Solution-Processed All-Oxide Solar Cell Based On Electrodeposited Cu O and Znmgo by Spray Pyrolysis
Solution-Processed All-Oxide Solar Cell Based On Electrodeposited Cu O and Znmgo by Spray Pyrolysis
Solution-Processed All-Oxide Solar Cell Based On Electrodeposited Cu O and Znmgo by Spray Pyrolysis
Electronic materials
ELECTRONIC M ATERIALS
1
Center for Energy, Photovoltaic Systems, AIT Austrian Institute of Technology, Giefinggasse 6, 1210 Vienna, Austria
2
Department of Physical Chemistry, University of Vienna, Währinger Straße 42, 1090 Vienna, Austria
https://doi.org/10.1007/s10853-018-2482-2
J Mater Sci
solution-based methods. Methods like spray pyroly- cell efficiencies for Cu2O-type solar cells [7, 18].
sis, chemical bath deposition and electrodeposition Alternatively, the electron affinity of materials such
are very attractive, because they can be integrated in as ZnO can be modified by alloying them, either on
high-throughput manufacturing and often yield film the anion or the cation site [31], to decrease the large
qualities comparable to films deposited by vacuum- conduction band offset of 0.9 eV for ZnO/Cu2O
based methods [7–10]. heterojunctions [30, 32]. For example, Mg doping of
Commercialized and emerging thin-film photo- ZnO lowers the electron affinity and widens the band
voltaic (TFPV) technologies use metal oxides as gap, leading to an improved conduction band align-
transparent electrodes [5], buffer/window layers ment with the Cu2O absorber and a higher open-
[11], hole and electron transport interfacial layers [12] circuit voltage compared to intrinsic ZnO [24, 33, 34].
and antireflection coatings [13]. As light absorber, the However, film compositions containing more than
p-type cuprous oxide (Cu2O) semiconductor is the 20 mol % of Mg are shown to result in a drastic
most investigated metal oxide, with research on its deterioration of the PV performance [24, 33], that may
properties dating back to the 1920s [14]. The material be related to deep-level traps [35]. In some cases the
has a band gap of * 2 eV [15], which means that a threshold for PV performance decrease is reported to
maximum efficiency of 20% [16] (Shockley–Queisser be lower, at * 10 mol % Mg [24, 33, 34]. In accor-
limit) can be achieved. Cu2O is mainly prepared by dance with these results from the literature, the pre-
Cu sheet oxidation at high temperatures ([ 1000 °C) sent work targeted to implement a ZnMgO buffer
[17–20] and by electrochemical deposition (ECD) at layer with Mg composition within the reported
temperatures well below 100 °C [7, 8, 21–24]. The first optimum range.
method is particularly energy-intensive, but delivers In most Cu2O-type solar cells, commercially avail-
high power conversion efficiencies, with the current able TCO substrates such as fluorine-doped tin oxide
record being 8.1% [17]. On the other hand, the highest (FTO) [9, 36] or indium tin oxide (ITO) [37, 38] are
efficiency obtained with ECD-deposited Cu2O is used. To lower the overall material costs, ZnO-based
3.97%, with an impressive open-circuit voltage (VOC) TCOs, which are feasible to fabricate by solution-
of 1.2 V [7]. However, in this case the absorber was based methods, are preferred. To increase the con-
deposited on a precious-metal electrode (Au), which ductivity, ZnO is often doped with group-III ele-
contradicts the target of cost reduction by using oxide ments. Among them, Al-doped ZnO (AZO) is often
photovoltaics. used in Cu2O cells [7, 17, 23, 39]. Doping the ZnO
A limitation of Cu2O-based cells is that doping of with In is for the long-term TCO stability favorable,
Cu2O with donors is extremely difficult, due to the due to its similar ionic radius to zinc [40], which
mechanism of self-compensation that tends to main- results in low lattice stress and transparent, conduc-
tain the p-character of the material [25]. Cu2O tive films. The higher In price compared to Al is not a
homojunction solar cell architectures are therefore significant factor, since methods like spray pyrolysis
very rare [26, 27]. By far the most common and suc- yield high-quality In-doped ZnO (IZO) films, even at
cessful approach is creating heterojunction cells with relatively low In contents (\ 4 mol %) [41–43].
a non-doped, n-type oxide. In principle, it would be All-oxide solar cells are increasingly reported in
possible to use the n-type transparent conducting the current literature and recent reviews
oxide (TCO) directly as counterpart of the hetero- [4, 9, 20, 21, 24, 37, 44]. However, in any of the
junction, but the use of degenerately doped TCOs in existing reports at least one of the following state-
direct contact with the Cu2O has always led to a ments is true: (a) The absorber is fabricated by the
deterioration of the PV performance [19, 28, 29], energy-intensive thermal oxidation of Cu sheets
mostly by lowering the VOC. For this, various buffer [17–20], (b) at least one of the layers is deposited by a
layers have been inserted between the TCO and vacuum-based technique [7, 17, 24, 33, 34, 37, 45],
absorber layer. An investigation on band offsets (c) at least one of the layers is a precious metal [7, 23].
between n-type materials and electrodeposited Cu2O This paper reports, for the first time, an all-solu-
is given by Buonassisi et al. [30]. tion-processed all-oxide solar cell, based on elec-
Suitable n-type buffer layers, such as Ga2O3, have a trodeposited Cu2O absorber along with buffer/TCO
similar low electron affinity as Cu2O [30]. Indeed, layers fabricated by ultrasonic spray pyrolysis (USP).
Ga2O3 has given rise to the highest VOC values and As buffer, zinc magnesium oxide was used with
J Mater Sci
tunable Mg content, whereas an indium-doped zinc [41–43] and for Zn1-xMgxO layers [46–48]. In the
oxide was applied as TCO. The entire solar cell was present work, a Sono-Tek ExactaCoatÒ system was
processed under atmospheric conditions by using used, equipped with a Sono-Tek ImpactÒ ultrasonic
low-cost and non-toxic raw materials as well as nozzle in the horizontal geometry, operating at
upscalable processes. All layers were deposited from 120 kHz.
aqueous solutions containing the corresponding For the deposition of IZO the flow rate was kept at
metal salts, without the use of organic solvents. 1.6 ml/min and 280 spraying cycles were used at a
temperature of 360 °C, resulting in a thickness of
1.8 lm. The solution recipe was similar to the one
Experimental reported by Edinger et al. [42], except that indium
acetate instead of indium acetylacetonate was used as
Cell construction indium dopant precursor. The sprayed aqueous
solution contained 0.2 M zinc acetate dihydrate
Figure 1a shows a sketch of the solar cell structure, in (ZnAc2*2H2O, Sigma-Aldrich 96459), 4 mol% indium
the superstrate configuration, where light enters the acetate (InAc3, Sigma-Aldrich 510270) and 8 vol%
cell from the glass side. acetic acid (HAc, Sigma-Aldrich A6283).
As substrate, borosilicate glass pieces (Schott Nex- For both buffer layers (Zn0.88Mg0.12O and undoped
terionÒ D, 7.5 9 2.5 cm2) were used. The substrates ZnO) the same spraying setup as in the deposition of
were ultrasonically cleaned at 50 °C for 30 min in IZO films was used; only the flow rate was lower
HellmanexÒ III washing solution, then rinsed with (0.8 ml/min) compared to the IZO deposition, to
deionized water (DI, 18 MX/cm) as well as iso- ensure a high film homogeneity. Five spraying cycles
propanol and finally dried in air stream. Directly on the led to a film thickness of 50 nm. ZnO buffer layers
substrate the IZO TCO and the Zn1-xMgxO or ZnO were sprayed from an aqueous precursor solution
buffer were deposited by USP. Cells without the buffer containing 0.2 M zinc acetate dihydrate (ZnAc2*2H2
layer were also prepared. The Cu2O absorber was then O, Sigma-Aldrich 96459) and 8 vol% HAc. For the
electrochemically deposited atop, and finally, graphite deposition of Mg-doped ZnO films the precursor
paste contacts were defined. solution contained 0.8 M zinc acetate dehydrate and
Figure 1b–d shows photographs of the coated glass various amounts (0–30 mol%) of magnesium acetate
substrates with IZO/ZnMgO buffer layer (Fig. 1b) as tetrahydrate (MgAc2*4H2O, Sigma-Aldrich M5661),
well as photographs with the Cu2O absorber taken to obtain different Mg contents in the deposited film.
from the top side (Fig. 1c) and from the glass side
(Fig. 1d). In the sections below, the fabrication of each ECD
of the solar cell’s components is detailed and finally
the cells’ PV performance is reported. For the ECD of Cu2O, the glass substrates coated with
IZO or IZO/buffer were immersed vertically in the
Spray pyrolysis bath and connected to the working electrode of the
AUTOLABÒ potentiostat/galvanostat, equipped
Among solution deposition methods, spray pyrolysis with an analog charge integration module. A pla-
at temperatures above 350 °C has been proven a tinized titanium mesh was used as counter electrode,
suitable method for high-quality In-doped ZnO films
and a potential of - 0.6 V against an Ag/AgCl ref- (FTIR, Bruker Vertex 70). The elemental composition
erence electrode was applied for the potentiostatic of the films was determined by inductively coupled
ECD on the IZO and IZO/ZnO substrates. For the plasma spectroscopy (ICP-OES, PerkinElmer Optima
IZO/Zn0.88Mg0.12O substrates a potential of - 0.65 V 5300 DV). The current voltage curves for the cells
was applied. The deposition potentials were deter- were measured at 25 °C under dark and illuminated
mined by cyclic voltammetry and correspond to the conditions using a solar simulator with an AM1.5G
limit between the kinetic and mixed control regime spectrum. For the capacitance–voltage measure-
for the film growth [24]. The deposition was stopped ments, a precision LCR meter (Agilent 4284A) was
after the charge of 6 C passed to the working elec- used.
trode during the cathodic reaction, as measured by
the AUTOLAB’s analog charge integrator.
The aqueous ECD solution contained 0.2 M copper Results and discussion
sulfate pentahydrate (CuSO4*5H2O, Sigma-Aldrich
C8027) and 3 M lactic acid (LA, Sigma-Aldrich In the sections below, the characterization of each of
W261114) as a complexant to avoid Cu(OH)2 pre- the solar cell’s layers is detailed and finally, the PV
cipitation [49]. The solution pH was adjusted to 12.5 performance characterization of the cells is reported.
(at 25 °C) with 3 M sodium hydroxide solution
(NaOH, Sigma-Aldrich S5881) under stirring. Fur- Layer characterization
ther, in 400 ml CuSO4 solution, 100 mg of sacrificial
IZO transparent conducting electrode
zinc oxide (ZnO, Sigma-Aldrich 205532) was added
to avoid the undesired etching of the underlying ZnO
For the deposition of IZO electrodes the chemical
layer as proposed by Musselmann et al. [38]. To
composition of the sprayed precursor solution was
ensure that the ZnO layer will not be dissolved
optimized to deposit films with a high conductivity
during ECD, 40 mg of ZnO powder was added to
and transparency. Acetate precursors were chosen
170 ml solution in a 250-ml beaker and heated under
because of their volatility, low cost and non-toxic
stirring to the deposition temperature of 70 °C. After
properties. To decrease material costs the amount of
one hour a small amount of ZnO (or Zn(OH)2) pre-
the indium dopant had to be as low as possible, while
cipitate was still present in the solution, which means
not compromising the film’s conductivity. Consider-
that the solution is saturated and ZnO etching is
ing this, the optimized indium acetate concentration
avoided.
in the solution was 4 mol%, since higher amounts of
indium did not improve the conductivity further. The
Contact formation and post-processing
addition of acetic acid was necessary to stabilize the
As contacts, graphite paste dots (ca. 3 mm2) were precursors in the solution in the form of volatile zinc
applied onto the cells (Alfa Aesar, 42466). The cell and indium acetate complexes (avoid Zn(OH)2 and
fabrication was completed by a 4-h, low-temperature In(OH)3 precipitation) that can deposit in a CVD-like
annealing step in air on a hot plate adjusted to 150 °C process onto the substrate [50]. The amount of acetic
to improve the PV performance, mainly due to an acid also influences significantly the growth rate of
improvement of the series and shunt resistance. IZO films, as investigated by Solorza-Feria et al. [41].
In the present work the precursor solution had a pH
Characterization methods value of 3.65 (at 25 °C), which resulted in a fast film
growth rate (50 nm/min). Temperature and flow rate
The film thickness and morphology for each layer were optimized in order to obtain a dense film
were characterized by scanning electron microscopy without low-temperature spraying artifacts, while
(SEM, Zeiss Ultra 40). The crystal structure was using a high flow rate for a fast film deposition. A
investigated by X-ray diffraction (XRD, Thermo film thickness of 1.8 lm resulted in a sheet resistance
Fisher Scientific ARL Equinox 100). Transmittance of 25 X/sq. with an average transparency of 72% in
and specular reflectance spectra (13° angle) in the the visible range between 450 and 700 nm. Cross
range between 300 and 1100 nm were recorded by section and plane view SEM images of the IZO films
Fourier transform infrared spectroscopy instrument
J Mater Sci
Figure 2 Plane view SEM images of (a) glass/IZO and cross section SEM of (b) glass/IZO/Zn0.88Mg0.12O.
compact films (see also Fig. 4). The optical band gap
Figure 3 X-ray diffractograms of the investigated films along of 3.26 eV was determined by a linear extrapolation
with the ZnO and Cu2O reference patterns. of the absorption edge using Tauc’s relation
ahm = A(hm - Eg)1/2 for direct band gap semicon-
are shown in Fig. 2a, b. The deposited films are ductors, where a, h, m, A and Eg are the optical
smooth and compact with small grain size. absorption coefficient, Planck’s constant, the photon
Figure 3 shows the crystal structure of the films frequency, a constant and the energy of the optical
analyzed by XRD. IZO films have a polycrystalline band gap, respectively [51].
zincite phase (COD: 96-900-4182) with mainly {1011}
and {1120} film textures. Minor reflections from Zn0.88Mg0.12O and ZnO as buffer layers
{1012},
{1010}, {1013}, {1122}
{2020}, and {2021}
planes
are also present. The peaks show a small shift to Undoped and Mg-doped ZnO layers were sprayed
lower 2H angles, because of the substitutional incor- onto cleaned glass substrates to investigate the Mg
poration of the slightly larger In3? ion compared to content in the film. ICP-OES showed that solutions
Zn2?. Transmittance spectra show Fabry–Perot containing 0–20 mol% Mg resulted in 0–16 mol%
interferences, which are commonly observed in incorporated Mg in the film, following a linear trend
J Mater Sci
Figure 5 a Mg content in
deposited films in dependence
of Mg content in the precursor
solution for the spray
pyrolysis, b band gap in
dependence of Mg content in
the film.
Figure 6 Plane view SEM images of a glass/IZO/Zn0.88Mg0.12O, b glass/IZO/ZnO, and cross section SEM of c glass/IZO/Zn0.88Mg0.12O.
as shown in Fig. 5a. For Mg concentration in the In comparison with glass/IZO, the transparency is
solution larger than 20 mol% an additional MgO not changing with the addition of the thin buffer
phase was observed in the XRD. For the solar cells we layer.
concentrated on 50 nm of 12 mol% Mg-doped ZnO To demonstrate the band widening by the incor-
films (Zn0.88Mg0.12O), sprayed from solution con- poration of Mg into the ZnO lattice, the band gaps of
taining 15 mol% Mg, in accordance with the reported Zn0.88Mg0.12O and intrinsic ZnO on glass were cal-
optimum range in the literature [24, 33]. culated from the Tauc plots shown in Fig. 4. Fig-
XRD measurements showed that all deposited ure 5b displays the linear increase in band gap with
films retained the wurtzite structure. In Fig. 3 we the amount of Mg in the film, in accordance with
show the X-ray diffractograms for the ZnO and what has been observed in the literature for ZnMgO
Zn0.88Mg0.12O films. Both films have pure zincite films deposited by different techniques [52–54].
phase. Zn0.88Mg0.12O shows a polycrystalline texture 12 mol% Mg incorporation enhances the band gap
with mainly {1010}, {0001} and {1011} reflections of from 3.28 eV (for ZnO) to 3.45 eV. This should
the same intensity and minor reflections of {1012}, translate to a lower electron affinity of Zn0.88Mg0.12O
{1120}, {1013}, {1122}. ZnO films show mainly a {0001} and, as a result, better conduction band alignment
surface texture with minor reflections of {1010}, with Cu2O.
{1011}, {1012}, {1120}, {1013}, {1122}.
Plane view and cross section SEM images of the Cu2O absorber
Zn0.88Mg0.12O and ZnO films on glass/IZO substrates
The Cu2O absorber was deposited by ECD, and the
are shown in Fig. 6a–c. All films are compact and
film thickness d was determined from Faraday’s
homogeneous, appropriate for the subsequent ECD
formula d = MQ/nFAq, with M the molar mass of
of Cu2O. Figure 4 displays transmittance spectra of
Cu2O (143.09 g/mol), Q the charge in C, n the
the IZO electrode with the two different buffer layers.
J Mater Sci
Figure 7 Plane view SEM images of a glass/IZO/Zn0.88Mg0.12O/Cu2O and b cross section SEM of the glass/IZO/Zn0.88Mg0.12O/Cu2O
cell stack.
number of electrons involved in the reaction (n = 2), The surface texture of the Cu2O absorber is a very
F the Faraday constant (96485.33 C/mol), A the important property that determines the heterojunc-
electrodeposited surface area in cm2 and q the den- tion quality. The morphology depends on many
sity of Cu2O (6 g/cm3). The formula gives d = 3.5 lm parameters, such as the nature of the substrate,
for Q = 6 C. In practice, only a 2-lm-thick film was solution properties (pH, molarity and complexing
deposited, which suggests that cathodic side reac- agents) and deposition conditions (temperature,
tions (such as Cu metal formation or partial reduction applied potential/current density). For the used
to CuO) and/or dissolution of Cu2O happen during deposition solutions and all substrates, it was shown
the ECD process. SEM pictures of the Cu2O mor- that using high pH values [ 12.5 leads to a {111}
phology (Fig. 7a) show round-shaped grains instead surface texture. The reason for this behavior is that
of the characteristic cubic faceted grains, which sug- planes with a high oxygen density, such as {111}, are
gests dissolution as the main reason for the Cu2O film favored if the oxygen supply is high. This can be
thickness discrepancy. The cross section of the IZO/ achieved by forming the Cu2O film mainly via the
Zn0.88Mg0.12O/Cu2O cell stack in Fig. 7b shows that reduction of copper-hydroxo-complexes, which are
the film is dense with grain sizes of a few lm. Large formed at higher pH values instead of copper-lactic-
grain size is desirable as it leads to less grain complexes [55].
boundary scattering of the charge carriers, i.e., better The band gap of the Cu2O films was determined to
electrical transport properties. be 1.92 eV by measuring the specular reflectance
XRD (Fig. 3) revealed that the Cu2O films are spectrum (see Fig. 8). This value fits well to the pre-
entirely of the cubic cuprite phase (COD: 96-900- viously reported band gaps of electrochemically
7498), without traces of CuO or metallic Cu. The main deposited Cu2O [24, 39].
surface orientation of the Cu2O films under these
experimental conditions is {111} with minor peaks of Solar cell characterization
{110}, {200}, {220}, {311}. For the ZnO small peaks
from the zincite phase are observed.
(such as {1120}) Following heterojunction solar cells were
Although the texture of the absorber is independent investigated:
of the buffer layer, the lattice strain differs. Taking the 1. glass/IZO (1.8 lm)/Cu2O (2 lm)/graphite contacts
position of the Cu2O {111} peak and calculating the 2. glass/IZO (1.8 lm)/ZnO (50 nm)/Cu2O (2 lm)/
distance between lattice planes, d, we find d = 2.469 graphite contacts
Å for the IZO and ZnO buffer and d = 2.497 Å for the 3. glass/IZO (1.8 lm)/Zn0.88Mg0.12O (50 nm)/Cu2O
Zn0.88Mg0.12O buffer, whereas the reference XRD (2 lm)/graphite contacts.
pattern yields d = 2.468 Å. Similar results are
obtained for the {200} peak. We find, therefore, that A schematic representation of the device structure
the Cu2O lattice has a larger strain in the case of the with a buffer layer is shown in Fig. 1. The dark and
Zn0.88Mg0.12O buffer. illuminated current density–voltage (j–V) curves of
J Mater Sci
Figure 9 a Dark and b illuminated (AM1.5G) current density–voltage (j–V) curves of the best cells.
reduced optical losses in the UV spectral region sizes of Cu2O obtained by this method. For ECD-
compared to ZnO. deposited Cu2O, the ALD-grown ZnMgO buffer [24]
Figure 10 displays the mean value and standard yielded higher efficiency compared to the buffer
deviation of the VOC, JSC, FF and g for 10 cells from deposited by MOCVD [33]. The high cell perfor-
each of the three heterojunctions. The average values mance achieved by ZnO-based ALD buffer layers
show a similar trend as the best cells. Indeed, the use was investigated by Lee et al. [56]. They showed that
of the Zn0.88Mg0.12O buffer leads to higher PV per- the chemical state of Cu at the heterojunction inter-
formance as compared to the ZnO buffer, while the face can be controlled by adjusting the ALD condi-
cells without (w/o) buffer have the lowest perfor- tions and by the used zinc precursor.
mance. We also note that the cells with the Zn0.88 It also has to be considered that the highest cell
Mg0.12O buffer have a larger standard deviation of efficiencies were achieved using the substrate cell
the PV parameters, which is attributed to a stronger architecture, where the buffer and the transparent
spatial inhomogeneity of the Cu2O thickness over the electrode are deposited on top of the absorber. Due to
sample area. that, the cells in this work can be most fairly com-
An improvement in VOC with increasing Mg con- pared to the superstrate cell from Duan et al. [33] and
tent (up to * 10 mol%) was also reported by Duan the one reported by Izaki et al. [21]. In the latter case
et al. [33], Kaur et al. [24] and Minami et al. [34]. A an undoped, electrodeposited ZnO buffer was used,
comparison of the literature values for ZnMgO/Cu2O forming therefore a solution-processed heterojunc-
heterojunctions, with different deposition methods tion, with PV performance values shown in Table 2.
for the absorber and the buffer layer, is shown in Compared to this work, the VOC obtained by Izaki
Table 2. et al. is notably larger. This may stem from various
The highest cell efficiencies (2.2% [20] and 4.31% differences, like the defect density at the heterojunc-
[34]) were observed when thermally oxidized copper tion, or the texture of the absorber. Indeed, Cu0 or
sheets were used as absorber, due to the larger grain Cu2? impurities at the heterojunction, even though
J Mater Sci
Table 2 Reported literature values for all existing ZnMgO/Cu2O solar cells and one relevant ZnO/Cu2O cell
Buffer deposition method Cu2O deposition method Architecture VOC (V) JSC (mA/cm2) FF (%) g (%) Reference
ZnMgO
PLD Thermal oxidation Substrate 0.73 9.52 63.0 4.31 [34]
AALD Thermal oxidation Substrate 0.65 6.90 49.2 2.20 [20]
ALD ECD Substrate 0.55 6.80 45.0 1.67 [24]
MOCVD ECD Superstrate 0.58 3.00 42.0 0.71 [33]
USP ECD Superstrate 0.34 3.76 52.7 0.67 This work
ZnO
ECD ECD Superstrate 0.59 3.80 58.0 1.28 [21]
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