Efficiency enhancement of ZnO/Cu2O solar cells with well oriented and micrometer

grain sized Cu2O films

Zhigang Zang

Citation: Appl. Phys. Lett. 112, 042106 (2018);

View online: https://doi.org/10.1063/1.5017002
View Table of Contents: http://aip.scitation.org/toc/apl/112/4
Published by the American Institute of Physics

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 APPLIED PHYSICS LETTERS 112, 042106 (2018)

Efficiency enhancement of ZnO/Cu2O solar cells with well oriented and

micrometer grain sized Cu2O films
Zhigang Zanga)
Key Laboratory of Optoelectronic Technology & Systems, Ministry of Education, Chongqing University,
Chongqing 400044, China
(Received 23 November 2017; accepted 12 January 2018; published online 25 January 2018)
Cu2O is one of the attractive photovoltaic materials for solar cells because of its low cost,
nontoxicity, and good mobility. In this paper, an obvious enhancement of power conversion
efficiency (PCE) for ZnO/Cu2O solar cells with perfectly oriented and micrometer grain sized
Cu2O films was experimentally demonstrated. Cu2O was fabricated using radical oxidation of Cu

foils at a low temperature of 500 C. When followed by a rapid quenching and post annealing
treatment, the perfectly oriented and micrometer sized Cu2O crystals (34 lm) could be obtained.
The crystal structure and optical properties of Cu2O were investigated in detail. Compared to
conventional solar cells without any treatment, the PCE of the solar cells based on Cu2O with
treatment was 3.18%, corresponding to a significant PCE improvement of 60.6%. Published by AIP
Publishing. https://doi.org/10.1063/1.5017002

Thin film solar cells based on CdS/CdTe and CdS/
CuInSe2 heterostructures play an important role in modern
life due to their high power conversion efficiency (PCE) and
high stability.1–3 Therefore, they have been widely used for
photovoltaic power stations, traffic lights, satellites, space
exploration, etc. Nevertheless, these traditional solar cells
are not eco-friendly because their constituent elements are
intrinsic toxicity (Cd) or rare in the earth (Te, In, and Se),
which cause serious damage to human health and the global
environment. Thus, it is urgent to develop heterostructure
materials with abundance, low cost, and nontoxicity for thin
film solar cells. All metal oxide semiconductors have the
potential to meet these requirements and are promising alter-
natives for applications to the heterojunction solar cells.4
Cuprous oxide (Cu2O) is such a potential oxide semiconduc-
tor material for low cost photovoltaic applications, as it
shows several significant advantages, such as low cost, non-
toxicity, good mobility, high absorption coefficient, and
direct bandgap (about 2.1 eV).5 These obvious advantages
make Cu2O suitable for acting as an efficient absorber layer
in solar cells. Cu2O has been fabricated using various techni-
ques such as thermal oxidation,6,7 chemical vapor deposi-
tion,8 electrodeposition,9 and reactive sputtering.10,11 In our
previous report, high quality Cu2O films could also be
obtained by radical oxidation of Cu films at a low tempera-
ture of 500  C,12,13 which is totally different with the method
of thermal oxidation of Cu films above 1000  C. The low
growth temperature (500  C) for Cu2O films is beneficial for
the cost reduction.
Until now, Cu2O based heterojunction architectures
combing with various n-type metal oxides have been widely
investigated, such as TiO2, CdO, and ZnO.14–16 In particular,
the heterojunction of p-Cu2O with n-ZnO is very attractive,
which is considered as one of the next generation solar cells,
as ZnO has been found to be most stable, efficient, and trans-
parent conductive metal oxides.17 The relative position of
a)
Author to whom correspondence should be addressed: zangzg@cqu.edu.cn
the energy band position of ZnO and Cu2O semiconductors
contributes to separation of photogenerated electrons and
holes, i.e., the conduction band minimum (CBM) of Cu2O is
a little higher than the CBM of ZnO and the valance band
maximum (VBM) of ZnO is lower than the VBM of Cu2O.
Moreover, all the constituent elements of Cu2O and ZnO are
nontoxic, low cost, and abundant. While ZnO/Cu2O solar
cells have such advantages, a reported PCE over 1% is diffi-
cult to achieve in the initial stage. Thus, a lot of ZnO/Cu2O
heterojunction solar cells using different fabrication techni-
ques have been proposed. For example, Cui et al.18 and
Musselman et al.19 reported the nanostructured ZnO/Cu2O
solar cells with a PCE of 0.88% and 0.47%, respectively.
Recently, the electrodeposited ZnO/Cu2O solar cells with a
PCE of 1.43% were reported by Fujimoto et al.20 More
recently, Minami et al. demonstrated a multi-junction of an
Al-doped ZnO (AZO)/non-doped ZnO (ZO)/Cu2O solar cell
with a PCE of 3.83%.21 The main reason for the PCE
improvements of the Al-doped ZnO (AZO)/non-doped ZnO
(ZO)/Cu2O solar cell is the optimization the n-type oxide
thin film and the resistivity of the Cu2O sheet while main-
taining high mobility. Although the multi-junction structure
contributes to improving the conversion efficiency, it
requires a complex fabrication process and is high cost. Till
now, the highest PCE of the single heterojunction of the
ZnO/Cu2O solar cell is about 2%,22 which is still much lower
than the theoretical maximum PCE of 20%. One main reason
for the low PCE of ZnO/Cu2O solar cells is that the reported
Cu2O has a small grain size and the interface between Cu2O
and the ZnO film is rough, causing poor separation of photo-
generated electrons and holes and low PCE.12 To solve this
issue, we develop a feasible and low cost strategy, i.e., dip-
ping the fabricated Cu2O films into HNO3 solution by a rapid
quenching technique followed by a rapid annealing tech-
nique, which could generate a large grain size and flat
surface.
In this letter, we report on the utilization of a rapid
quenching and post annealing treatment to obtain perfectly

0003-6951/2018/112(4)/042106/5/$30.00 112, 042106-1 Published by AIP Publishing.

042106-2 Zhigang Zang
FIG. 1. (a) and (b) Photograph of the synthesized Cu2O films and (c) and
(d) their corresponding scanning electron microscopy (SEM) images. (a)
and (c) With rapid quenching and post annealing treatment and (b) and (d)
without treatment. The insets are the corresponding magnified SEM images.
(e) EDS spectra and (f) XPS spectra of the synthesized Cu2O films with
treatment.
oriented and micrometer grain sized Cu2O crystals to
enhance the PCE of ZnO/Cu2O solar cells. A detailed analy-
sis for the crystal structure and optical properties of Cu2O is
given. The fabricated solar cells based on Cu2O with treat-
ment show an improved open-circuit voltage (Voc ¼ 0.557 V)
and a short-circuit current density (Jsc ¼ 11.43 mAcm2). In
particular, a high PCE of 3.18% is demonstrated.
Cu2O crystals used in this experiment were fabricated
by racial oxidation of high purity Cu foils (99.9%) with a
2.5  2.5 cm2 size. The fabrication process consists of three
steps. In the first step, Cu foils with a thickness of 100 lm
Appl. Phys. Lett. 112, 042106 (2018)
were exposed to oxygen (O 2) plasma for 90 min at 500  C in
a remote-plasma-enhanced chemical vapor deposition (RPE-
CVD) chamber, in which the O 2 plasma power and flow rate
were kept at 30 W and 50 sccm, respectively, with a pressure
of 0.11 Torr. The detailed fabrication of this step can be
found in our previous report.13 The second step is dipping
the oxidized samples into 8M HNO3 solution immediately to
remove very thin CuO. The third step was post annealing of
the samples under an argon (Ar) and hydrogen (H2) gas
(Ar:H2 ¼ 3:1) atmosphere for 1 h at 500  C. The high perfor-
mance of Cu2O crystals as a substrate for solar cells could be
obtained after these three steps. The obtained Cu2O crystals
were placed on the RPE-CVD chamber again for ZnO depo-
sition to form a ZnO/Cu2O hetero-junction. The flow rate of
the O2 reaction gas and Zn was fixed at 20 sccm and 8 lmol/
min, respectively. Finally, to form the electrical contact and
fabricate ZnO/Cu2O solar cells, the Ag film and indium tin
oxide (ITO) film were deposited on the back side of the
Cu2O sheet and on the top side of ZnO, respectively. We can
get the thickness of each layer by using DEKTAK 150. The
thickness of the Cu2O sheet, ZnO, ITO, and Ag is 170 lm,
200 nm, 120 nm and 100 nm, respectively.
Two different types of Cu2O films were treated by two
different methods, and their structural, morphological, and
optical properties were investigated in detail. The photo-
graphs of the as-prepared Cu2O films with and without rapid
quenching and post annealing treatment are shown in Figs.
1(a) and 1(b), respectively, and their corresponding top-view
scanning electron microscopy (SEM) images are shown in
Figs. 1(c) and 1(d). With rapid quenching and post annealing
treatment, the color of Cu2O films shows bright red, and the
surface is smoother than that of Cu2O films without treat-
ment. Figure 2(c) shows the SEM image of Cu2O films
treated by rapid quenching and post annealing treatment,
which shows that the Cu2O crystals have an average size of
around 3 lm. We can observe a large crystal size and smooth
surface in the case of Cu2O films with treatment. For Cu2O
films without treatment, the Cu2O films are well-defined
cubic shape with sharp edges and uniform shape but with a
relatively small size distribution and rough surface, as shown
in Fig. 2(d). Thus, the SEM images clearly indicate that the
influence of rapid quenching and post annealing treatment on
the growth of Cu2O films with different morphologies, i.e.,
the rapid quenching and post annealing treatment, leads to
FIG. 2. (a) X-ray diffraction patterns
and (b) UV-vis absorption spectra of
the synthesized Cu2O films with and
without rapid quenching and post
annealing treatment.
042106-3 Zhigang Zang
better smooth Cu2O films with large grain size. The chemical
composition of Cu2O was confirmed by energy-dispersive
spectroscopy (EDS), as shown in Fig. 1(e). The EDS spec-
trum measured from the surface of Cu2O films indicates that
the main chemical elements are Cu and O existing in the
samples, the percentages of which are 67.3% and 32.4%
(nearly 2:1), respectively, which is consistent with Cu2O
film formation. The EDS spectrum of Cu2O films is in accor-
dance with the data in the previous published literature.23
Chemical states of Cu2O films were studied by X-ray photo-
electron spectroscopy (XPS). The binding energy peaks at
932.25 eV and 952.15 eV are Cu 2p3/2 and Cu 2p1/2 of Cu2O,
respectively, corresponding to a monovalent Cu.24 Thus, the
XPS results confirm that there is no existence of CuO.
The crystal structure and composition of the obtained
Cu2O films are analysed by X-ray diffraction (XRD). Figure
2(a) shows their diffraction patterns and the standard card
(JCPDS No. 05–0667). Both synthesized Cu2O films exhibit
(110), (111), (220), and (222) diffraction peaks of cubic
phase Cu2O, indicating that no other impure phases such as
Cu or CuO are observed. The diffraction peaks are strong
and sharp, which means that the synthesized Cu2O films are
highly crystalline. For the Cu2O films without rapid quench-
ing and post annealing treatment, the strongest intensity of
the diffraction peak is the (220) crystal direction. However,
in the case of Cu2O films with rapid quenching and post
annealing treatment, a highly (111) oriented Cu2O film was
generated, and the intensity of the (220) diffraction peak is
much lower than that of Cu2O films without rapid quenching
and post annealing treatment. Meanwhile, as shown in Fig.
1(a), we observe that the intensity of (220) and (222) diffrac-
tion peaks is low. Thus, Cu2O films show the (111) preferen-
tial orientation after rapid quenching and post annealing
treatment, which may suggest that there is only main growth
direction along the (111) direction. It has been known that
the crystal faces with a main growth direction will be
exposed to less different facet and consequently exhibit rela-
tively smoothness on the surface morphology. These results
are also confirmed by the SEM images.
The optical properties of the as-prepared Cu2O films
were investigated by UV-visible spectrometry. The wave-
length dependent absorption spectra of both synthesized
Cu2O films with the same thickness are shown in Fig. 2(b).
The absorption spectra for both Cu2O films exhibit a broad
absorption in the UV and visible ranges. It is remarkable that
there is strong absorption at photon energies greater than
2 eV, which coincides with the optical bandgap of Cu2O.
There is no sharpness peak in the whole absorption spectra
because of the “direct bandgap” nature of Cu2O. By inter-
cepting the two linearly extrapolated lines, the estimated
bandgap of both samples is 2.1 eV according to the absorp-
tion edge positions. The absorption of Cu2O films with treat-
ment is higher than that of Cu2O films without treatment,
which will contribute to improving the performance of the
solar cell. The absorbance property of the Cu2O films may
be influenced by grain size and morphology.25 As the serious
roughness appears on the surface of Cu2O films without
treatment, the optical absorption of the Cu2O films without
treatment is obviously reduced in almost the full visible
region compared to those of Cu2O films with treatment.
Appl. Phys. Lett. 112, 042106 (2018)
To evaluate the photo-electrical performance of the fabri-
cated Cu2O films, we measured the photocurrent of the Cu2O
films under light irradiation of a continuous laser (k ¼ 532 nm
and the optical power of 20 mW), as shown in Fig. 3. It is
obvious that the Cu2O films with treatment show a significant
photocurrent enhancement as compared to the Cu2O films
without treatment. The photoresponse results verify our
assumptions that the Cu2O films with large grain size will
enhance the photocurrent, as the large grain crystal effectively
contributes to the separation of the photo-generated carriers,
which has already been confirmed by the previous report.26
We think that the enhanced photocurrent in Cu2O films with
treatment will also contribute to the performance enhance-
ment in the solar cell. Thus, we fabricated the solar cells based
on Cu2O films. For comparison, both the solar cells have the
same thickness of Cu2O and ZnO, as schematically shown in
Fig. 4(a). The external quantum efficiency (EQE) spectra of
the ZnO/Cu2O heterojunction solar cell are shown in Fig.
4(b); it can be seen that the EQE of the solar cell with treat-
ment is higher than that of the solar cell without treatment,
thus indicating a good absorbance and charge collection in
this cell. The current density-voltage (J-V) curves of the devi-
ces with and without rapid quenching and post annealing treat-
ment are shown in Fig. 4(c). It was found that the rapid
quenching and post annealing treatment contributed to a signif-
icant performance improvement on the devices. Compared to
the devices without treatment, both the open-circuit voltage
(Voc) and short-circuit current density (Jsc) of the devices
treated by rapid quenching and post annealing improved
remarkably, with improvement in Voc (from 0.502 to 0.557 V)
and Jsc (from 7.47 to 11.43 mAcm2). The fill factor (FF) for
all the devices exceeds 0.50. More importantly, the former
exhibited a maximum PCE of 3.18% under 100 mW/cm2 illu-
mination of simulated AM 1.5G sunlight, while the latter
showed only 1.98%. This result corresponds to a significant
PCE improvement of 60.6%. The detailed photovoltaic param-
eters of ZnO/Cu2O solar cells are summarized in Table I. By
combining the rapid quenching and post annealing treatment
on the surface of Cu2O films, high PCE was achieved due to
the increase in the grain size and the improvement of the
FIG. 3. Photoresponse of the synthesized Cu2O films with and without rapid
quenching and post annealing treatment.
042106-4 Zhigang Zang
smooth surface. Meanwhile, the photoluminescence (PL) spec-
tra of the ZnO/Cu2O heterojunction with and without rapid
quenching and post annealing treatment were measured to
observe the charge generation of the solar cells. As shown in
Fig. 4(d), a strong PL emission of the heterojunction without
treatment was observed. In contrast, we observed a significant
PL quenching effect when Cu2O subject to a treatment.
Obviously, the PL of the ZnO/Cu2O heterojunction with treat-
ment was quenched much more seriously than the ZnO/Cu2O
heterojunction without treatment. The large grains will contrib-
ute larger nonradiative relaxation rates over the surface states,
which leads to a decrease in PL intensity.26–28 These results
indicate that electrons and holes can be more efficiently
extracted by the ZnO/Cu2O heterojunction with treatment,
resulting in higher efficient solar cells, accordingly.
To well understand the working principle of the single
hetero-junction of ZnO/Cu2O solar cells, a schematic band
alignment of ZnO and Cu2O by using the Anderson model
is shown in Fig. 5. As the bandgaps of ZnO and Cu2O mate-
rials are 3.3 eV and 2.1 eV, respectively, the ZnO/Cu2O
hetero-junction will be capable of absorbing a broad region
TABLE I. Photovoltaic parameters of ZnO/Cu2O solar cells with and with-
out treatment.
ZnO/Cu2O solar cell VOC JSC FF PCE (%)
Without treatment 0.503 7.48 0.529 1.99
With treatment 0.557 11.42 0.498 3.17
Appl. Phys. Lett. 112, 042106 (2018)
FIG. 4. (a) Schematic of ZnO/Cu2O
solar cells, (b) external quantum effi-
ciency (EQE) spectra,(c) current-density
(J-V) characteristics of the device, and
(d) photoluminescence spectrum of the
ZnO/Cu2O heterojunction.
of incident light. When ZnO and Cu2O are coupled for a
hetero-junction system, the band bending will appear in
their interface and can form a good type-II band alignment,
i.e., the CBM of Cu2O is a little higher than the CBM of
ZnO and the VBM of ZnO is lower than the VBM of Cu2O.
Thus, the photo-generated carrier recombination is greatly
inhibited, as the electrons are excited from the valence
band to the conduction band and then transfer to ZnO films
rapidly.
In conclusion, we fabricated perfectly oriented and
micrometer sized Cu2O crystals by a rapid quenching and
post annealing treatment of radical oxidized Cu2O. The per-
fectly oriented and micrometer sized Cu2O crystals improved
the PCE of ZnO/Cu2O solar cells. A maximum PCE
FIG. 5. (a) Schematic diagram of energy levels of Ag, ZnO/Cu2O, and ITO.
042106-5 Zhigang Zang Appl. Phys. Lett. 112, 042106 (2018)

10
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