser et al. demonstrated synthesis of
CuO nanoparticles via flame spray pyrolysis with various
3.2 CVD methods diameter from 6 to 50 nm by varying precursor solution and
oxygen flow rate.172
CVD processes have become popular deposition techniques Apart from CuO and Cu2O films, Cu4O3 films can also be
owing to their inherent flexibility and potential to tailor the obtained via spray pyrolysis techniques. Albores et al. have
CuxO phase composition by simply varying the operating successfully demonstrated the deposition of Cu4O3 films on
conditions and precursors. Many forms of CVD have been used ZnO nanorods.170 The formation of Cu4O3 films is a gradual
for depositing different CuxO stoichiometries, including process. Initially, the possible lattice matching of ZnO and
atmospheric pressure CVD,13, 162, 163 aerosol assisted CVD,164- CuO promotes the growth of CuO. In the presence of methanol,
167
and plasma assisted CVD.168 Such films are typically of at elevated temperatures, the Cu2+ in CuO is reduced to Cu1+
compact structure, consisting of micro- or nanometer-sized forming Cu2O as:170
grains.
Generally, precursors such as bis–(2,4–pentanedionato) CH 3OH (g) + 6CuO → 3Cu 2O + CO 2(g) + 2H 2 O(g) (5)
copper (II) or Cu(acac)2 (acac = acetylacetonate) are used due
to their high sublimation rate (activation energy of 105.6 kJ
mol–1) and low sublimation temperature between 140 to 190 Then at these elevated temperatures, the solid reaction between
ºC.162 Valtierra et al. have demonstrated the synthesis of CuO and Cu2O results in paramelaconite phase formation
nanostructured Cu4O3 and CuO thin films with crystallite size which can be described by:170
of 6.5 to 8.4 nm on fiberglass substrates using Cu(acac)2 as a
precursor and oxygen as a carrier-reactant gas via atmospheric 2CuO + Cu 2 O → Cu 4 O 3 (6)
pressure CVD.162 The deposition temperature of CuO and
Cu4O3 were recorded at 315 ºC and 345 ºC, respectively. In
addition, thin films of Cu2O have also been synthesized on
fiberglass substrates using a similar technique and precursors 3.3 Liquid phase synthesis
by Ortiz et al. at a deposition temperature of 320 ºC.163
However, precursors such as Cu(acac)2, Cu(dpm)2 (dpm = Liquid phase techniques include methods such as
dipivaloylmethanate) and Cu(hfa)2 (hfa = electrodeposition, hydrothermal/solvothermal and sol–gel.
hexafluoroacetylacetonate) may present drawbacks in terms of These methods are generally chosen due to their low capital
poor thermal characteristics, reduced shelf life, halide cost and better control of the material’s morphology in
incorporation or instability upon prolonged utilization due to comparison to vapour phase deposition techniques as well as

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the deposition at relatively low temperatures, which is crucial of nanostructured CuO and Cu2O including leaf-like183,
for low-heat-tolerant substrates. Among a variety of liquid nanospindles184, nanocubes185, nanorod186 and cauliflower-
phase synthesis methods, hydrothermal/solvothermal and like187. Interestingly, Seigfried and Choi have demonstrated a
chemical precipitation techniques have been widely used to new level of tuning and engineering the morphology of Cu2O
synthesize CuxO nanostructures. crystals via electrodeposition technique.188, 189 They
manipulated deposition parameters such as potential and
3.3.1 Electrodeposition current to engineer to Cu2O crystals as illustrated in Figure
7.189
Electrodeposition is a process in which metal ions in an
electrolyte are reduced at a conducting electrode under 3.3.2 Hydrothermal and Solvothermal
potential control. The process uses electrical current to reduce
Cu2+ ions from an aqueous solution. The electrolyte generally Hydrothermal and solvothermal processes are facile and cost-
contains a mixture of a Cu salt such as copper sulphate, copper effective deposition techniques. They have the capability of
acetate or copper nitrate and a chelating agent such as lactic producing nanostructured CuxO of different morphologies
acid, ammonium nitrate, amino acids or tartaric acids.29, 173-177 including nanodendrites,190 nanowires,71 nanorings,191
The deposition is carried out in alkaline environment with the nanorods,192-195 nanoribbons,191, 194
nanotubes,192
addition of sodium hydroxide or ammonia to control the pH microspheres194, 196 and macrowhiskers.197 (Figure 8)
level. The electrodeposition technique is commonly used for The synthesis of nanostructured CuxO has been
depositing CuO and Cu2O films.3, 29, 173-175, 177-180 Such films are hydrothermally achieved using various precursors such as
typically of compact structure, consisting of micro- or copper (II) chloride, copper (II) acetate or copper (II) sulphate.
nanometer-sized grains. The stoichiometry of the Generally, a lower concentration of Cu(OH)42– precursors
electrodeposited films is very much dependent on the type of favours tubular formation, whereas a higher concentration
the chelating agent and applied potential used during the leads to rodlike morphologies.192, 194 In most cases, the
electrodeposition process. Generally, CuO films are obtained hydrothermal synthesis of CuxO starts with the preparation of a
upon the application of a positive voltage/current bias, where solution that contains copper salts, sodium hydroxide and
oxidation of Cu is expected and this process is well known as solvents, typically deionized water. Such a solution is then kept
anodic electrodeposition. Inversely, Cu2O films are deposited at an elevated temperature (100 – 300 ºC) for a certain period
at a negative bias, in which the reduction process occurs of time, allowing the nucleation and growth of CuxO
(cathodic electrodeposition).173, 174, 181 crystallites.
Synthesis of CuO films via anodic electrodeposition in an Solvothermal methods are almost identical to hydrothermal
alkaline solution containing copper (II) nitrate, ammonium methods except that organic solvents are used instead of
nitrate and ammonia has been reported by Izaki et al. at +0.9 V water.198, 199 In comparison with the hydrothermal method, the
vs Ag/AgCl.174 Sasano et al. demonstrated that CuO films solvothermal method exhibits many advantages such as easier
formed by applying potential pulses are more crystalline than morphological control, free foreign anions and macroscopic
the ones deposited using a constant potential.176 The quantity.200, 201 Recent reports have shown that high-aspect-
mechanism for the electrodeposition of CuO films is outlined ratio of CuxO nanostructures can be synthesized via
in equations (7)–(10). The reaction starts via electrolysis of solvothermal methods.202-205 Zhao et al. have demonstrated a
water to generate oxygen and protons (reaction 7). facile method to synthesize pure polycrystalline Cu4O3
Consequently, these protons react with ammonia Cu(II) microspheres using copper (II) nitrate as the precursor in the
complexes to yield free Cu(II) ions in the vicinity of a presence of N,N−dimethylformamide and ethanol.201 They have
substrate’s surface (reaction 8). The free Cu(II) ions are then successfully manipulated the CuO/Cu2O stoichiometry ratio to
hydrolyzed to form CuO films on the substrate (reactions 9 and generate Cu4O3 films with the reaction of
10).174, 181 ( 2CuO + Cu 2 O → Cu 4 O 3 ) in a closed system. 201

2H 2 O → O 2 + 4H + 4e − (7) 3.3.3 Solution-based Chemical Precipitation Methods

Cu (NH 3 )24 + + 4H + → Cu 2 + + 4NH +4 (8)
Cu 2 + + 2OH− → Cu (OH)2 (9) In most cases, the chemical precipitation synthesize of CuO
Cu (OH )2 → CuO + H 2 O (10) nanoparticles starts with the preparation of a solution that
contains copper salts, sodium hydroxide and solvents, typically
Similarly, syntheses of Cu2O films have been reported via deionized water. In order to avoid agglomerate of the CuO
cathodic electrodeposition using an alkaline aqueous solution nanoparticles, an external energy such as ultrasonic or high
containing copper (II) sulphate or copper (II) acetate and lactic pressure need to be applied during the synthesize process. Zhu
acid as the chelating agent.10, 173, 175, 179, 180, 182 Zoolfakar et al. et al. prepared highly dispersed CuO nanoparticles of 6 nm
have demonstrated the electrodeposition of Cu2O films onto with various morphologies including spherical, ellipsoidal and
ZnO for forming heterojunction solar cells.173 The needle-shape CuO.206 Wu et al. prepared CuO nanoparticles
electrodeposition process was carried out at –0.55 V vs with different sizes and morphologies in organic solvents such
Ag/AgCl. Cu2O was formed according to the following as dimethylacetamide (DMAC).207 They found that the
electrochemical reaction.175 nucleation and growth kinetic of CuO nanoparticles can be
tuned by varying the processing parameters including the
volume ratio of DMAC and water, increasing the temperature
2Cu 2 + + 2e − + 2OH − → Cu 2 O + H 2O (11)
of the solution and the molar ratio of Cu2+ and OH−.207 Apart
from nanoparticles, chemical precipitation synthesis has
Apart from depositing thin films CuxO, electrodeposition commonly used to synthesize different morphologies of CuO
techniques have been used to synthesize various morphologies

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including nanowires208-210, nanoribbons211, flower-like212, 213, 4.0 APPLICATIONS CuxO

hierarchical nanochains214 and nanosheets215, 216. Recent
comprehensive review on nanostructured CuO via solution- CuxO has been employed for a variety of applications ranging
based chemical precipitation technique is found elsewhere.1 from optical devices to high thermal conductivity systems. In
There are many reports of synthesis of nanostructured Cu2O this section, some of the most common applications of CuxO
via chemical precipitation.53, 217-224 Gou et al. demonstrated a materials are presented. Particular emphasis is placed on the
synthesis of highly uniform and monodisperse Cu2O enhancements that can be achieved by exploiting the
nanocubes. The process involved the use of sodium ascorbate nanostructured forms of CuxO.
to reduce Cu(II) salts in water, in the presence of a surfactant
and NaOH. The nanocubes dimensions were tuned by varying
the concentration of the surfactant.217 Zhang et al. reported 4.1 Solar Cells and Light Emitting Diodes
synthesis of monodisperse Cu2O and CuO nanospheres. It has
also been shown that by modulating the concentration of CuxO films are possible candidates for developing different
solvent, the diameter, crystallization and monodispersity of types of optical devices, including solar cells based on
Cu2O nanospheres can be kinetically controlled.53 Interestingly, dye−sensitized and heterojunction architectures as well as
various groups have reported facile method for the synthesis of organic light emitting diodes.
Cu2O nanocrystals with systematic shape evolution (Figure The quest and need for a clean and economical energy
9).220-223 Recently, Susman et al. demonstrated precise source have increased interest in the development of solar
morphology control of Cu2O nanocrystals covering the entire applications. Amongst various metal oxide materials for solar
range of morphologies from complete cubes, via the energy applications, Cu2O has attracted increasing interest due
intermediate morphologies truncated octahedral, cuboctahedra to its theoretical power conversion efficiency (PCE) of 18%
and truncated cubes, to complete octahedral.220 The highly and an absorption coefficient higher than single crystalline
effective morphology control is attributed to competitive Si.173, 231
adsorption of hydroxide and citrate anions on the [100] and As described previously CuxO is an intrinsically p-type
[111] planes of the growing crystallite.220 material. However, self−compensation problems and dopant
solubility have inhibited the synthesis of n−type CuxO to
produce efficient homojunctions for photovoltaic applications.3,
72, 232
Therefore, heterojunction architectures have been
3.3.4 Other film formation methods
employed with other n−type semiconductors such as ZnO,10, 173,
175
CdO,233 TiO2,234-236 Ga2O3237 and GaN.2 Amongst the
A sol–gel process involves the formation of a colloidal solution aforementioned n−type semiconductors, ZnO has been found to
(sol) from selected chemicals that acts as a precursor for an be the most stable and exhibit relatively low lattice mismatch
integrated network (gel) of either discrete particles or of 7.6% between the (002) ZnO and (111) Cu2O phase.3, 175, 177
connected networks. During the gelation (aging process), Despite the predicted PCE value of 18%, in practice the
various forms of hydrolysis and polycondensation processes ZnO−Cu2O solar systems have yet to reach high efficiencies.3,
can take place. Film deposition is generally carried out during 10, 238
To date, the highest efficiency ever reported for bilayer
the gelation process via dip-coating, spin coating or drop– ZnO−Cu2O heterojunction solar cells has been 3.83%.239 This
casting onto the substrates. Armelao et al. have reported CuxO is due to the fact that theoretically their intrinsic electronic
thin films via sol–gel synthesis, using ethanolic solutions of band structures do not permit an open circuit voltages larger
copper (II) acetate.225 Films were obtained by dip–coating at than 0.7 V.238 To date, the largest ever short circuit current that
room temperature in air and were subsequently heat−treated at has been reported by Zoolfakar et al. using electrodeposited
different temperature (100–900 ºC) in oxidizing (air), inert (N2) ZnO and Cu2O films was 12.7 mA cm−2 (Figure 10).173
or reducing (4% H2 in N2) atmospheres to observe different Apart from heterojunction cells, CuxO has also been widely
crystalline phases of CuxO as a function of the annealing used in dye−sensitized solar cell (DSSC) technology. CuO is
conditions with an average crystallite size lower than 20 nm.225 commonly used as a blocking layer that prevents
Ray has also reported a similar technique, however he recombination reactions by forming a potential barrier between
experimented with methanolic solutions of cupric chloride.226 the anode and the electrolyte which enhances the PCE of the
Under an atmospheric heat-treatment condition, Armelao et al. device.240-243 Yet in other experiments, the use of Cu2O at the
have only managed to observe the CuO phase with 900 ºC photoanode of a DSSC was found to decrease the overall
annealing, while Ray has successfully demonstrated the PCE.244 This is due to dissociation of copper in liquid−based
deposition of CuO and Cu2O at 360 ºC and 400-500 ºC, electrolytes, inducing numerous extrinsic defects that increases
respectively.225, 226 carrier recombination, resulting in photovoltaic performance
Templating is a modification of the sol−gel synthesis degradation.244
technique and can be very effective for the preparation of CuxO CuxO has also been used in organic light emitting diodes
nanowires.141 Nanostructured CuxO is deposited onto porous (OLEDs).134, 245 In order to construct efficient OLEDs, it is
templates such as anodic alumina membranes and important to optimize the carrier injection ability at the
polycarbonate membranes.227-229 Generally, templates are used interface of the active layer and anode materials. The CuxO
for assisting the growth of the CuxO by controlling the films are commonly used as hole injection layers (HILs) to
diameters, lengths and densities of the nanowires.227 At the end lower the hole injection barrier.134, 246, 247 Kim et al. have
of the deposition process, the templates must be removed either reported the advantage of using a mixed stoichiometry of CuO
by chemical reactions229 or a selective burn-away at high and Cu2O for increasing the performance of OLEDs as
temperatures230. Consequently, this procedure may prolong the illustrated in Figure 11.134 Mixed stoichiometry of CuxO
process as well as degrade the quality of the CuxO.141 contains high density of defects such as oxygen vacancies or
unbonded oxygen atoms, which act as an extra energy state
within the energy gap of the CuxO layer. Interestingly, when

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the energy levels of these gap states are aligned with the free radicals. The radicals penetrate into the inner cell
highest occupied molecular orbital (HOMO) level of the hole membranes which lead to the disruption of the internal contents
transporting layer, no potential barrier is produced at the anode of the cell.264, 265 The effectiveness of the antimicrobial agent
interfaces, which can lead to an increase in the hole injection appears to be related to the nature of the cell wall structures.263,
efficiency.134 265-267
S. aureus is composed of multiple layers of
peptidoglycan with numerous pores, which are suggested to be
4.2 Photo–catalytic Applications more susceptible to intracellular transductions. In contrast, the
cell walls of E. coli are relatively thin, mainly consisting of
peptidoglycan and outer layers of lipopolysaccharide,
CuxO is a promising photo–catalyst that is used in many
lipoprotein and phospholipids, which are less prone to being
chemical processes, such as organic contamination degradation
attacked by CuO nanoparticles. As a result, nanostructured
and water splitting under visible–light irradiation owing to their
CuO has a higher antimicrobial activity against S. aureus than
small band gap and low cost.13, 248-255 Under illumination, CuxO
E. coli.263, 264
produces electron/hole pairs that can generate hydroxyl radicals
It has been demonstrated that nanostructured CuO
(•HO) from water. This radical is capable of mineralizing most
antimicrobial activity can be enhanced by exposing it to
organic molecules.250 For water splitting applications, the
light.11, 264, 268-270 As described in section 4.2, light irradiation
majority charge carriers of the CuxO (holes) oxidize water to
generates excited electron–hole pairs in the CuO and
oxygen gas (O2), while the photo–generated minority charge
deactivation of the bacteria is possible via a photo–catalytic
carriers (electrons) reduce water to hydrogen gas (H2).248, 254, 255
process.11, 268 Akhavan et al. have reported an improvement of
Significantly, the CuxO conduction band is more negative than
22% of CuO antibacterial activity under illumination.11
the redox potential of H+/H2, which allows sunlight to produce
H2 from water. 253
Unfortunately, the general photo–instability of CuxO 4.4 Electrochemical Applications
greatly hinders its direct application in photo–catalysis.248, 256
To overcome this photo–instability effect, CuxO is typically The electrochemical properties of nanostructured CuxO as
coupled with other semiconductors to form heterojunctions and electrodes for lithium ion batteries (LIB) have also been of
it has been reported that TiO2 is one of the best candidates for growing research interest. CuxO has many attractive advantages
this purpose.256, 257 Additionally, nanostructuring of CuxO can over conventional materials including high theoretical capacity
also significantly improve overall stability.256 Fortunately, the (>600 and >350 mAhg–1 for CuO and Cu2O, respectively) and
large surface area to volume ratio, which is provided by low cost.271-273 One of the major issues with the use of CuxO in
nanostructuring, significantly increases the effective surface LIBs is its large volume variation during the Li+ ion
area available for photo–catalytic reactions.249, 250, 252 insertion/extraction processes, which leads to severe
It has also been reported that the photo–catalytic production mechanical strains and a rapid decay in capacity.271 Recently,
rate of H2 can be significantly improved in the presence of there have been various reports demonstrating LIBs with high
alcohol, which provides suitable electron donors (also known reversible capacity and cycling stability by synthesising
as sacrificial agent/reagent).258-260 Barreca et al. have CuxO/graphene nanocomposites.271, 274, 275 Mai et al. reported
successfully demonstrated excellent performance of Cu2O an excellent reversible capacity of 583.5 mAhg−1 with high
photo–catalysis for generating H2 in the presence of cycling stability by incorporating CuO nanoparticles (~30 nm)
methanol.13 They have suggested that methanol inhibits onto graphene sheets (Figure 12a). The graphene sheets serve
electron–hole recombination and acts partially as a hydrogen as a conductive network for fast electron transfer as well as
source.13 However, efficient photo–catalytic activity of CuO buffered spaces to accommodate the CuO volume
for H2 production has not been reported. This is despite that expansion/contraction during Li+ insertion/extraction
fact that the band gap of CuO is 1.2 eV, which makes CuO an process.274
efficient material to absorb sunlight. However, the position of Nanostructuring CuxO into hollow nano/microstructures
the conduction band level limits its activity. Therefore, such as spheres, cubes or urchin–like structures increases its
introducing a sacrificial agent is crucial to enable it to be used LIB performance.201, 275-277 For example, Park et al. have
as a photo−catalyst. For example, Yao et al. have reported that successfully demonstrated that hollow CuO urchin–like
CuO exhibits high photo−catalytic activity in oxalic acid nanoparticles possess a charge capacity above 560 mAhg–1
solutions.253 Oxalic acid, which is a common pollutant in (Figure 12b).276 Wei et al. have discussed and listed three main
industrial wastewater, is a strong reductive agent and acts as an advantages of hollow structures as anode materials for LIBs.277
electron donor.261, 262 Zhou et al. have reported excellent LIB performance by
integrating hollow nanostructures of CuO with graphene.275
4.3 Antimicrobial Applications The composites exhibited a durable lifetime with reversible
capacities as large as 640 mAhg–1 (Figure 12c).275
The antimicrobial properties of CuxO, in particular CuO, have
attracted growing research interest. Nanostructured CuxO
commonly offers a strong degree of chemical and physical 4.5 Electrochromic Devices
stability. Most bacterial cells have cellular membranes that
contain pores in the nanometer range. CuxO, with dimensions Nanostructured Cu2O electrochromic based systems, such as
less than 20 nm, have shown antibacterial properties.11, 263 The smart windows and optical displays, have been studied since
antimicrobial activity of CuO has been attributed to the the 1990s.130 It has been found that Cu2O exhibits cathodic
production of reactive oxygen species (ROS) such as •O2−, electrochromism, being transparent under visible illumination
•
HO2, •OH and H2O2 which can also occur without exposure to in their oxidized state and almost black when switched to their
any visible light owing to the small band gap of CuO.264, 265 reduced state in the presence of an electrolyte containing
The generated ROS interact with outer cell walls to generate positive ions such as H+, Li+ and Na+.130, 278-281 Generally, it has

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been found that the electrochromic process corresponds to the been reported.305-307 Though non-enzymatic sensors are, by
conversion of Cu2O (transparent) to CuO (black) in a reversible design, quite selective, CuO-based glucose sensors have a fast
reduction–oxidation process (redox).278, 281 To date, the best response times, possess a high degree of repeatability and are
coloration efficiency obtained by Cu2O nanostructures has been extremely stable.303
up to 37 cm2C–1, which is only one–fourth of the best of those
made from WO3 nanoporous (141.5 cm2C–1).278, 282
Unfortunately, nanostructured Cu2O requires high coloration
4.7 Tribology and Heat Transfer Applications
voltage and shows poor stability279, and further work should be
carried out to solve such important issues.
A large number of studies have reported that adding metal
oxides such as CuxO in the form of nanoparticles to lubricants
4.6 Sensing Applications is an effective means to reduce wear and friction.12, 80, 308-310
The friction–reduction and anti–wear behaviours are dependent
CuxO offers great potential for the development of highly on the characteristics of the nanoparticles including size
sensitive, yet low cost sensors. This includes optical, gas and (mostly in the range of 2 – 120 nm), morphology and
bio sensors. Photodetectors are important devices that can be concentration.12 The colloidal effect, rolling friction effect,
used in various applications, including thermal imaging third body generation with nanomaterials and protective thin
systems, free-space communications, navigator aids and ozone- films formation mechanism have been proposed to justify the
layer monitoring.283, 284 Among the semiconductor materials, role of nanomaterials’ anti–wear and friction–reduction
CuxO has proven an attractive material for making properties.80
photodetectors due to its relatively low band gap and Wu et al. have compared the tribological properties of two
remarkable optoelectronics properties.70, 284-287 lubricating oils (API–SF engine oil and Base oil) with CuO,
Sahoo et al. have demonstrated excellent performance of TiO2 and diamond nanoparticles used as additives. They found
photodetector based on Cu2O nanowires.285 They adopted that CuO suspensions showed the highest reduction of friction
metal-semiconductor-metal (MSM) technique for photon coefficient (due to viscosity and rolling effect) and worn scar
sensing under dark and illumination conditions. Figure 13(a-d) depth (owing to reduction of shearing stress) as compared to
illustrated SEM micrographs of four such MSM devices with standard oils without nanoparticles.12 The shapes of
channel lengths (i.e. spacing between the electrodes) of 210, nanoparticles such as sphere, rods, sheets and wires play
260, 580 and 720 nm, respectively.285 They observed that the crucial roles in tribology in monitoring the friction and anti–
channel length significantly influenced the photocurrent and wear properties. Recently, Gausian et al. have revealed that
bias dependence of the photo-to-dark-current ratio (Figure lubricity enhancement is attributed to the synergistic effect of
13(e-h)).285 Liao et al. reported the photoconductivity of Cu2O uninterrupted supplies of CuO nanorods under contact surfaces
nanowires measured under dark and blue (488 nm) laser and their rolling mechanism.80
illumination and the conductance of nanowires increased from In addition to the enhancement of tribological properties,
0.7 to 4.3 µS under illumination. Remarkably, the nanofluids with dispersed CuxO nanoparticles have great
photoconductivity response time was less than three seconds potential for improving heat transfer especially in improving
with good reversibility and stability.70 CuO has also been the efficiency of chillers, refrigerators and air–conditioners.81,
extensively used in photodetector applications under visible 310, 311
Many studies have reported that mixtures with
and IR illumination (due to its relatively low band gap).284, 286- suspended CuO nanoparticles have higher thermal conductivity
288
Recent comprehensive reviews on the usage of CuO in than the conventional host fluid.81 This is due to the thermal
photodetection are found elsewhere.1 conductivity of CuO (76.5 W mK−1 which is much higher than
CuxO also offers a great possibility for developing highly ethylene glycol that has a value of 0.26 W mK−1). Lee at al.
sensitive semiconductor-based gas sensors. The sensing have compared the thermal conductivity of CuO and Al2O3
properties of CuxO can be improved by decreasing its size to nanoparticles suspended in ethylene glycol and found that the
nanoscale dimensions (comparable to twice of the Debye thermal conductivity of the CuO suspensions is 7% higher than
length) and by adding appropriate dopants.126, 289 Catalytic the Al2O3 system.312
nanoparticles such as Pd,290 Pt,291 Ag292 and Au291, 293, 294
attached to the CuxO surface, further increases its sensitivity,
4.8 Field Emission Applications
mainly due to spill−over effects.289 CuxO thin films have been
demonstrated to be highly sensitive towards various gas species
including C2H5OH,14, 126, 294-298 CO,296, 299, 300 NO214, 300 and The field emission (FE) properties of CuxO are far less reported
H2S53, 290, 301 (Figure 14). than other oxides materials such as ZnO, SnO2 and In2O3. Due
The ability to tune the shape and dimensions of CuxO to its relatively narrow band gap, nanostructured CuxO offers
thereby creating superior chemical and physical properties can an attractive alternative to serve as a FE emitter.313-315 In a FE
be exploited for chemosensors and biosensors. They also show system the emitting capability is believed to be highly
unique surface chemistry, thermal and electrical properties and dependent on both the properties of the material and
high surface-to-volume ratio which enhance the sensitivity and configuration of the cathode.34 It is known that materials with
response of electrochemical sensors.302 higher aspect ratios and sharp edges generally produce higher
CuxO has been used as a working electrode in FE currents.55, 313, 315 Zhu et al. have reported FE measurements
electrochemical based biosensors including in glucose of CuO nanowire films with a low turn−on field of 3.5−4.5 V
sensors.303 Most electrochemical glucose sensors involve the µm−1. They obtained a large current density of 0.45 mA cm−2 at
use of the enzyme glucose oxidase. However, the greatest an applied electric field of 7 V µm−1.314 Nanostructured Cu2O
drawback of enzymatic sensors is their lack of stability due to also exhibits relatively high FE performance. Shi et al. have
the intrinsic nature of enzymes.304, 305 Development of non- demonstrated Cu2O micro−porous cubes with a low turn−on
enzymatic sensors, using CuxO as the working electrode, has field of 3.1 V µm−1. They showed a high current density of

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1 mA cm−2 at an applied electric field of 11 V µm−1.55 It has structures, the potential gains from developing a low-cost,
also been reported that Cu2O can be coupled with other metal nanostructured material, like Cu4O3 for any of these
oxides such as ZnO or TiO2 to enhance its FE performance applications is extremely enticing and expected to be explored.
(Figure 15).315-317 This enhanced FE is attributed to the
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16 | J. Mater. Chem. C, 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 17 of 34 Journal of Materials Chemistry C

Table 1. Crystallographic properties of CuO, Cu2O and Cu4O3 1-6

CuO Cu2O Cu4O3

Lattice Monoclinic Cubic Tetragonal
a = 4.6837 Å a = 4.2696 Å a = 5.837 Å
b = 3.4226 Å b = 9.932 Å
c = 5.1288 Å
β = 99.54º
α = γ = 90º
Shortest distance
Interatomic distances Cu ― O 1.95 Å 1.84 Å 1.87 Å
Interatomic distances O ― O 2.62 Å 3.68 Å 2.56 Å
Interatomic distances Cu ― Cu 2.90 Å 3.01 Å 2.92 Å
Formula weight 79.57 143.14 302.18
-3 -3
Density 6.52 gcm 5.75 gcm 5.93 gcm-3
Melting point 1201 ºC 1235 ºC 400 ºC
Cell volume 81.08 Å3 77.833 × 10–24 cm–3 338 Å3
 Journal of Materials Chemistry C Page 18 of 34

Figure 1. Monoclinic, cubic and tetragonal crystal structure of the copper oxide compounds (a) CuO,

(b) Cu2O and (c) Cu4O3 (gray and red spheres represent copper and oxygen atoms, respectively). For

the antiferromagnetic CuO and Cu4O3 the arrows on the copper ions indicate the orientation of local

magnetic moments. Reprinted figure with permission from (M. Heinemann, B. Eifert and C. Heiliger,

Phys. Rev. B, 2013, 87) copyright (2013) by the American Physical Society.
Page 19 of 34 Journal of Materials Chemistry C

Figure 2. (i) Electronic band structure and density of states from hybrid functional DFT calculations

and (ii) Brillouin zones with special high symmetry k points of the three copper oxide compounds to:

(a) Cu2O, (b) CuO and (c) Cu4O3. Reprinted figure with permission from (M. Heinemann, B. Eifert and

C. Heiliger, Phys. Rev. B, 2013, 87) copyright (2013) by the American Physical Society.
 Journal of Materials Chemistry C Page 20 of 34

Figure 3. Gaussian fit to the imaginary part of the dielectric ε 2 for (a) Cu2O, (b) CuO and Cu4O3.

Reprinted with permission from (B. K. Meyer, A. Polity, D. Reppin, M. Becker, P. Hering, P. J. Klar, T.

Sander, C. Reindl, J. Benz, M. Eickhoff, C. Heiliger, M. Heinemann, J. Blaesing, A. Krost, S. Shokovets,

C. Mueller and C. Ronning, Phys. Status Solidi B, 2012, 249, 1487-1509) copyright (2012) by WILEY-

VCH Verlag GmbH & Co. KGaA, Weinheim.

Page 21 of 34 Journal of Materials Chemistry C

Figure 4. Experimental Raman spectra of Cu2O, CuO and Cu4O3. The calculated frequencies of Raman

active vibrational modes are indicated by vertical bars. Reprinted with permission from (L. Debbichi,

M. C. M. de Lucas, J. F. Pierson and P. Kruger, J. Phys. Chem. C, 2012, 116, 10232-10237) copyright

(2012) American Chemical Society.

 Journal of Materials Chemistry C Page 22 of 34

Figure 5. (a) Temperature dependence for electrical conductivity and Seebeck coefficient of CuO in

oxygen (●), in air (∆) and in 3% O2–Ar (□), (b) Electrical conductivity of Cu2O single crystal vs 1/T, (c)

Seebeck coefficient of Cu2O single crystal vs 1/T, calculated and experimental heat capacities, Cp of

(d) CuO: (□ ∆ ○) Ref 89, (∙ ∙ ∙) Ref 90, (---) Ref 91, and (e) Cu2O: ( ) Ref 88, (○) Ref 92 (●) Ref 93.

Reprinted with permission from (a) (S. Suda, S. Fujitsu, K. Koumoto and H. Yanagida, Jpn. J. Appl.

Phys. 1, 1992, 31, 2488-2491) copyright (1992) by The Japan Society of Applied Physics, (b and c)

Reprinted from J. Phys. Chem. Solids, 30, A. P. Young and C. M. Schwartz, 249-25, copyright (1969)

with permission from Elsevier, (d) Reprinted from Thermochim. Acta, 348, J. Leitner, D.

Sedmidubský, B. Doušová, A. Strejc and M. Nevřiva 49-51, copyright (2000) with permission from

Elsevier, (e) (P. A. Korzhavyi, I. L. Soroka, E. I. Isaev, C. Lilja and B. Johansson, P. Natl. Acad. Sci. USA,

2012, 109, 686-689) copyright (2012) National Academy of Science, USA.

Page 23 of 34 Journal of Materials Chemistry C

Figure 6. (i) Schematic illustration of the synthesis process for CuO nanowires on nickel foam. (ii) (a)

cross-sectional view of CuO nanowires synthesized on the CuO adhesion layer (AL)/Si substrate, (b)

magnified view from the nanowire root region marked by the red dashed square, (c) top-view of

CuO nanowires synthesized on Ni foam and (d) illustration of the mechanism for CuO nanowires

growth. Reproduced from Ref. 148 with permission from The Royal Society of Chemistry.
 Journal of Materials Chemistry C Page 24 of 34

Figure 7. SEM images of deposited octahedral Cu2O crystals that display systematically varying

degrees of branching with (100) planes parallel to the substrate (a–d) and with (111) planes parallel

to the substrate (e–h). These crystals were obtained at a constant temperature (60 °C) and

concentration of Cu2+ (0.02 M) and by applying a deposition conditions of 0.10 mA cm−2 ≤ I ≤ 0.12

mA cm−2 and 0.08 V ≤ E ≤ 0.12 V. All figures have scale bars of 1 μm. Reprinted with permission from

(M. J. Siegfried and K. S. Choi, Angew. Chem. Int. Edit., 2005, 44, 3218-3223) copyright (2012) by

WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Page 25 of 34 Journal of Materials Chemistry C

Figure 8. SEM images of various morphologies via hydrothermally/solvothermally synthesized of (a)

Cu2O nanowires synthesized at 180 °C in Copper (II) acetate aqueous solution with pyrrole, (b) CuO

flake–like synthesized at 200 °C in Copper (II) sulphate aqueous, (c) CuO/Cu2O dendrite–like

synthesized at 200 °C in Copper (II) sulphate aqueous with 10 ml ethylene glycol (EG), (d) CuO/Cu2O

flower–like synthesized at 200 °C in Copper (II) sulphate aqueous with 20 ml EG, and CuO/Cu2O

composite hollow microspheres obtained in a Copper (II) acetate aqueous solution at 200 °C for (e) 1

hour and (f) 5 hours. Reprinted with permission from (a) (Y. W. Tan, X. Y. Xue, Q. Peng, H. Zhao, T. H.

Wang and Y. D. Li, Nano Lett., 2007, 7, 3723-3728) copyright (2007) American Chemical Society,

(b,c,d) (S. Z. Li, H. Zhang, Y. J. Ji and D. R. Yang, Nanotechnology, 2004, 15, 1428-1432) copyright

(2004) by IOP Publishing Ltd, (e,f) (H. Yu, J. Yu, S. Liu and S. Mann, Chem. Mater., 2007, 19, 4327-

4334) copyright (2007) American Chemical Society.

 Journal of Materials Chemistry C Page 26 of 34

Figure 9. (i) Schematic illustration of the procedure used for growing Cu2O nanocrystals of different

shapes. (ii) (a-d) Respective SEM images of the Cu2O nanocrystals synthesized in sample containers

A, B, C and D with increasing amounts of NH2OH•HC added to the solutions. The particle

morphologies are (a) truncated cubic, (b) cuboctadheral, (c) truncated octahedral and (d) octahedral

in shape. Insets show the enlarged views of individual nanocrsytals. The scale bars in the insets are

100 nm. Reprinted with permission from (C.-H. Kuo and M. H. Huang, J. Phys. Chem. C, 2008, 112,

18355-18360) copyright (2007) American Chemical Society.

Page 27 of 34 Journal of Materials Chemistry C

Figure 10. (a) 3D schematic of the electrodeposited ZnO–Cu2O heterojunction solar cells, (b) J–V

characteristic curves of ZnO–Cu2O heterojunction solar cells. Reproduced from Ref. 173 with

permission from The Royal Society of Chemistry.

 Journal of Materials Chemistry C Page 28 of 34

Figure 11. (i) Phase diagram of a copper-oxygen binary system and schematic diagram of electronic

states and film structure of stoichiometric and non-stoichiometric CuxO, (ii) (a) current-density

voltage (J−V) and (b) luminance-voltage (L−V) characteristics of OLED with CuxO HIL deposited at
Page 29 of 34 Journal of Materials Chemistry C

different rates. Inset: schematic diagram of OLEDs. Reproduced from Ref. 134 with permission from

The Royal Society of Chemistry.

 Journal of Materials Chemistry C Page 30 of 34

Figure 12. Cycling profile of (a) bare CuO, graphene and CuO/graphene electrode at current density

of 67 mAg−1, (b) CuO nanoparticles with three types morphologies (urchin−like, hollow cubes and

hollow spheres) at a current density of 150 mAg−1, (c) CuO hollow nanoparticles/graphene

(CuO−HNPs/G) and CuO hollow nanoparticles (CuO−HNPs) at 50 mAg−1. (a) Reprinted from

Electrochim. Acta, 56, Y. J. Mai, X. L. Wang, J. Y. Xiang, Y. Q. Qiao, D. Zhang, C. D. Gu and J. P. Tu,

2306-2311, copyright (2011) with permission from Elsevier, (b) Reprinted with permission from (J. C.

Park, J. Kim, H. Kwon and H. Song, Adv. Mater., 2009, 21, 803) copyright (2009) by WILEY-VCH Verlag
Page 31 of 34 Journal of Materials Chemistry C

GmbH & Co. KGaA, Weinheim, (c) Reprinted from Electrochem. Commun., 13, J. Zhou, L. Ma, H.

Song, B. Wu and X. Chen, 1357-1360, copyright (2011) with permission from Elsevier.
 Journal of Materials Chemistry C Page 32 of 34

Figure 13. (a−d) SEM micrographs of Cu2O nanowire base devices having electrode spacings of 210,

260, 580, and 720 nm, respectively. The electrodes are 3.2 μm wide for all of the devices. The scale

bars are 100 nm. The current−voltage (I−V) measurements are carried out at dark and under

illumination conditions for all four samples. Depending on the interelectrode spacing, the samples

are categorized into two sets, set I: sample-1 and sample-2; set II: sample-3 and sample-4. (e,f) I−V

characteristics of set I and set II, respectively. (g,h) Plot of the ratio of photocurrent (Iphoto) to the

dark current (Idark) vs bias voltage for set I and set II, respectively. Insets of (g) and (h) represent the

photocurrent as a function of bias for set I and set II, respectively. Reprinted with permission from

(S. Sahoo, S. Husale, B. Colwill, T.-M. Lu, S. Nayak and P. M. Ajayan, ACS Nano, 2009, 3, 3935-3944)

copyright (2007) American Chemical Society.

Page 33 of 34 Journal of Materials Chemistry C

Figure 14. (a) Sensor response curves of the CuO and Cu2O based sensors towards ethanol (12.5

ppm) at different operating temperatures, dynamic response of (b) CuO based sensors towards

ethanol at the optimum operating temperature of 180 °C and (c) Cu2O based sensors towards

ethanol at the optimum operating temperature of 260 °C. Reprinted from Sens. Actuator B Chem.,

185, A. S. Zoolfakar, M. Z. Ahmad, R. A. Rani, J. Z. Ou, S. Balendhran, S. Zhuiykov, K. Latham, W.

Wlodarski and K. Kalantar-zadeh, 620-627, copyright (2013) with permission Elsevier.

 Journal of Materials Chemistry C Page 34 of 34

Figure 15. (a) Field emission J−E curves, (b) corresponding F−N plots of the samples. (c)−(e) Electron

emission images of the pure Cu2O nanopines, Cu2O−TiO2−ZnO composite samples, respectively.

Reprinted with permission from (Y. Wang, K. Yu, H. H. Yin, C. Q. Song, Z. L. Zhang, S. C. Li, H. Shi, Q. F.

Zhang, B. Zhao, Y. F. Zhang and Z. Q. Zhu, J. Phys. D Appl. Phys., 2013, 46), copyright (2013) by IOP

Publishing Ltd.