materials

Review
Current Status and Future Prospects of Copper Oxide
Heterojunction Solar Cells
Terence K. S. Wong 1, *, Siarhei Zhuk 1,2 , Saeid Masudy-Panah 2 and Goutam K. Dalapati 2, *
1 NOVITAS, School of Electrical and Electronic Engineering, Block S2, Nanyang Technological University,
Nanyang Avenue, Singapore 639798, Singapore; ZHUK0003@e.ntu.edu.sg
2 Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research),
2 Fusionopolis Way, #08-03, Innovis 138634, Singapore; SAEID1@e.ntu.edu.sg
* Correspondence: ekswong@ntu.edu.sg (T.K.S.W.); dalatapig@imre.a-star.edu.sg (G.K.D.);
Tel.: +65-6790-6401 (T.K.S.W.); +65-6319-4743 (G.K.D.)

Academic Editor: Lioz Etgar

Received: 21 February 2016; Accepted: 31 March 2016; Published: 7 April 2016

Abstract: The current state of thin film heterojunction solar cells based on cuprous oxide (Cu2 O),
cupric oxide (CuO) and copper (III) oxide (Cu4 O3 ) is reviewed. These p-type semiconducting
oxides prepared by Cu oxidation, sputtering or electrochemical deposition are non-toxic, sustainable
photovoltaic materials with application potential for solar electricity. However, defects at the
copper oxide heterojunction and film quality are still major constraining factors for achieving
high power conversion efficiency, . Amongst the Cu2 O heterojunction devices, a maximum
of 6.1% has been obtained by using pulsed laser deposition (PLD) of Alx Ga1x O onto thermal Cu2 O
doped with Na. The performance of CuO/n-Si heterojunction solar cells formed by magnetron
sputtering of CuO is presently limited by both native oxide and Cu rich copper oxide layers at
the heterointerface. These interfacial layers can be reduced by using a two-step sputtering process.
A high of 2.88% for CuO heterojunction solar cells has been achieved by incorporation of mixed
phase CuO/Cu2 O nanopowder. CuO/Cu2 O heterojunction solar cells fabricated by electrodeposition
and electrochemical doping has a maximum efficiency of 0.64% after surface defect passivation and
annealing. Finally, early stage study of Cu4 O3 /GaN deposited on sapphire substrate has shown a
photovoltaic effect and an of ~102 %.

Keywords: cuprous oxide; cupric oxide; heterojunction; solar cell; oxidation; magnetron sputtering;
pulsed laser deposition

1. Introduction
When oxidized, copper can form three types of oxides, namely: cuprous oxide (Cu2 O, cuprite),
cupric oxide (CuO, tenorite) and Cu4 O3 (paramelaconite) [1]. All three forms of copper oxides
are semiconductors, and Cu2 O, in particular, is one of the first semiconductors studied for device
applications. In the early 20th century, Cu2 O Schottky junctions were intensively investigated for use
as rectifiers in radio receivers [2]. A review of the research conducted during this period, including the
difficulty of n-type doping, was written by Brattain in 1950 [3]. After the invention of the point contact
transistor in 1947 and the metal oxide semiconductor field-effect transistor in 1960, interest in Cu2 O
declined because of the availability of single crystal silicon and germanium, which can be doped n-
and p-type [2]. During the 1970s, there was a resurgence of interest in Cu2 O as a semiconductor for
photovoltaics (PV) because of the need to develop terrestrial PV devices for solar energy conversion
in response to the first oil crisis of 1973. The Cu2 O solar cells investigated during this period were
Schottky junction PV devices [46]. Two research projects on these devices supported by the U.S.
National Science Foundation were carried out at the Joint Center for Graduate Study [5,6]. This focus

Materials 2016, 9, 271; doi:10.3390/ma9040271 www.mdpi.com/journal/materials

Materials 2016, 9, x 2 of 21
Materials 2016, 9, 271 2 of 21

Study [5,6]. This focus on the Schottky junction structure was due to the difficulty of forming p-n
homojunctions
on the Schottky in Cu 2O. Owing
junction to chemical
structure was due reduction of theofCu
to the difficulty 2O surface
forming p-n to Cu during sputter
homojunctions in Cu2 O.
deposition,
Owing to the best reduction
chemical obtained of wastheonly
Cu2 Oofsurface
the orderto Cu of during
1% regardless of the metal
sputter deposition, thedeposited [6].
best obtained
Nevertheless, it was recognized that a heterojunction or metal-inuslator-semiconductor
was only of the order of 1% regardless of the metal deposited [6]. Nevertheless, it was recognized that structure
should improve the
a heterojunction orperformance of Cu2O PV devices.
metal-inuslator-semiconductor The low
structure that
should couldthe
improve be performance
achieved in of these
Cu2 O
CuPV2O PV devices
devices. Theeventually
low that ledcould
to another waninginofthese
be achieved interest
Cuby 2 O the
PV 1980s.
devices A review
eventually of the
led literature
to another
onwaning
Cu2O Schottky junction
of interest by the devices
1980s. Aduring
reviewthis period
of the can beonfound
literature Cu2 OinSchottky
[7]. Despite this,devices
junction researchduringon
Cuthis
2O PV devices
period continued
can be found inin [7].Japan,
DespiteItaly and
this, elsewhere
research on Cu after
2 O the
PV 1990s.
devices The Cu
continued 2O in
PV research
Japan, Italy inand
thiselsewhere
recent period is concerned with a search for newer dopants for Cu
after the 1990s. The Cu2 O PV research in this recent period is concerned with a search for
2 O, suitable transparent
n-type
newer semiconductors
dopants for Cufor 2 O,heterojunction
suitable transparentformation
n-type and low damage junction
semiconductors formation formation
for heterojunction techniques.and
Aslowa result,
damagethere has been
junction significant
formation improvements
techniques. in the there
As a result, reportedhas of Cu
been 2O PV devices.
significant This can in
improvements
be the
seenreported
from Figure 1, which is based on a compilation of published values
of Cu2 O PV devices. This can be seen from Figure 1, which is based on a compilation in the PV literature [8]. of
In published
2015, an value
values ofin6% thewasPV reported
literaturefor[8].aInheterojunction
2015, an value PVofdevice
6% was based on Cu
reported 2Oaand
for another
heterojunction
n-type semiconductor.
PV device based on Cu This 2 Ovalue
and is exactly
another triple
n-type that of the
semiconductor. best value
This reported
value is in
exactly 2006
triplefor a Cuof
that 2Othe

heterojunction PV device (see Section 3). Figure 1 shows that, in addition

best value reported in 2006 for a Cu2 O heterojunction PV device (see Section 3). Figure 1 shows to Cu 2 O, there has been
growing
that, inresearch
additioninterest
to Cu2 O, in there
CuO has PV devices in recent
been growing years.interest
research The highest
in CuOreported
PV devices as ofin 2015
recent foryears.
a
CuO based PV device is 1.2%.
The highest reported as of 2015 for a CuO based PV device is 1.2%.

Figure 1. 1.
Figure Reported
Reportedpower
power conversion
conversion efficiency of Cu
efficiency O 2and
of 2Cu O andCuO heterojunction
CuO solar
heterojunction cells
solar vs. vs.
cells
publication year. For Cu O, the efficiency for 2008 refers to a device prepared by an electrodeposition
publication year. For Cu2 O, the efficiency for 2008 refers to a device prepared by an electrodeposition
2

method instead
method of the
instead PLD
of the PLDmethod
method[8].[8].

It is useful to first consider why an old semiconductor such as copper oxide still attracts such a
It is useful to first consider why an old semiconductor such as copper oxide still attracts such
niche interest at a time when many new semiconductors such as the perovskite and organic
a niche interest at a time when many new semiconductors such as the perovskite and organic
semiconductors are being studied for PV applications. In the latest solar cell efficiency tables
semiconductors are being studied for PV applications. In the latest solar cell efficiency tables
(version 47) [9], there is no listing for copper oxide devices. Textbooks on PV devices usually have no
(version 47) [9], there is no listing for copper oxide devices. Textbooks on PV devices usually have no
coverage of copper oxide PV devices [10,11]. The main exception is the reference by Fonash, which
coverage of copper oxide PV devices [10,11]. The main exception is the reference by Fonash, which
has brief mention of Cu2O [12]. Sustainability is the main reason for the sustained interest in the
has brief mention of Cu2 O [12]. Sustainability is the main reason for the sustained interest in the
copper oxides for PV. Both copper and oxygen are abundant elements like silicon and thus there can
copper oxides for PV. Both copper and oxygen are abundant elements like silicon and thus there can
be no supply concern in the long run [13]. This is one of the four requirements for a semiconductor to
be no supply concern in the long run [13]. This is one of the four requirements for a semiconductor
be usable for large scale PV power generation [14]. As discussed extensively in [15,16], a careful
to be usable for large scale PV power generation [14]. As discussed extensively in [15,16], a careful
sustainability analysis of a large number of semiconductor materials showed that Cu2O and CuO are
sustainability analysis of a large number of semiconductor materials showed that Cu2 O and CuO are
sustainable PV materials. In addition, all three oxides of copper are non-toxic and can be deposited
sustainable PV materials. In addition, all three oxides of copper are non-toxic and can be deposited as
as thin films relatively simply at low cost. The copper oxides are p-type oxide semiconductors
thin films relatively simply at low cost. The copper oxides are p-type oxide semiconductors uniquely
uniquely suitable for PV applications. Although there are a few alternative p-type binary oxides
suitable for PV applications. Although there are a few alternative p-type binary oxides such as tin
such as tin monoxide (SnO) and nickel oxide (NiO), their energy band gaps of 2.5 eV and 3.64.0 eV,
monoxide (SnO) and nickel oxide (NiO), their energy band gaps of 2.5 eV and 3.64.0 eV, respectively,
Materials 2016, 9, 271 3 of 21

are too wide for PV applications [17]. Hence, at present, these transition metal oxides are mainly used
for transparent
Materials 2016,semiconductors.
9, x 3 of 21
This review will focus on recent developments in copper oxide heterojunction solar cells and
respectively,
complements theare too wide
earlier for by
review PVRakhshani
applications[7].
[17].
It Hence, at present,
is organized into these
seventransition
sections.metal oxides2, we
In Section
are mainly
first outline theused
theoryfor of
transparent semiconductors.
heterojunction solar cells with emphasis on the copper oxide heterojunction
and bandThis review will focus on recent developments in copper oxide heterojunction solar cells and
diagram. Sections 3 and 4 review the Cu2 O and CuO heterojunction solar cells, respectively.
complements the earlier review by Rakhshani [7]. It is organized into seven sections. In Section 2, we
Section 5 describes the electrodeposited Cu2 O/CuO heterojunction and its PV properties. Section 6
first outline the theory of heterojunction solar cells with emphasis on the copper oxide
will briefly discuss preliminary studies on solar cells based on Cu4 O
heterojunction and band diagram. Sections 3 and 4 review the Cu 3 . This is followed by a conclusion
2O and CuO heterojunction solar
and outlook on the remaining challenges in the field of copper
cells, respectively. Section 5 describes the electrodeposited Cu2O/CuO oxide solar cells.
heterojunction and its PV
properties. Section 6 will briefly discuss preliminary studies on solar cells based on Cu4O3. This is
2. Heterojunction Solar Celland
followed by a conclusion Device Physics
outlook on the remaining challenges in the field of copper oxide
solar cells.
Before reviewing the copper oxide heterojunction solar cells, it is useful to consider the energy
band diagram and the theory of heterojunction solar cells. Cu2 O and CuO form type II heterojunctions
2. Heterojunction Solar Cell Device Physics
with another semiconductor such as ZnO or Si in these solar cells. In a type II (or staggered)
Beforeonly
heterojunction, reviewing
one ofthethecopper
band oxide
edgesheterojunction
(either Ec or Esolar cells, it is useful to consider the energy
v ) of one semiconductor is situated within the
band diagram and the theory of heterojunction
band gap of the other semiconductor forming the heterojunction [12]. solar cells. CuFigure
2O and CuO form type II
2 illustrates the schematic
heterojunctions with another semiconductor such as ZnO or Si in these solar cells. In a type II (or
energy band diagram of a copper oxide n-type semiconductor heterojunction with interface defects
staggered) heterojunction, only one of the band edges (either Ec or Ev) of one semiconductor is
to be discussed in the next section. The n-type layer has the wider energy gap in this heterojunction
situated within the band gap of the other semiconductor forming the heterojunction [12]. Figure 2
and therefore
illustrates sun
the light is incident
schematic through
energy band this window
diagram of layer to reach
a copper oxidethen-type
Cu2 O substrate. There is
semiconductor
band heterojunction
bending on both withsides of this
interface junction
defects and
to be the built-in
discussed in theelectric field separates
next section. The n-type thelayer
photo-generated
has the
electrons
widerand holes
energy gap asin
inthis
a homojunction
heterojunctionsolar cell. By applying
and therefore sun light isthe one-dimensional
incident through this theory
windowof the
semiconductor-semiconductor
layer to reach the Cu2O substrate. heterojunction
There is cell
bandinbending
[12], theoncurrent
both sidesdensity J from
of this the device
junction under
and the
built-in electric field
illumination can be written as: separates the photo-generated electrons and holes as in a homojunction solar
cell. By applying the one-dimensional theory of the semiconductor-semiconductor heterojunction
L`d`W L`d`W
cell in [12], the current density J from the device under illumination can be written as:
J qr G ph p, xq ddx R pxq dx JST p0q JSB pL ` d ` Wq J IR s. (1)
0 0
= [ , 0 + + ]. (1)
Here, q is the electronic charge; d is the thickness of the neutral p-type layer; W is the depletion
layer width andq Lisisthe
Here, the thickness
electronic of thedneutral
charge; n-type layer.
is the thickness of the The freep-type
neutral carrier photogeneration
layer; function,
W is the depletion
layer width and L is the thickness of the neutral n-type layer. The free carrier
Gph is integrated with respect to wavelength over the full spectrum of incident sunlight and over the photogeneration
function,
thickness Gph solar
of the is integrated
cell. Rwith respect to
represents thewavelength over the full spectrum
rate of recombination of incident
in the neutral sunlight
bulk regionsandof the
over the thickness of the solar cell. R represents the rate of recombination in the
p- and n-type regions of the heterojunction. JST and JSB are the reductions in current density due neutral bulk regions
of the p- and n-type regions of the heterojunction. JST and JSB are the reductions in current density
to recombination in the top and bottom contacts, respectively. The last term JIR on the right hand
due to recombination in the top and bottom contacts, respectively. The last term JIR on the right hand
side of Equation (1) is unique to heterojunction solar cells and accounts for recombination at the
side of Equation (1) is unique to heterojunction solar cells and accounts for recombination at the
heterojunction interface.
heterojunction Although
interface. Although another
another closed
closedform
formanalytical expressionfor
analytical expression forthe
thecurrent
current density of
density
the heterojunction
of the heterojunction solar cell exists [18], the equation given above especially shows clearlyeffects
solar cell exists [18], the equation given above especially shows clearly the the of
recombination on the current density obtainable from the heterojunction solar
effects of recombination on the current density obtainable from the heterojunction solar cell. cell.

Figure
Figure 2. Schematic
2. Schematic energy
energy band
band diagramfor
diagram forheterojunction
heterojunction solar
solarcell of of
cell copper oxide
copper and and
oxide an n-type
an n-type
semiconductor.
semiconductor. Interface
Interface states
states areare representedby
represented by -- ..
Materials 2016, 9, 271 4 of 21

The rate of recombination is characterized by the minority carrier lifetime n . For a p-type
semiconductor with dopant density NA , n is given by:

n1 BNA . (2)

Here, B is the radiative recombination coefficient [19]:

*3{2 "
p2q1{2 hq2
" *
m m m
B ` 2 1` ` nE2g , (3)
3 m2 c3 pkTq3{2 me ` mh me mh

where h is the Planck constant; k is the Boltzmann constant; T is the absolute temperature and c is
the speed of light. m is the free electron mass and me and mh are the electron and hole effective
mass, respectively. n is the refractive index and Eg is the energy band gap of the semiconductor.
The quadratic dependence of B on Eg shows that a semiconductor with a narrower band gap will have
a longer minority carrier lifetime. On the other hand, a lower dopant density can also increase n .
In addition to the reduction in current density, the main effect of carrier recombination within a
heterojunction solar cell is a decrease in the open circuit voltage, V oc . For a p-type layer thickness of w
and low level excitation conditions, V oc is given by [20]:

Eg kT qwBNc Nv
Voc ln , (4)
q q Jph

where Nc and Nv are the effective density of states for the conduction band and valence band,
respectively, and Jph is the photocurrent density. The second term of this equation shows that for
both increased B and reduced Jph , the magnitude of V oc is reduced. This shows the crucial impact of
recombination on the photovoltaic performance of heterojunction solar cells.

3. Cu2 O Thin Film Heterojunction Solar Cells

Cu2 O can be formed by thermal oxidation of high purity Cu foils in a furnace [21]. The material
properties of Cu2 O have been studied in detail and can be found in other reviews [1]. Here, for the sake
of completeness, only a summary of those properties of Cu2 O relevant to solar cells will be described.
Cu2 O has a cubic unit cell structure and an energy band gap of 1.72 eV depending on the deposition
conditions [1]. Since the band gap of Cu2 O is direct, the absorption coefficient of Cu2 O is relatively
high (~105 cm1 ) and is comparable to some organic semiconductors. As-deposited undoped Cu2 O is
a p-type semiconductor with a majority carrier mobility of ~100 cm2 /Vs. The p-type conductivity is
due to Cu vacancies in the Cu2 O [1]. For extrinsic doping, N and Cl are known to be p-type dopants
for Cu2 O [22]. The search for n-type dopants for Cu2 O has until recently been elusive [3]. However, as
will be discussed in Sections 4 and 5 respectively, methods for preparing n-type CuOx and Cu2 O are
now available.
Cu2 O heterojunction solar cells have a device structure similar to other thin film solar cells
(Figure 3a). The Cu2 O is both the absorber and a substrate upon which is deposited a thin layer of
n-type wide band gap semiconductor. This layer may have a third transparent conducting oxide
(TCO) layer deposited on top of it. Ohmic contacts are formed to both the top and bottom of the
device. The first published report of Cu2 O heterojunction solar cells with this structure was that by
Herion et al. in 1980 [23]. These investigators used the sputtering technique to deposit ZnO onto Cu2 O
sheets. The PV characteristics of this device is tabulated in Table 1 (see Section 5) together with other
key devices discussed in this review. Although an of 0.14% was measured for the ZnO-Cu2 O device,
the photovoltaic effect was not due to a ZnO-Cu2 O heterojunction. Rather, it was due to the Schottky
barrier between a thin Cu film formed by reduction of the Cu2 O surface during the ZnO sputter
deposition. This paper highlights the susceptibility of the Cu2 O surface to solid state reaction and
Materials 2016, 9, 271 5 of 21

Materials
hence the2016,
need9, x to choose a low energy, low damage deposition method to form a true semiconductor
5 of 21

heterojunction with Cu2 O.

(a) (b)
TCO
n-type CuO

Cu2O n-Si(100)

CuO NP
(c)
CuO
ZnO
ITO glass
Figure 3. Schematic device structure for (a) Cu2O/ZnO heterojunction solar cell; (b) CuO/n-Si
Figure 3. Schematic device structure for (a) Cu2 O/ZnO heterojunction solar cell; (b) CuO/n-Si
heterojunction solar cell; and (c) CuO/ZnO heterojunction solar cell enhanced by mixed phase
heterojunction solar cell; and (c) CuO/ZnO heterojunction solar cell enhanced by mixed phase
CuO/Cu2O nanopowder.
CuO/Cu2 O nanopowder.

A more recent example of a thin film p-Cu2O/n-ZnO heterojunction solar cell fabricated on
A more recent
glass substrates byexample
sputtering of aisthin
thefilm
work p-Cu O/n-ZnOetheterojunction
of 2Akimoto al. [24]. In thissolar study, cellthe
fabricated
Cu2O layer on glass
was
substrates
depositedby bysputtering
reactive radio is thefrequency
work of Akimoto et al. [24].sputtering
(rf) magnetron In this study, using theaCu Cu 2O layer while
target was deposited
the ZnO
by reactive
layer radio frequency
was deposited (rf) magnetron
by magnetron sputtering
sputtering. using a Cu
The sequence target while
of deposition wasthefound
ZnO layer wasa
to have
deposited by magnetron sputtering. The sequence of deposition
major influence on the photovoltaic properties of the heterojunction fabrication. For the was found to have a major influence on
the photovoltaic2O/i-ZnO/n-ZnO
glass/Au/p-Cu properties of the heterojunction fabrication.
(Cu2O first) structure, theFor the glass/Au/p-Cu
reverse leakage current 2 O/i-ZnO/n-ZnO
was relatively
(Cu O first) structure, the reverse leakage current was
high and a photovoltaic effect was almost unobservable [24]. On the other hand,
2 relatively high and a photovoltaic effect was the
almost unobservable [24]. On the other hand, the glass/n-ZnO/i-ZnO/p-Cu
glass/n-ZnO/i-ZnO/p-Cu2O (ZnO first) structure showed much better rectification 2 O (ZnO and an structure
first) of 0.4%
showed
was obtained much better
[24]. The rectification
difference and an of the
between 0.4%two
wasdevice
obtained [24]. The
structures wasdifference
attributed between
to thethe two
similar
device structures was attributed to the similar atomic arrangements
atomic arrangements in the crystal structures of ZnO and the Cu2O for the ZnO first structure, which in the crystal structures of ZnO
and the in
results Cufewer
2 O for interface
the ZnO first structure,
defects. However,whichboth results
Voc in
and fewer
short interface
circuit defects.
current However,
density Jscboth are Vlowoc
and shortofcircuit
because defects.density Jsc are low because of these defects.
these current
In
In order
order to to achieve
achieve above above1%, 1%,ititisisnecessary
necessaryto toidentify
identifysuitable
suitablen-type
n-typesemiconductors
semiconductors that that
can
can bebe deposited
depositedonto ontoCu Cu22OO [25].
[25]. This
This isis because
because solar
solar cells
cells fabricated
fabricated from fromCu Cu22O O substrates
substrates tend tend toto
have higher efficiency than cells made from Cu O thin films [7]. In
have higher efficiency than cells made from Cu22O thin films [7]. In one such study [26], Tanaka et al. one such study [26], Tanaka et al.
deposited
depositedseveral severaltransparent
transparent conducting
conducting oxides
oxides(TCO)
(TCO)thin thin
films,films,
namely In2 O3 In
namely , In2O
2O :Sn2O(ITO),
3, 3In ZnO,
3:Sn (ITO),
ZnO:Al
ZnO, ZnO:Al (AZO) (AZO)
and ZnO-In O3 by PLD
and 2ZnO-In 2O3 byonto PLDCu2onto
O sheets.
Cu2OBoth In2 OBoth
sheets. 3 andInITO 2O3 gave
and ITO poorly rectifying
gave poorly
heterojunctions and poor PV performance. ZnO-Cu O formed
rectifying heterojunctions and poor PV performance.2 ZnO-Cu2O formed rectifying junctions and the rectifying junctions and the current
voltage
current characteristics
voltage characteristicsboth in the both dark and
in the under
dark andillumination
under illuminationwere found weretofound be affected by the Oby
to be affected 2
pressure during deposition
the O2 pressure during deposition [26]. The [26].
highestThe obtained
highest for ZnO-Cufor
obtained 2 O was
ZnO-Cu 0.9%2O under
was illumination
0.9% under
by air mass AM
illumination by2 airsolar spectrum.
mass AM 2 On thespectrum.
solar other hand, On anthe ofother
over 1% hand,can an be achieved
of overby1% using
canthe be
AZO-Cu
achieved2 Oby heterojunction.
using the AZO-Cu This is because AZO has a smaller
2O heterojunction. This is work function
because AZO thanhas ZnO a [26].
smallerFor AZO,
work
the criticalthan
function parameter
ZnO [26]. is theFordeposition
AZO, thetemperature during is
critical parameter PLD.
the By controlling
deposition this temperature
temperature duringtoPLD. the
range of 150 C200 C, a rectifying junction and an of 1.2% under AM2 illumination was obtained.
By controlling this temperature to the range of 150 C200 C, a rectifying junction and an of 1.2%
The
under improvement
AM2 illumination in of the was AZO-Cu
obtained.2 O junction is attributedinto a broader
The improvement of the AZO-Cu spectral2response
O junction that is
results in higher
attributed to a broader J sc [26]. The results of refs [25] and [26] show that ZnO and AZO
spectral response that results in higher Jsc [26]. The results of refs [25] and [26] are suitable n-type
semiconductors
show that ZnO and for forming
AZO areheterojunctions
suitable n-typewith Cu2 O.
semiconductors for forming heterojunctions with Cu2O.
Until
Until 2006,
2006,thetheofofCu Cu2O2O heterojunction
heterojunction solar cells
solar reported
cells reported in the literature
in the literatureremained
remained under 2%.
under
Since this is obviously inferior to competing second generation
2%. Since this is obviously inferior to competing second generation semiconductor solar semiconductor solar technologies and
much lower than
technologies andthe muchtheoretical
lower limitthan of theCutheoretical
2 O deviceslimitof 20% of for
Cuthe2O AM1devices spectrum
of 20%[5], forsystematic
the AM1
studies were carried out to improve the fabrication
spectrum [5], systematic studies were carried out to improve the fabrication technique of the Cu 2 O cells.
technique of thestudy,
In one such Cu2O
cells. In one such study, Minami et al. investigated four techniques for depositing the n-type thin film
semiconductor on a Cu2O absorber substrate [27]. These include: (i) DC magnetron sputtering; (ii) rf
magnetron sputtering; (iii) PLD and (iv) vacuum arc plasma evaporation (VAPE). The VAPE
Materials 2016, 9, 271 6 of 21

Minami et al.
Materials 2016, 9, xinvestigated four techniques for depositing the n-type thin film semiconductor6on a
of 21
Cu2 O absorber substrate [27]. These include: (i) DC magnetron sputtering; (ii) rf magnetron sputtering;
(iii) PLD and
technique (iv) vacuum
involves the usearc ofplasma evaporation
a low voltage (VAPE).
discharge The VAPE
to generate antechnique
arc plasma involves the usethe
to evaporate of
a low voltage discharge to generate an arc plasma to evaporate
source material [28]. AZO was deposited by DC and RF magnetron sputtering at different substrate the source material [28]. AZO was
deposited
temperatures by DC andand for RF magnetron
different sample sputtering
orientation at different substrate
and positions temperatures
in the and for different
sputtering system. The film
sample
properties orientation
of the AZO andsuch positions in the sputtering
as crystallinity, system. The film
carrier concentration, Hallproperties
mobility and of the AZO such
resistivity wereas
crystallinity, carrier concentration, Hall mobility and resistivity were
all strongly dependent on the substrate temperature and sample orientation. Since the properties of all strongly dependent on the
substrate
the AZO temperature
film affect the andproperties
sample orientation.
of the AZO/Cu Since 2the propertiesthe
O junction, of photovoltaic
the AZO film parameters
affect the properties
show a
of the AZO/Cu
similar dependence 2 O junction, the photovoltaic
on deposition conditions. parameters show a similar
It was concluded that atdependence
the optimum on deposition
substrate
conditions.
temperatureItand wasfor concluded
a samplethat at thetooptimum
normal the target, substrate temperature
the improved and for a sample
PV performance was anormal
result to of
the
fewer target, the improved
defects PV performance
at the heterojunction and an wasimproved
a result ofcrystallinity
fewer defects of at
thetheAZOheterojunction
[27]. This in and an
turn
improved
suggests that crystallinity
magnetron of the AZO [27].
sputtering, DCThis in turn
or RF, maysuggests thatbest
not be the magnetron
depositionsputtering,
technique DCfor or forming
RF, may
not be the best deposition technique
the AZO/Cu2O heterojunction. PLD and VAPE were therefore for forming the AZO/Cu 2 O heterojunction.
used to deposit ZnO on Cu2were
PLD and VAPE O in
therefore
addition to used
DC to and deposit ZnO on Cu
RF magnetron 2 O in addition
sputtering. Both PLD to DCandandVAPERF magnetron
do not involve sputtering. Both PLD
ion bombardment
and
of the VAPECu2do not involve
O surface which ion can
bombardment of the Cu2defects.
generate electronic O surfaceFurthermore,
which can generate electronic
the absence defects.
of reactive
Furthermore,
oxygen species thepreclude
absence of thereactive
oxidation oxygen
of thespecies
Cu2Opreclude
surface the[27].oxidation
As a result,of thetheCu2 Oofsurface
ZnO/Cu [27].
2O

As a result,
devices the ofbyZnO/Cu
fabricated PLD (1.42%) 2 O devices
and byfabricated
VAPE (1.52%) by PLDwere (1.42%) and bythan
both higher VAPE (1.52%)
devices were both
fabricated by
higher
magnetron thansputtering
devices fabricated
[27]. Thisbyis magnetron
the reason sputtering
why the highest[27]. This is the reason
performance Cu2O why the highest
heterojunction
performance
devices are usually Cu2 O heterojunction
fabricated by PLD devices are usually fabricated by PLD nowadays.
nowadays.
A Cu22O O heterojunction
heterojunction solar solar cell
cell with
with an an above 2% was reported by Mittiga et al. al. in
in 2006
2006 [29].
[29].
This device
devicehas hasa afour fourlayer
layerstructure
structure andand
consists of a thermally
consists oxidized
of a thermally Cu2 O Cu
oxidized substrate, a ZnO an-type
2O substrate, ZnO
layer,
n-typeanlayer,
indium doped tin
an indium oxidetin
doped (ITO) window
oxide layer andlayer
(ITO) window an antireflection MgF2 layer.
and an antireflection MgFThe oxidation
2 layer. The
conditions used for
oxidation conditions used for the Cu O layer resulted in a polycrystalline structure with
2 the Cu2O layer resulted in a polycrystalline structure with large grain large grain size and
high
size andholehigh
mobility. A low resistivity
hole mobility. (~1 km)
A low resistivity (~1 was
km) realized by quenching
was realized by quenchingthe Cuthe 2 O Cu
sheets after
2O sheets

cooling to 450to C
after cooling 450in C
a furnace [29]. The
in a furnace [29].ZnO
The layer was deposited
ZnO layer onto the
was deposited ontoCuthe
2 O Cu
substrate by ionby
2O substrate beam
ion
sputtering (IBS) followed by a thicker layer of ITO deposited by
beam sputtering (IBS) followed by a thicker layer of ITO deposited by the same technique. Underthe same technique. Under AM 1.5G
(global)
AM 1.5Gillumination, the Au/Cuthe
(global) illumination, 2 O/ZnO/ITO/MgF
Au/Cu2O/ZnO/ITO/MgF 2 device 2has a measured
device of 2.01%
has a measured [29].
of 2.01%This [29].
was
higher
This was than the reference
higher than the Au/Cureference 2 O/ITO/MgF
Au/Cu 2 device
O/ITO/MgF
2 as
2 shown
device asby the
shown J-Vbycharacteristics
the J-V in Figure
characteristics 4.
in
The
Figure V oc4.values
The V for
oc both
values devices
for both weredevices
consideredweretoconsidered
be influenced to beby influenced
defects at the by heterointerface.
defects at the
These cause reduction
heterointerface. These in the shunt
cause reductionresistance
in theand increased
shunt the reverse
resistance saturation
and increased thecurrent.
reverse As a result,
saturation
improvement of interface defects should
current. As a result, improvement of interface defects should increase the V oc and .
increase the Voc and .

Figure 4.
4. Current
Currentdensity-voltage
density-voltagecharacteristics
characteristicsofof Au/CuO/ZnO/ITO/MgF
Au/Cu 2O/ZnO/ITO/MgF2 device (upper) and
Figure 2 2 device (upper) and
Au/Cu 2O/ZnO/MgF2 device (lower) under AM 1.5G illumination Reprinted from Applied Physics
Au/Cu2 O/ZnO/MgF2 device (lower) under AM 1.5G illumination Reprinted from Applied Physics
Letters 88,
Letters 88, 163502
163502 (2006)
(2006) with
with the
the permission
permission of
of AIP
AIP Publishing
Publishing [29].
[29].

The first report of a Cu2O heterojunction solar cell with an above 3% was reported by the
The first report of a Cu2 O heterojunction solar cell with an above 3% was reported by the
Kanazawa Institute of Technology in 2011. In the first of a series of papers [3033], Minami and
Kanazawa Institute of Technology in 2011. In the first of a series of papers [3033], Minami and
co-workers demonstrated an improved device architecture for Cu2O devices. In this structure, a
polycrystalline Cu2O substrate and absorber was first formed from Cu by using a three step
oxidation process [30]. Subsequently, an n-type layer of undoped ZnO and a transparent
conductor layer of AZO were deposited sequentially by PLD. The ZnO forms a heterojunction
Materials 2016, 9, 271 7 of 21

co-workers demonstrated an improved device architecture for Cu2 O devices. In this structure, a
polycrystalline Cu2 O substrate and absorber was first formed from Cu by using a three step oxidation
process [30]. Subsequently, an n-type layer of undoped ZnO and a transparent conductor layer of
AZO were deposited sequentially by PLD. The ZnO forms a heterojunction with Cu2 O and the AZO
acts as a window layer. The back contact consists of an ohmic contact formed from either Au or Cu2 S.
The photovoltaic parameters V oc , Jsc , fill factor FF and were studied as a function of the ZnO layer
thickness. For a ZnO thickness in the range of 3050 nm, the reached a maximum of 3.83% [30].
This was mainly due to improvement in ZnO film properties such as fewer interface defects and
reduced resistivity. For a ZnO layer thicker than 50 nm, both V oc and FF decreased because of a short
minority carrier lifetime [30]. By comparison, the of an AZO/Cu2 O reference device of ~1.6% was
lower than the optimized AZO/ZnO/Cu2 O device. This shows that the ZnO buffer layer forms a
better quality junction with Cu2 O in comparison with AZO. However, both the deposition condition
and thickness of the ZnO layer must be carefully controlled to obtain high efficiency.
A more in-depth study of the n+ AZO/ZnO/Cu2 O device structure was carried out by
Nishi et al. [31]. The device fabrication process was similar to that in [30]. The thickness of the
ZnO buffer layer was varied between 0 nm and 150 nm where a zero ZnO thickness corresponded
to an n+ AZO/Cu2 O Schottky barrier junction. At the optimum ZnO thickness of 50 nm, an of
4.08% was measured. Dark current voltage measurements showed that the inserted ZnO buffer layer
forms a heterojunction with the Cu2 O with a built in potential (or barrier height) that is greater than
that of the Schottky junction. The increased barrier height could be related to the higher quality
interface obtained when ZnO is deposited at room temperature conditions [31]. In addition, the
lower carrier concentration of the undoped ZnO layer results in a finite depletion width in the ZnO
that increases the total active layer thickness. This is shown by photovoltage spectral response
measurement. When compared with the n+ AZO/Cu2 O device, the n+ AZO/ZnO/Cu2 O device has a
broader photovoltage spectrum below 460 nm because of the heterojunction formation [31].
A still higher was obtained by Minami et al. when the undoped ZnO layer was substituted by
undoped n-type Ga2 O3 in an AZO/Ga2 O3 /Cu2 O/Au device structure [32]. The choice of Ga2 O3 was
motivated by the fact that the photovoltaic properties of a Cu2 O heterojunction cell are determined
by the energetics of the heterointerface. For the Ga2 O3 /Cu2 O heterojunction, the conduction band
offset (Ec ) is smaller because the electron affinity of Ga2 O3 is in between that of Cu2 O and ZnO
(Figure 5) [32,33]. This smaller Ec should lead to a higher device efficiency. The Ga2 O3 layer in this
device was also deposited by PLD using Ga2 O3 pellets in the presence of oxygen. The and other
photovoltaic properties were found to be dependent on the oxygen pressure during PLD and the
thickness of the Ga2 O3 layer. At optimum conditions, an of 5.38% was obtained. The photovoltaic
parameters (V oc , Jsc , FF) were better than those of a comparable AZO/ZnO/Cu2 O/Au device.
The high V oc (=0.8 V) was attributed to reduced carrier recombination due to reduced defects
at the heterointerface. This was demonstrated using dark current voltage and external quantum
efficiency measurements.
The Cu2 O heterojunction solar cell with the highest (as of 2015) was reported by
Minami et al. [34]. This cell was fabricated on a Cu2 O substrate formed by thermal oxidation of
high purity Cu sheets. The Cu2 O sheet serves as both the solar absorber and the device substrate.
In order to reduce the series resistance of the heterojunction solar cell, the resistivity of the Cu2 O
substrate was reduced by Na doping [34]. This was carried out by heating the substrate with NaI
in an inert atmosphere at 500 C1000 C [34]. The reason for doping by Na is that, unlike other
dopants, the Cu2 O resistivity decrease is not accompanied by a decrease in the Hall mobility for Na
dopants. From their experiments, an optimum resistivity of the Cu2 O:Na was found to be ~15 cm.
The heterojunction was formed by successive ArF excimer laser PLD of a layer of n-type aluminum
gallium oxide (Alx -Ga1-x -O) and a top window layer of AZO. The photovoltaic performance of the
device was found to depend strongly on the composition of the Alx Ga1-x O. At an optimized Al
concentration of 2.5 at% (i.e., Al0.025 -Ga0.975 -O), the highest of 5.72% was achieved [34]. This was
 Materials 2016, 9, 271 8 of 21

increased
Materials further
2016, 9, x to 6.1% with the use of MgF2 antireflection layer and an optimized Al0.025 -Ga80.975
of 21-O
layer thickness [34].

Figure
Figure Schematic
5. 5.Schematic energyband
energy banddiagram
diagramofof(a)
(a) ZnO/Cu
ZnO/Cu 2O2 Oand
and(b)
(b)Ga
Ga2O
2O 3 /Cu
3/Cu 2O2 O heterojunction
heterojunction
showing
showing difference
difference in in conduction
conduction band
band offset.
offset. Interface
Interface states
states areare represented
represented byby - .- .

TheThechronological
chronological discussiondiscussionabove above showsshows that substantial
that substantial progressprogress
has indeed hasbeen indeed been
accomplished
accomplished in recent years in polycrystalline Cu O heterojunction
in recent years in polycrystalline Cu2 O heterojunction solar cells. This advancement can be attributed
2 solar cells. This advancement
cantobe attributed
four to four key developments.
key developments. The first is the The first is the improvement
improvement in the thermal in the thermalofoxidation
oxidation Cu resulting of
Cuinresulting in Cu O with improved crystallinity. The second is
Cu2 O with improved crystallinity. The second is the use of thin buffer layers and CuO etching
2 the use of thin buffer layers and
CuOprioretching
to n-typepriorsemiconductor
to n-type semiconductor
deposition. deposition.
This resultsThis in anresults
improved in aninterfacial
improvedlayer interfacial layer
with reduced
with reduced
defects. Third,defects. Third, the
the synthesis synthesis
of n-type oxide ofsemiconductors
n-type oxide semiconductors
with tailored band withedgetailored
offsetband
with edgerespect
offset with respect to Cu O can enhance junction properties. Finally,
to Cu2 O can enhance junction properties. Finally, the use of PLD for n-type oxide semiconductor
2 the use of PLD for n-type oxide
semiconductor
deposition crucially deposition improves crucially improves the
the heterojunction heterojunction
interface. However,interface.
the PLD processHowever, the PLD
is difficult to be
process
scaledisup difficult
to large to area
be scaled up to large
substrates. Thisarea substrates.
is because This is because
the source materialthe source material
is ablated from a pointis ablated
on the
from a point
target. on context,
In this the target. weInbriefly
this context,
highlight wetwo briefly highlight
related process two related process developments.
developments.
TheThe first is the
first is photo-metalorganic
the photo-metalorganic chemical vaporvapor
chemical deposition (MOCVD)
deposition of Cu2OofbyCu
(MOCVD) Gupta
2 O by
et Gupta
al. [13].etIn this photo-MOCVD process, an organometallic precursor
al. [13]. In this photo-MOCVD process, an organometallic precursor containing Cu carried containing Cu carried by
ultra high purity gases into a deposition chamber is used
by ultra high purity gases into a deposition chamber is used for Cu2 O deposition onto p-Si for Cu 2 O deposition onto p-Si
substrates.
substrates. The deposition
The deposition at at
750750CisC assisted
is assisted by byultraviolet
ultraviolet photons
photons fromfrom a Xenon
a Xenon flashflashlamp.lamp.
Although structural, optical and electrical characterization of these
Although structural, optical and electrical characterization of these Cu2 O films on p-Si and quartz Cu 2 O films on p-Si and quartz
were
were performed,
performed, nono data
data onon PVPVdevices
devices waswas reported
reported [13].
[13].
TheThe second
second concerns
concerns thethe
useuseof of
atomic
atomic layer
layer deposition
deposition (ALD)
(ALD) to to
control
control thethe
interface
interface quality
quality of of
CuCu2O heterojunction soloar cells. In a study by Lee et al. [35], an ultra thin
2 O heterojunction soloar cells. In a study by Lee et al. [35], an ultra thin buffer layer of amorphous
buffer layer of amorphous
zinc
zinctintinoxide
oxide (a-ZTO)
(a-ZTO) was wasdeposited
depositedbyby ALD ALD onto onto electrochemically
electrochemically deposited
deposited Cu2 O.Cu 2O. a-ZTO
a-ZTO reduces
reduces recombination at the interface by acting as an electron blocking
recombination at the interface by acting as an electron blocking layer. The J-V characteristics for three layer. The J-V characteristics
forZnO:Al/a-ZTS/Cu
three ZnO:Al/a-ZTS/Cu 2O/Au devices with different Zn:Sn cationic ratios in a-ZTS is shown in
2 O/Au devices with different Zn:Sn cationic ratios in a-ZTS is shown in Figure 6.
Figure 6. At optimized
At optimized composition composition
of a-ZTO,of a-ZTO,
an ofan of 2.65%
2.65% was measured
was measured for thesefor these
devices devices
whichwhich is
is higher
higher than the control device without a-ZTO. In a subsequent
than the control device without a-ZTO. In a subsequent study [36], it was further demonstrated that study [36], it was further
demonstrated
the ALD reaction that the ALD reaction
conditions conditions
can be used can the
to control be used to control
oxidation state of theCu oxidation
and prevent statethe
of formation
Cu and
prevent the formation
of an undesirable CuOofinterfacial
an undesirable CuO interfacial
layer. When layer. When
the ALD temperature of the
the ALD
a-ZTOtemperature of the
layer was decreased,
a-ZTO layer was decreased, the V oc of ZnO:Al/a-ZTS/Cu 2 O/Au devices
the V oc of ZnO:Al/a-ZTS/Cu2 O/Au devices increased, indicating reduced defects at the a-ZTS/Cu2 O increased, indicating reduced
defects
interface.at the
The a-ZTS/Cu
highest 2of O 3.06%
interface. The highest
was observed of 3.06%
at a deposition was observed
temperature of 70 at a deposition
C. This group also
temperature of 70 C. This group also demonstrated that insertion
demonstrated that insertion of 20 nm thick extrinsic Cu2 O:N between the Cu2 O and Au layers of 20 nm thick extrinsic Cu2O:N can
between the Cu 2 O and Au layers can effectively reduce contact resistance
effectively reduce contact resistance of this device structure and improve FF. This is because Cu2 O:N of this device structure
and improve
acts as a p-typeFF. This is because
transport layerCu and2O:N acts as hole
facilitates a p-type transport
transport layer and[37].
by tunneling facilitates
It should holebetransport
noted that
byCutunneling [37]. It should be noted that Cu 2 O films have also
2 O films have also been used as hole transport layers in perovskite solar cells [38].
been used as hole transport layers in
perovskite solar cells [38].
Materials 2016, 9, 271 9 of 21
Materials 2016, 9, x 9 of 21

Figure 6.6. Current

Figure Current density-voltage
density-voltage characteristics
characteristics ofofZnO:Al/a-ZTO/Cu
ZnO:Al/a-ZTO/Cu22O O devices
devices with different
different
composition of
composition ofALD
ALDbuffer
bufferlayer
layerand
andnono buffer
buffer layer
layer under
under AMAM1.5G 1.5G illumination.
illumination. Energy
Energy Environ.
Environ. Sci.
2013, 6, 2112Published
Sci. 2013, by The
6, 2112Published Royal
by The Society
Royal of Chemistry
Society [35]. [35].
of Chemistry

4. CuO
CuOThin
ThinFilm
FilmHeterojunction
Heterojunction Solar
Solar Cells
Cells
Relatively little is known known about the material material properties of CuO. CuO. CuO CuO has has aa monoclinic
monoclinic crystal
crystal
structure. It has a direct energy band gap of ~1.5 ~1.5 eV and the absorption
absorption coefficient
coefficient isis also
also high
high [1].
Since for a single p-n junction solar cell, the optimum band gap is 1.4
Since for a single p-n junction solar cell, the optimum band gap is 1.4 eV, the optical properties of CuO eV, the optical properties of
CuO make
make it a very it asuitable
very suitable semiconductor
semiconductor absorberabsorber
materialmaterial
for solarfor cellsolar cell applications
applications [11]. In
[11]. In addition,
addition,
the electricaltheproperties
electrical of properties
CuO suchofasCuO majoritysuchcarrier
as majority
mobilitycarrier mobilitycarrier
and minority and minority
diffusion carrier
length
diffusion length
are also adequate. are also adequate.
Although the narrower band gap of CuO is a better match to the solar spectrum compared with
Cu22O, little
littleresearch
researchon onCuOCuOheterojunction
heterojunction solar
solarcells hashas
cells been published
been published untiluntil
recently [3944].
recently The
[3944].
The structure of the CuO heterojunction solar cells reported so far typically involves deposition the
structure of the CuO heterojunction solar cells reported so far typically involves deposition of
films onto
CuO thin films onto aa semiconductor
semiconductor substratesubstrate such such as as crystalline
crystalline Si Si wafers
wafers (Figure
(Figure 3b).
3b). The thermal
oxidation method widely used used forfor Cu
Cu22O devices has has not
not been
been used.
used. In 2012,
2012, Gao
Gao etet al.
al. reported a
p-CuO/n-Si heterojunction solar cell fabricated by the reactive magnetron sputtering technique [39].
p-CuO/n-Si heterojunction solar cell fabricated by the reactive magnetron sputtering technique
The CuO
The CuO layer
layer waswas deposited
deposited by using a Cu target and and aa sputtering
sputtering plasma consisting of Ar and O22.
When the flow rate ratio of O to Ar was
When the flow rate ratio of O2 to Ar was optimized, the deposited
2 optimized, the deposited
CuO hasCuO has a nanocrystalline
a nanocrystalline structure
structure
with with a crystallite
a crystallite size of ~8 size of ~8 The
nm [39]. nm [39].
optical The optical
band gapbandof thegapCuO of the
layer CuOwaslayer
1.07 was
eV and 1.07the
eVhole
and
the holededuced
mobility mobilityfrom deduced from Hall measurements
Hall measurements was ~0.15 cm2was /Vs ~0.15 cm2/Vs
[39]. Under AM[39].
1.5GUnder AM 1.5G
illumination, the
illumination, the current density voltage (J-V) characteristic showed
current density voltage (J-V) characteristic showed a modest photovoltaic effect and an of 0.41% was a modest photovoltaic effect
and an of
measured for0.41% was measured fordevice
a Cu/p-CuO/n-Si/Al a Cu/p-CuO/n-Si/Al
structure [39]. Both device V ocstructure
and FF were[39]. Both Voc and the
low because FF were
high
low because the high series resistance of the nanocrystalline CuO layer
series resistance of the nanocrystalline CuO layer and defects at the p-CuO/n-Si interface resulted in and defects at the p-CuO/n-Si
interface
carrier resulted in carrier
recombination. The veryrecombination.
thin CuO layer The (100
verynm) thinandCuOthe layer (100 top
Cu grid nm)electrode
and the Cu gridhave
might top
electrode
also limited might have also
the amount of limited the amount
light absorbed by this of light
device absorbed
structure. by this device structure.
Another early study of the CuO/Si heterojunction
Another early study of the CuO/Si heterojunction is that by Kumar is that byet al. Kumar et al. investigators
[40]. These [40]. These
investigators
used the RF argon used sputtering
the RF argon of asputtering
CuO targetoftoa deposit CuO target CuOto ontodeposit CuO After
n-Si(100). onto n-Si(100).
deposition, After
the
deposition, theCuO
polycrystalline polycrystalline CuO films
films were annealed in were
nitrogen annealed
at 300 inC. nitrogen at 300 structure
The crystalline C. The of crystalline
the film
structure
was of the by
determined film wasdiffraction
X-ray determined by predominantly
to be X-ray diffraction CuO to phase
be predominantly
for an annealing CuO phase for an
temperature of
annealing
300 C [40].temperature
Under dark of 300 C [40].
conditions, theUnder
CuO/Si dark conditions, showed
heterojunction the CuO/Si heterojunction
a rectifying showed a
J-V characteristic
rectifying
with J-V characteristic
a rectification ratio of 10 with
4 (ata +3
rectification
V and 3ratio of 10
V) [40]. 4 (at +3 V and 3 V) [40]. When illuminated,
When illuminated, a photovoltage response
a photovoltage
was observed [40]. response
It is also wasworthobserved
noting [40]. It is also
that there worth noting
is a presence that there
of interfacial oxideis layer
a presence
between of
interfacial
the silicon oxide layer
substrate and between
p-CuOthe silicon
layer. High substrate
resolution andtransmission
p-CuO layer.electron High resolution
microscope transmission
(HRTEM)
electron microscope (HRTEM) analysis reveals that the thickness of
analysis reveals that the thickness of the interfacial layer is around 4 nm. Furthermore, a Cu-richthe interfacial layer is around 4 nm.
Furthermore,
interfacial layer a between
Cu-rich interfacial
p-CuO andlayer between
silicon substrate p-CuO and
is also silicon substrate
observed is also interface
and the Cu-rich observedlayer and
the Cu-rich interface
significantly dependslayer on the significantly depends
sputtering power, ason the sputtering
shown in Figure 7. power, as shown in Figure 7.
Materials 2016, 9, 271 10 of 21
Materials 2016, 9, x 10 of 21

Figure 7. Cross-sectional
Cross-sectionalTEMTEMofofp-CuO/n-Si
p-CuO/n-Siheterostructure.
heterostructure.Sputter
Sputterdeposited CuO
deposited at 150
CuO W on
at 150 Wn-Si
on
substrate
n-Si for (a)for
substrate as-deposited; and (b)and
(a) as-deposited; after(b)
thermal
after treatment at 300 C at
thermal treatment for300
1 min;
C (c)
forCuO deposited
1 min; (c) CuOat
50 W sputtering power and annealed at 300 C for 1 min.
deposited at 50 W sputtering power and annealed at 300 C for 1 min.

A
A CuOCuO heterojunction
heterojunction solar solar cell
cell with
with PCEPCE approaching
approaching 1% 1% was
was reported
reported recently
recently by by
Masudy-Panah et al. [41]. The heterostructure studied was Al/Ti/n-Si/p-CuO/Ti/Al.
Masudy-Panah et al. [41]. The heterostructure studied was Al/Ti/n-Si/p-CuO/Ti/Al. The CuO The CuO layer
was
layerdeposited
was deposited by argon RF sputtering
by argon RF sputtering of aofCuOa CuO target
targetat at
a fixed
a fixedpower
powerofof150 150W W and
and working
working
pressure
pressure inin the
the range
range of of 33 to
to 35
35 mTorr. After deposition,
mTorr. After deposition, the the CuO
CuO film
film was
was further
further annealed
annealed at at 300
300 CC
from 1 min to 1 h. The CuO film properties are influenced strongly by
from 1 min to 1 h. The CuO film properties are influenced strongly by both the working pressure andboth the working pressure
and annealing
annealing time.time. By using
By using X-rayX-ray diffraction
diffraction andand Raman
Raman spectroscopy,
spectroscopy, thethe
CuO CuO phase
phase waswas found
found to
to have improved crystallinity when a higher working pressure was
have improved crystallinity when a higher working pressure was used. In addition, when annealed used. In addition, when
annealed for a prolonged
for a prolonged period, thereperiod,
is athere
phaseis atransformation
phase transformation from CuO fromtoCuO
Cu2 O to and
Cu2Oa and a mixture
mixture of CuO of
CuO
and Cu and Cu2O was formed as a result. This phase transformation is corroborated by X-ray
2 O was formed as a result. This phase transformation is corroborated by X-ray photoelectron
photoelectron spectroscopy
spectroscopy analysis. analysis.ofThe
The position theposition
Cu 2p peak of the Cu 2pfrom
shifted peak934.0
shifted
eV tofrom 934.0
932.4 eV eV
[41].toIn932.4
the
eV [41]. In the Raman spectrum, the formation of Cu O is signified
Raman spectrum, the formation of Cu2 O is signified by the appearance of peaks between 119 cm1
2 by the appearance of peaks
between
and 500 cm 1191cm 1 and 500 cm1. In addition, a
. In addition, a peak at 1110 cm peak at 1110that
1 indicates cm1elemental
indicatesCu thatis elemental
present inCu theisCuO
present
as a
in the CuO as a Cu rich copper oxide. This Cu rich copper oxide within
Cu rich copper oxide. This Cu rich copper oxide within the CuO was observed by HRTEM to be about the CuO was observed by
HRTEM to be about ~30 nm thick for a CuO film thickness of 150 nm, as
~30 nm thick for a CuO film thickness of 150 nm, as shown in Figure 8 [41]. In between the Cu rich shown in Figure 8 [41]. In
between the Cu
copper oxide andrichthecopper oxideisand
Si substrate the Si substrate
an amorphous is an amorphous
interfacial layer (IL) due interfacial
to residuallayer (IL) due
oxygen to
in the
residual oxygen in the sputtering system. Its composition was found
sputtering system. Its composition was found by energy dispersive X-ray (EDX) spectroscopy to be by energy dispersive X-ray
(EDX) spectroscopy
comprised of Si, Cu andto beOcomprised
[41]. of Si, Cu and O [41].
Materials 2016, 9, 271 11 of 21
Materials 2016, 9, x 11 of 21

Figure 8.8. Cross

Crosssectional
sectional
TEM TEM image
image of nm
of 150 150thick
nm CuO
thickfilms
CuOdeposited
films deposited
on n-typeon n-type
Si(100) Si(100)
substrates
substrates
at a working at pressure
a workingofpressure
3.3 mTorr: of(a)
3.3as-deposited;
mTorr: (a) as-deposited;
(b) annealed(b)
at 300 C forat
annealed 300 C
1 min; for(c)
and 1 min; and
annealed
(c)
at 300
annealed
C forat50300 CThe
min. for 50
samemin. The same
thickness thickness
CuO CuO filmatdeposited
film deposited a working atpressure
a workingof pressure
30 mTorrofand30
annealed
mTorr and for
annealed 3001min
1 min atfor C is at
shown
300 Cinis(d) 2014
shown inJohn
(d) Wiley & Sons,
2014 John Ltd.&[41].
Wiley Sons, Ltd. [41].

Both the Cu
Both the Curich
richcopper
copperoxide
oxideandand thethe amorphous
amorphous IL are
IL are detrimental
detrimental to interface
to interface qualityquality and
and thus
thus
need toneed to be minimized
be minimized by controlling
by controlling the sputtering the conditions
sputteringofconditions
the CuO. Thisof was
the demonstrated
CuO. This was by
demonstrated by photocurrent voltage characteristics of Al/Ti/p-CuO/n-Si/Ti/Al
photocurrent voltage characteristics of Al/Ti/p-CuO/n-Si/Ti/Al devices. The V oc of devices devices. The Vwith
oc of

devices with CuO

CuO deposited at deposited
low working at low working
pressure andpressure
annealed andat annealed
300 C forat 1300
minCwasfor 1380
min mV wasand 380the
mV
and the was only 0.14% [41]. When the annealing time was increased, the
was only 0.14% [41]. When the annealing time was increased, the V oc decreased further due to theV oc decreased further due

to the thickening
thickening of the ILof and
the ILtheand
Cu the
richCu rich copper
copper oxideOn
oxide layer. layer.
the On thehand,
other otherthehand,
V oc the Voc device
of the of the
device
increasedincreased
to 509 tomV 509 mV when
when the CuO the layer
CuO layer was deposited
was deposited at 30at 30 mTorr
mTorr and and annealed
annealed at 300at 300 C
C for
for 1 min [41]. This improvement in V oc is due to thinner interfacial layers and better CuO
1 min [41]. This improvement in V oc is due to thinner interfacial layers and better CuO crystallinity.
crystallinity.
As As a
a result, a higher result, a higher
of 0.36% of 0.36%
was obtained. was obtained.
This study shows thatThis study
the CuO shows that
deposition the CuO
and annealing
deposition and annealing
conditions play a crucial roleconditions play a the
in determining crucial role in determining
achievable the achievable
photovoltaic performance ofphotovoltaic
p-CuO/n-Si
performance of p-CuO/n-Si heterojunction solar cells. Furthermore, through
heterojunction solar cells. Furthermore, through the introduction of highly nitrogen doped CuO thin the introduction of
highly nitrogen doped CuO thin film in between CuO layer and top metal contact,
film in between CuO layer and top metal contact, the fill factor of the device improved significantly the fill factor of
the
and,device improved
as a result, significantly
efficiency and, as
of the device a result,toefficiency
increased of theindevice
1%, as shown Figureincreased
9. to 1%, as shown
in Figure 9.
Materials 2016, 9,
Materials 2016, 9, 271
x 12
12of
of21
21

Figure 9. (a) Comparison of dark current and photocurrent densities of p-CuO/n-Si heterojunction
Figure 9. (a) Comparison of dark current and photocurrent densities of p-CuO/n-Si heterojunction
solar cells with CuO deposited at 3.3 and 30 mTorr working pressures. The open circuit voltage and
solar cells with CuO deposited at 3.3 and 30 mTorr working pressures. The open circuit voltage and
photocurrent increased significantly for the sample deposited under high working pressure. Inset of the
photocurrent increased significantly for the sample deposited under high working pressure. Inset of
figure shows schematic diagram of nitrogen-doped CuO device; (b) Variation of open circuit voltage
the figure shows schematic diagram of nitrogen-doped CuO device; (b) Variation of open circuit
and short circuit current of the solar cells 2014 John Wiley & Sons, Ltd. [41].
voltage and short circuit current of the solar cells 2014 John Wiley & Sons, Ltd. [41].

Since
Since the
the poor
poor photovoltaic
photovoltaic performance
performanceof ofp-CuO/n-Si heterojunction solar
p-CuO/n-Si heterojunction solar cells
cells was
was attributed
attributed
to
to native oxide formation and a Cu rich IL during the sputtering process, a comprehensive study
native oxide formation and a Cu rich IL during the sputtering process, a comprehensive study on on
the IL properties was carried out by Masudy-Panah et al. [42]. CuO films
the IL properties was carried out by Masudy-Panah et al. [42]. CuO films were deposited at different were deposited at different
RF
RF power
power(50 (50W,W,100 100WW andand150150
W) onto
W) ontoSi using a stoichiometric
Si using a stoichiometricCuO target. The composition
CuO target. The compositionprofile,
crystallinity and theand
profile, crystallinity structure of the CuO/Si
the structure interface
of the CuO/Si was studied
interface was studiedby time of flight
by time secondary
of flight secondary ion
mass spectrometry (TOF-SIMS), Raman spectroscopy, TEM and X-ray
ion mass spectrometry (TOF-SIMS), Raman spectroscopy, TEM and X-ray diffraction respectively. diffraction respectively. For an
RF power of 50 W, the composition of the CuO layer was quite uniform.
For an RF power of 50 W, the composition of the CuO layer was quite uniform. When the RF power When the RF power was
increased
was increasedto 150toW,150 theW, Cuthe
richCu IL became
rich IL thicker
becameand the crystalline
thicker quality of quality
and the crystalline the CuOofimproved
the CuO
without compromising the optical band gap of the thin film CuO
improved without compromising the optical band gap of the thin film CuO determined from determined from the Tauc plot of the
the
absorption coefficient and photon energy h (Figure 10). This finding
Tauc plot of the absorption coefficient and photon energy h (Figure 10). This finding leads to aleads to a two-step sputtering
process
two-stepinsputtering
which a thin layer in
process of which
CuO isafirst
thinsputtered
layer of CuO at low power
is first (i.e., 50 W)
sputtered at lowfollowed
powerby(i.e.,a thicker
50 W)
layer of CuO deposited at 150 W. The resulting CuO can have
followed by a thicker layer of CuO deposited at 150 W. The resulting CuO can have both both good crystallinity and a thin Cu
good
rich IL (Figure
crystallinity and11).a thin
In order to demonstrate
Cu rich IL (Figure 11).the Inimproved
order tofilm propertiesthe
demonstrate forimproved
the two step filmprocess,
propertiesthe
photovoltaic performances of several p-CuO/n-Si devices were
for the two step process, the photovoltaic performances of several p-CuO/n-Si devices werecompared for one-step and two-step
deposition
compared of forCuO. For the
one-step andone-step
two-step process, the lowest
deposition RF power
of CuO. For the (50one-step
W) led toprocess,
the highest of 0.38%.
the lowest RF
At higher
power (50RFW)power,
led to thethehighest
increased ofthickness
0.38%. Atofhigher
the CuRF ILpower,
alludedthe to increased
above ledthickness
to a loss of of efficiency.
the Cu IL
When
alluded thetotwo-step
above led process
to a lossis used instead with
of efficiency. When thetheCuO layer deposited
two-step process isat higher
used power
instead and
with doped
the CuO
with
layer deposited at higher power and doped with nitrogen, an of 1.21% was obtained. This is cell
nitrogen, an of 1.21% was obtained. This is the first report of a CuO heterojunction solar the
with an above 1% [42].
first report of a CuO heterojunction solar cell with an above 1% [42].
Materials 2016, 9, 271 13 of 21
Materials 2016, 9, x 13 of 21

0.5 vs. photon energy of CuO thin film grown at sputtering power of 50 W
Figure 10. Tauc
Figure 10. Tauc plot
plot of
of (h)
(h)0.5 vs. photon energy of CuO thin film grown at sputtering power of 50 W
and C for 1 min. The extrapolated intercept gives
and 150
150 W
W followed
followed by
by rapid
rapid thermal
thermal treatment
treatment at
at 300
300 C for 1 min. The extrapolated intercept gives
the
the optical
optical band
band gap
gap of
of CuO.
CuO.

Since high sheetsheet resistance

resistance and low low carrier
carrier concentration
concentration of a CuO CuO absorber
absorber layer
layer areare possible
possible
reasons of poor photovoltaic
photovoltaic performance
performanceof ofcopper
copperoxide
oxidesolar
solarcells,
cells,a adetailed
detailedstudy
study onon doping
doping of
CuO
of CuO thin films
thin films waswascarried outout
carried by byMasudy-Panah
Masudy-Panah et al.
et [43,44]. These
al. [43,44]. Theseinvestigators
investigators report thatthat
report the
impact
the impactof nitrogen
of nitrogen doping
doping onon thethecrystal
crystalquality
qualityofofCuO
CuOthin thinfilms
films significantly
significantly depends
depends on its its
concentration and annealing temperature [43]. Thermal treatment of lightly doped samples with N
concentration ofof1.5%
concentration 1.5% diddid
notnot
cause cause significant
significant changes
changes in its structure
in its crystal crystal structure
regardlessregardless
of annealing of
annealing temperature.
temperature. However, CuO-Cu However, CuO-Cu
2 O mixed 2O was
phase mixed phase
formed forwas formeddoped
the highly for the highly
samples doped
annealed
samples
at annealed atand
low temperatures low temperatures
a dominant Cu2 Oand a dominant
phase was formed Cufor2O the
phase
highlywasdoped
formed for the
samples highly
annealed
doped
at high samples annealed at high temperatures.
temperatures.
reflectance and transmittance
The reflectance transmittance of N-doped CuO thin films in in the
the wavelength
wavelength range range of of
200 nm1500 nm was found to be increased with increasing increasing nitrogen
nitrogen concentration.
concentration. It was explained
by Masudy-Panah
Masudy-Panah in terms terms of of CuO
CuO bandgap
bandgap widening
widening and and the
the presence
presence of of Cu
Cu22O phase.
phase. It was also also
shown that by tuning the nitrogen concentration during sputter growth growth of of CuO
CuO film
film (in
(in situ nitrogen
doped), the color of the copper copper oxide
oxide film can can be
be tuned
tuned for for as-deposited
as-deposited and and also
also for
for the
the annealed
annealed
films as
films as shown
shown in in Figure
Figure 12.12.
Impact of of N-doping
N-doping on on photovoltaic
photovoltaic properties
properties of ofp-CuO(N)/n-Si
p-CuO(N)/n-Si based heterojunction
heterojunction solar solar
cells was
was also
also studied
studied [43].
[43]. VVoc
oc of doped samples
of doped samples was found to degrade with increasing N doping
doping
concentration. According to the investigators,investigators, nitridation of Cu-richCu-rich interfacial
interfacial layer
layer and
and formation
formation
poor quality
of poor quality copper
copper oxide
oxide nitride/Si
nitride/Si interface could be the reasons reasons of of the
the VVococ degradation.

Photovoltaic properties of highly doped samples were found to be

Photovoltaic properties of highly doped samples were found to be significantly lower because significantly lower because
of CuO of
CuO bandgap
bandgap widening widening
and Cu and
2 O Cu 2O formation
formation despitedespite
of lower of sheet
lowerresistance.
sheet resistance.
However, However, lightly
lightly doped
doped samples showed better photovoltaic performance over highly
samples showed better photovoltaic performance over highly doped samples and control samples. doped samples and control
samples. Improvements
Improvements in Jsc,were
in Jsc , FF and FF and weretoattributed
attributed the reduction to the reduction
of series of series
resistance resistance
of N-doped CuO of
N-doped
thin films.CuO thin films.
Materials 2016, 9, 271 14 of 21
Materials 2016, 9, x 14 of 21

Figure
Figure 11.
11. HRTEM
HRTEM image
image of
of p-CuO/n-Si
p-CuO/n-Sihetreojunction.
hetreojunction.p-CuO
p-CuOwas wasdeposited
depositedononn-Si
n-Siusing
using different
different
radio frequency power
radio frequency powerofof5050W,W,
100100
W, W,
150150 W and
W and by using
by using two-step
two-step sputter.
sputter. There There is significant
is significant impact
impact
of radiooffrequency
radio frequency
power onpower on the quality
the material materialand
quality andproperties.
interface interface properties.
Reprinted Reprinted with
with permission
permission
from Journalfrom JournalPhysics
of Applied of Applied Physics
116, 074501 116,Copyright
(2014) 074501 (2014)
2014,Copyright 2014,LLC
AIP Publishing AIP[42].
Publishing
LLC [42].
In another study, Masudy-Panah et al. showed that, by Ti-doping, it is possible to significantly
In another study, Masudy-Panah et al. showed that, by Ti-doping, it is possible to
reduce resistivity of CuO thin films while maintaining its optical properties and structural quality [44].
significantly reduce resistivity of CuO thin films while maintaining its optical properties and
The crystal structure of Ti-doped CuO thin films maintained good quality when Ti concentration was
structural quality [44]. The crystal structure of Ti-doped CuO thin films maintained good quality
increased up to 0.099%. Doping with higher Ti concentrations resulted in formation of secondary defect
when Ti concentration was increased up to 0.099%. Doping with higher Ti concentrations resulted in
phases which decreased crystalline ordering. The transmittance and reflectance of Ti-doped CuO were
formation of secondary defect phases which decreased crystalline ordering. The transmittance and
found to be independent of Ti dopant concentration. Furthermore, Ti doping has insignificant impact
reflectance of Ti-doped CuO were found to be independent of Ti dopant concentration.
on surface morphology of CuO films.
Furthermore, Ti doping has insignificant impact on surface morphology of CuO films.
The p-CuO(Ti)/n-Si heterojunction solar cells with Ti concentration of 0.099% showed better
The p-CuO(Ti)/n-Si heterojunction solar cells with Ti concentration of 0.099% showed better
performance over undoped samples and other Ti-doped samples. Both V oc and Jsc improved in
performance over undoped samples and other Ti-doped samples. Both Voc and Jsc improved in
comparison with control samples and other Ti-doped samples. Masudy-Panah et al. explained these
comparison with control samples and other Ti-doped samples. Masudy-Panah et al. explained these
improvements by reducing of series resistance and enhancing of collection efficiency. When the
improvements by reducing of series resistance and enhancing of collection efficiency. When the
two-step process was used instead to deposit the Ti-doped CuO absorber layer at high working
two-step process was used instead to deposit the Ti-doped CuO absorber layer at high working
pressure of 30 mTorr, an of 1.2% was obtained. However, overall performance of highly doped
pressure of 30 mTorr, an of 1.2% was obtained. However, overall performance of highly doped
samples significantly reduced because of high recombination rate with CuO layer.
samples significantly reduced because of high recombination rate with CuO layer.
Dalapati et al. reported that CuO thin films deposited by RF magnetron sputtering at high working
Dalapati et al. reported that CuO thin films deposited by RF magnetron sputtering at high
pressure of 30 mTorr have better crystal quality than the films deposited at lower working pressure of
working pressure of 30 mTorr have better crystal quality than the films deposited at lower
3.3 mTorr while optical properties remain the same [45]. Investigators showed that CuO thin films
working pressure of 3.3 mTorr while optical properties remain the same [45]. Investigators showed
grown at high working pressure exhibit lower defect density and higher carrier concentration.
that CuO thin films grown at high working pressure exhibit lower defect density and higher
carrier concentration.
Materials 2016, 9, 271 15 of 21
Materials 2016, 9, x 15 of 21

Figure
Figure 12.
12. Tuning
Tuning of
of film
film color
color and
and optical
optical transmittance
transmittance through
through inin situ
situ nitrogen
nitrogen doping
doping for
for sputter
sputter
grown
grown CuO
CuO andand Cu
Cu22OO thin
thin films.
films. For
For each
each deposition
deposition condition,
condition, thermal
thermal annealing
annealing modifies
modifies film
film
colorand
color andtransmittance.
transmittance. The
Thewider
wider band
band gap
gap of
of Cu
Cu22OOresults
resultsin
inhigher
highertransmittance
transmittanceasasshown
shownbybythe
the
printed characters beneath these films.
printed characters beneath these films.

In
In the
the CuO
CuO devices
devices discussed
discussed thus thus far,
far, the
the sputtered
sputtered CuO CuO layer
layer is is always
always p-type.
p-type. Recently,
Recently,
however, Lee et al. has observed n-type behavior in nanoscale
however, Lee et al. has observed n-type behavior in nanoscale non-stoichiometric CuO non-stoichiometric CuO x deposited by
x deposited
reactive
by reactive magnetron
magnetron sputtering
sputtering [46].[46].The Then-type
n-type conductivity
conductivity which
whichwas wasconfirmed
confirmedby byHall
Hall effect
effect
measurements results from the fact that in the initial stage of deposition,
measurements results from the fact that in the initial stage of deposition, the CuOx is Cu rich and this the CuO x is Cu rich and this

causes
causes electrons
electrons to to be
be majority
majority carriers.
carriers. By By depositing
depositing 50 50 nmnm of of n-CuO
n-CuOxx ontoonto intrinsic
intrinsic i-a-Si:H
i-a-Si:H in in aa
heterojunction
heterojunction p-i-n p-i-n device
device structure,
structure, aa maximum maximum of of 3.04%
3.04% was was measured
measured [46]. [46]. This
This cancan be be further
further
increased
increased to 4.79% by inserting a thin n-mc Si:H depletion assisting layer (DAL) between the CuO
to 4.79% by inserting a thin n-mc Si:H depletion assisting layer (DAL) between the CuOxx
and i-a-Si:H layer. The DAL enhances of the
and i-a-Si:H layer. The DAL enhances of the device by increasing V oc . device by increasing V oc.

The
Theperformance
performanceofofCuO CuO heterojunction
heterojunction solar cellscells
solar can canbe further enhanced
be further by theby
enhanced usethe of mixed
use of
phase copper oxide nanopowders (NP). This innovative
mixed phase copper oxide nanopowders (NP). This innovative approach to boost light absorption approach to boost light absorption was
demonstrated
was demonstrated by Bhaumik
by Bhaumik et al. et al.in 2014in 2014 [20].
[20].TheThe device
devicestructure
structurestudied
studied consists
consists of of
glass/ITO/ZnO/CuO/NP(Cu 2O, CuO) (Figure 3c). This structure is different from all the device
glass/ITO/ZnO/CuO/NP(Cu2 O, CuO) (Figure 3c). This structure is different from all the device
structures
structures discussed
discussed thus thus farfar because
because sunlight
sunlight is is incident
incident from from the the transparent
transparent substrate
substrate ratherrather than
than
from
from thethe top
top of of the
the device.
device. In In addition,
addition, both both ZnOZnO and and CuOCuO layers
layers werewere deposited
deposited by by PLD
PLD fromfrom the the
respective targets using a krypton fluoride (KrF) excimer laser
respective targets using a krypton fluoride (KrF) excimer laser to minimize the defect density at the to minimize the defect density at the
interface.
interface. The Themixed
mixedphase phaseNP NP containing
containingboth both cupric
cupric oxideoxide and and cuprous
cuprous oxideoxide was was synthesized
synthesized
from CuSO
from CuSO4 and KOH by a hydrothermal process within a sealed autoclave at 80 C. Aftersynthesis,
4 and KOH by a hydrothermal process within a sealed autoclave at 80 C. After synthesis,
the
the mixed
mixed phasephase NP NP dispersed
dispersed in in toluene
toluene was was drop
drop cast
cast onto
onto the the surface
surface of of the
the CuO
CuO thin thin film
film and
and
annealed
annealedin inoxygen
oxygenfor forup uptototwo twohours.
hours.For Forthethedevice
device annealed
annealed in in
this manner
this manner forfortwotwo hours,
hours, thethe
Jsc
under AM1.5 solar illumination was 20.9 mA/cm 2 [20].2This is much higher than the Jsc of the control
Jsc under AM1.5 solar illumination was 20.9 mA/cm [20]. This is much higher than the Jsc of the
device
controlwith
device onlywiththeonly
thinthefilm thinlayers
film(290 layersA/cm 2) and another
(290 A/cm device with
2 ) and another devicecommercial
with commercial coppercopperoxide
micro-powder
oxide micro-powder (4.22 mA/cm 2
(4.22 mA/cm ). Interestingly, the Voc of
2 ). Interestingly, the
the V ocdevice
of thewas also was
device improved by the NP
also improved byand
the
annealing. After annealing for 2 h, the V oc increased from 0.3 V to 0.4 V. As a result, a high of 2.88%
NP and annealing. After annealing for 2 h, the V oc increased from 0.3 V to 0.4 V. As a result, a high
was achieved.
of 2.88% This is the
was achieved. Thishighest reportedreported
is the highest efficiency for a CuO
efficiency for aheterostructure
CuO heterostructure solar device. The
solar device.
high performance
The high performance was was explained
explained in terms
in terms of: of:
(i) (i)
increased
increased light
lightabsorption
absorptioncausedcausedby bythe thecopper
copper
oxide
oxide NP; and (ii) improved diffusion of electrons and holes due to removal of ligands from the
NP; and (ii) improved diffusion of electrons and holes due to removal of ligands from the NPNP
after
after annealing.
annealing. As As forforVVococ,, the
theincrease
increasewas wasattributed
attributed to tothethe increase
increase in band
in band gap gap and improved
and improved band
band alignment
alignment for the forcopper
the copperoxideoxide layer.layer.
Another
Another copper oxide nanostructure isisthe
copper oxide nanostructure thenanoleaf
nanoleaf(NL). (NL).CuO CuONL NLcan canbebe solution
solution synthesized
synthesized by
by a two-step
a two-step process
process on crystalline
on crystalline Si subtrates.
Si subtrates. In [47],In CuO
[47], NLsCuOwere NLsgrownwere grown on commercial
on commercial surface
surface
texturedtextured n+-p Si
n+ -p Si solar solar
cells cells without
without passivation passivation
layer. Afterlayer. After growth,
growth, the NLs the haveNLs have an length
an average average of
length of ~280 nm and width of ~83 nm (Figure 13). The NL layer enhances light absorption in the
Si solar cell by acting as a graded index layer, which increases light scattering and trapping across
Materials 2016, 9, 271 16 of 21

Materials
~280 nm2016,
and9,width
x of ~83 nm (Figure 13). The NL layer enhances light absorption in the Si solar 16 of 21
cell
by acting as a graded index layer, which increases light scattering and trapping across a broad spectral
a broadIn spectral
region. addition, region.
the smallInCuO/n
addition, the small CuO/n
+ Si heterojunction beneath
+Si heterojunction beneath each NL
each NL facilitates charge extraction
facilitates
from chargeWhen
the device. extraction from the device.
the morphology When
of the NL the morphology
is optimized, of theNL/n
the of CuO NL is optimized,
+ -p the
Si solar cell
can
of CuO NL/n +-p Si solar cell can reach 11.07%, which is significantly higher than the control
reach 11.07%, which is significantly higher than the control device (9.39%) [47]. Very recently, CuO
device (9.39%)prepared
nanoparticles [47]. Very
by recently, CuO nanoparticles
green synthesis have also beenprepared by green
used as counter synthesisofhave
electrodes also been
dye sensitized
used as counter
solar cells [48]. electrodes of dye sensitized solar cells [48].

13. Cross-sectional
Figure 13. Cross-sectional field emission scanning electron microscope image of CuO NL grown on
pyramid-textured Si substrates for (a) 30 min; (b) 45 min; (c) 60 min; and (d) 90 min in a two-step
process. Inset
Inset of each image shows the corresponding
corresponding top view. Reproduced
Reproduced in
in part from J,J, Mater.
part from Mater.
Chem. A, 2014, 2, 6796 with permission from The Royal Society of Chemistry [47].
from The Royal Society of Chemistry [47].

recent years,
In recent years, the
the photovoltaic
photovoltaic behavior
behaviorof ofCuO/fullerene
CuO/fullerene (C60 60)) heterojunctions has also been

investigated. This
This inorganic-organic heterojunction structure is motivatedby
inorganic-organic heterojunction structure is motivated bythe
thefact
factthat
thatCuO
CuOis isa
ap-type
p-typematerial
materialwhile
whilefullerene
fullereneisisan
ann-type
n-type(acceptor)
(acceptor) material
material used
used for
for both heterojunction and
bulk heterojunction organic solar solar cells.
cells. Oku et al. used electrochemical deposition to deposit CuO
onto ITO working electrode by by using
using anan aqueous
aqueous electrolyte
electrolyte consisting
consisting of of CuSO
CuSO44 and 1-lactic acid at
65 C
C [49]. The C60
60 powder
powderand and top
top Al
Al electrode
electrode were
were deposited
deposited onon to
to CuO
CuO by
by vacuum
vacuum evaporation.
evaporation.
The measured
measured ofof the
the device,
device, however,
however,was wasextremely
extremelylow (~1044%)
low(~10 %) due to low V oc , FF andJscJ.sc .
due to low V oc, FF and
summary, the
In summary, the key
key developments
developments in in CuO
CuO devices
devices are
are the
the RF sputter deposition of both p-type
n-type CuO
CuO and n-type CuOxx. Both oxides form heterojunctions with Si, but DAL is needed needed for for CuO
CuOxx and
control of the
the interfacial
interfacial layer isis critical.
critical. The performance of CuO devices can be enhanced by the
incorporation of CuO NP and NL to enhance enhance light
light absorption.
absorption.

5. Cu
Cu2O/CuO
2 O/CuOThin
ThinFilm
FilmHeterojunction
HeterojunctionSolar
SolarCells
Cells
Since CuO has a narrower
narrower energy
energy band
band gap gap than
than Cu
Cu22O, a heterojunction
heterojunction comprising these two
oxides of CuCu can
can be be formed
formed fromfromjustjusttwotwochemical
chemicalelements.
elements. One
Oneadvantage
advantageofofthetheCuO/Cu
CuO/Cu22O
heterojunction is is that
that the
therefractive
refractiveindices
indicesofofCu Cu
2O 2O
andand
CuOCuOareare quite
quite similar,
similar, and,and,
as aasresult,
a result,
the
the reflectance
reflectance of the
of the CuO/Cu
CuO/Cu 2 O interface
2O interface is relatively
is relatively smallsmall
and and
thus thus canbeneficial
can be be beneficial to solar
to solar cell
cell performance
performance [50]. [50].
In 1986,In 1986,
SiripalaSiripala et al.anused
et al. used an electrochemical
electrochemical deposition
deposition technique technique to
to prepare
prepare
n-Cu2O n-Cu 2 O thin
thin films byfilms
using byausing
slightlya slightly acidic aqueous
acidic aqueous electrolyte
electrolyte duringduring the deposition
the deposition [51].
[51]. This
This technique
technique waswas adapted
adapted by by Wijesundera
Wijesundera to to fabricatep-CuO/n-Cu
fabricate p-CuO/n-Cu 2O 2 O heterojunction
heterojunction PVPV devices
devices [52].
[52].
In this study, a layer of Cu O was first deposited at potentiostatic conditions at 55 C using an
study, a layer of Cu22 was first deposited at potentiostatic C
electrolyte comprising copper (II) acetate acetate monohydrate
monohydrate and and sodium
sodium acetate.
acetate. This layer was then
completely oxidized to p-CuO by heating in air at 500 C. A second layer of Cu2O was deposited by
the same electrolyte at a higher bias potential to complete the formation of the heterojunction.
Materials 2016, 9, 271 17 of 21

completely oxidized to p-CuO by heating in air at 500 C. A second layer of Cu2 O was deposited by
the same electrolyte at a higher bias potential to complete the formation of the heterojunction.
Very recently, Jayathilaka et al. demonstrated a simple electrodeposition technique to fabricate
p-CuO/n-Cu2 O heterojunction solar cells [50]. The first p-CuO layer was deposited onto a Ti substrate
at potentiostatic condition in a three electrode electrochemical cell using an alkaline electrolyte
comprising lactic acid, copper (II) sulphate and sodium hydroxide. After post-deposition thermal
annealing, the second layer of Cu2 O was deposited at potentiostatic condition using a mixture of
sodium acetate and copper (II) acetate. The conductivity types of the two electrodeposited layers were
determined by the photocurrent response of a photoelectrochemical cell (PEC) using the Cu2 O and CuO
layers as a photocathode [50]. For the CuO photocathode, a negative spectral photocurrent shows that
the CuO has p-type conductivity. A positive spectral photocurrent for Cu2 O photocathode shows that
the Cu2 O has n-type conductivity. When the CuO/Cu2 O heterojunction was used as photocathode,
the spectral photocurrent exhibits opposite signs at different spectral regions. This shows that a
p-CuO/n-Cu2 O heterojunction has formed with longer wavelength radiation penetrating deeper
into the junction. After surface defect passivation treatment of the Cu2 O layer by ammounium
sulphide (NH4 )2 S [50], a Ti/p-CuO/n-Cu2 O/Au solar cell based on this heterojunction has a measured
V oc = 0.19 V, Jsc = 6.4 mA/cm2 and = 0.52%. The increased further to 0.64% after annealing at
100 C for 45 min [50].

Table 1. Photovoltaic parameters of Cu2 O and CuO heterojunction solar cells.

Heterojunction Short Circuit

Open-Circuit Fill
(Deposition Occurs on Deposition Current (%) at
Voltage V oc Factor Ref.
First Named Method Density Jsc (AM)
(mV) FF
Semiconductor) (mA/cm2 )
Cu2 O/ZnO rf sputtering 342 2.29 0.3 0.14 () [23]
Cu2 O/ZnO:Al PLD 400 7.1 0.4 1.2 (2) [26]
Ion beam
Cu2 O/ZnO 595 6.78 0.5 2 (1.5G) [29]
sputtering
Cu2 O/ZnO PLD 690 0.55 3.85 (1.5G) [30]
Cu2 O/Ga2 O3 /ZnO:Al PLD 800 9.99 0.67 5.38 (1.5G) [32]
Cu2 O:Na/Alx Ga1-x O/
PLD 840 10.95 0.66 6.1 (1.5G) [34]
ZnO:Al (x = 0.025)
Atomic layer
Cu2 O/a-ZTO/ZnO:Al 553 7.37 0.65 2.65 (1.5G) [35]
deposition
n-Si/CuO rf sputtering 330 6.27 0.2 0.41 (1.5D) [39]
n-Si/CuO:N rf sputtering 494 6.4 0.32 1.0 (1.5) [41]
Plasma,
p-c-Si:H/i-a-Si:H/n-CuOx reactive 495 13.68 0.449 3.04 (1.5) [46]
sputtering
ZnO/CuO/copper oxide PLD,
400 20.9 0.343 2.88 (1.5) [20]
nanopowder hydrothermal
CuO/Cu2 O Electrochemical 220 6.8 0.64 (1.5) [50]
GaN/Cu4 O3 rf sputtering 870 0.15 0.67 0.009 (1.5 G) [1]
D: direct.

6. Cu4 O3 Thin Film Heterojunction Solar cells

Thus far, there has only been one report on the application of Cu4 O3 in thin film heterojunction
solar cells. In [1], Meyer et al. reported preliminary results on a Cu4 O3 /GaN solar cell that was
fabricated on double polished sapphire substrate. The n-type GaN was grown on sapphire and the
heterojunction was formed by RF sputtering of Cu4 O3 onto GaN. The combined absorber thickness
was ~600 nm. Under AM 1.5G illumination, the heterojunction device showed a Jsc = 0.15 mA/cm2 ,
V oc = 0.87 V, FF = 67% and = 0.009%. All photovoltaic parameters are lower than those of a
Cu2 O/GaN heterojunction solar cell fabricated for comparison.
Environmentally stable and efficient solar cells are crucial to meet the future demand for
rewnewable energy. Thus, materials selection and suitable fabrication methods are essential.
Earth abundant low cost material such as metal oxides and nitrides, sulphide based compounds
Materials 2016, 9, 271 18 of 21

and thin film silicon are very important [5359]. As the copper oxides provide the suitable band gaps
for single junction and tandem solar cells, it is worthwhile to find n-type materials with suitable band
gap. Moreover, the sputter deposition technique is industry compatible and suitable for large scale
deployment [6064].

7. Conclusions
In this paper, the technological development of heterojunction solar cells based on Cu2 O, CuO
and Cu4 O3 has been comprehensively reviewed. Amongst these three oxides of Cu, Cu2 O devices are
at the most advanced stage of development with the highest reported . The rapid improvement in the
past few years has been due to the use of low damage deposition processes for n-type semiconductors,
improved band alignment and improved crystallinity of the junction materials. The main outsanding
problems that merit further research are the passivation of electronic defects at the interface between
Cu2 O and the n-type semiconductor. The studies by Lee et al. using ALD buffer layers can be viewed
as a first step in this direction [34]. The nature, energy distribution and mechanism of recombination at
these interface states are not well understood at present. A more fundamental understanding of these
defects should explain why the of state of the art Cu2 O devices are still well short of the theoretical
maximum efficiency of 20% [6]. Deposition of semiconductors over a large area of Cu2 O is another
challenge that requires further technological development.
For CuO heterojunction solar cells, the best reported is still much lower than Cu2 O devices.
In order for further progress to be made, the basic material properties such as crystal structure,
electronic structure, optical absorption and electronic properties will need to be determined. As with
Cu2 O, the control of the interface properties is crucial. Specifically, a low damage deposition process for
CuO deposition on n-Si must be developed to avoid the formation of a Cu rich CuOx layer. A deposition
process called successive ion layer adsorption and reaction (SILAR) that can deposit Cu2 O and CuO at
mild solution process conditions without ion bombardment is especially promising [65]. The recent
observation of n-type behavior in CuOx suggests that CuO/CuOx junctions should be fabricated by
sputtering and investigated for homojunction behavior [46].
Given the current stage of technological development of copper oxide heterojunction solar cells, a
plausible near-term application of these earth abundant PV materials may be the mutli-junction,
multi-terminal solar cells [14]. These devices consist of silicon cells connected in parallel with
heterojunction solar cells based on other semiconductor materials. Unlike conventional tandem
cells, each cell can be individually optimized in device design. The wider band gap of both Cu2 O and
CuO relative to Si can enhance the performance of Si cells, which are already near their theoretical
limits by absorbing shorter wavelength photons. This critical review of the recent literature on copper
oxide heterojunction solar cells has shown that, far from being an obsolete material system, the copper
oxides are a versatile, sustainable PV material of growing interest and importance.

Acknowledgments: Goutam K. Dalapati gratefully acknowledge John Wiley & Sons Inc. for permission to reprint
Figures 8 and 9 from Progress in Photovoltaics Research and Applications 2015; 23 637-645 in this paper.
Author Contributions: Terence K. S. Wong and Goutam K. Dalapati conceived the idea of writing this paper.
Terence K. S. Wong performed the literature search and wrote Sections 13 Sections 5 and 6. Goutam K. Dalapati,
Siarhei Zhuk and Saeid Masudy-Panah wrote Sections 4 and 7.
Conflicts of Interest: The authors declare no conflict of interest.

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