Advances in Physics: X

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Tandem photoelectrochemical cells for solar water

splitting

Qi Chen, Guozheng Fan, Hongwei Fu, Zhaosheng Li & Zhigang Zou

To cite this article: Qi Chen, Guozheng Fan, Hongwei Fu, Zhaosheng Li & Zhigang Zou (2018)
Tandem photoelectrochemical cells for solar water splitting, Advances in Physics: X, 3:1, 1487267,
DOI: 10.1080/23746149.2018.1487267

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ADVANCES IN PHYSICS: X
2018, VOL. 3, NO. 1, 1487267
https://doi.org/10.1080/23746149.2018.1487267

REVIEW ARTICLE

Tandem photoelectrochemical cells for solar water

splitting
Qi Chena, Guozheng Fana, Hongwei Fua, Zhaosheng Li a,b
and Zhigang Zoua,b
a
Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State
Microstructures, and College of Engineering and Applied Sciences, Nanjing University, Nanjing,
China; bJiangsu Key Laboratory for Nano Technology, Nanjing University, Nanjing, China

ABSTRACT ARTICLE HISTORY

Photoelectrochemical (PEC) water splitting without an exter- Received 5 March 2018
nal bias is a potential solution to the growing energy crisis Accepted 30 May 2018
because this method can directly convert solar energy into KEYWORDS
chemical energy. A tandem cell is a frequently used config- Solar energy;
uration for unassisted overall water splitting because of the photoelectrochemical cell;
advantages that each component are tied together to form tandem cell
a highly efficient integration. A tandem PEC water splitting
device is based on different photoelectrode absorbers, and PACS
there are two main models including photoanode/photo- 88.30.ep Electrochemical
photolytic hydrogen; 88.05.
cathode (PEC/PEC) and photoelectrode/photovoltaic (PEC/ Ec Renewable energy
PV) tandem cells. In this review, we will focus on the con- targets; 88.05.Gh Energy
cepts, configurations and recent progress of PEC/PEC and conservation; electricity
PEC/PV cells. Light absorption and energy band matching demand reduction; 88.30.E-
are the key points to enhance the solar-to-hydrogen (STH) Hydrogen production with
efficiency. Promoting the performance of a standalone semi- renewable energy
conductor material and finding new materials, coupled with
an optimized configuration, are future steps for the practical
application of tandem PEC cells.

Abbreviations: PEC: Photoelectrochemical; STH: Solar-to-

hydrogen; PV: Photovoltaic; PV-EL: Photovoltaic-electro-
lysis; CIGS: Cu(In,Ga)Se2; CGS: CuGa3Se5; ACGSe: (Ag,Cu)
GaSe2 ; Co-Ci: Cobalt carbonate; Co-Pi: Cobalt phosphate;
cDBR: conductive distributed Bragg reflector; DSC: Dye-
sensitized solar cell; IMM: Inverted metamorphic multi-
junction; PED: Photoelectrodeposition; S-P: Sputtering +
Photoelectrodeposition.

CONTACT Zhaosheng Li [email protected] Collaborative Innovation Center of Advanced Microstructures,

National Laboratory of Solid State Microstructures, and College of Engineering and Applied Sciences, Nanjing
University, Nanjing, 210093, China
© 2018 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecom
mons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original
work is properly cited.
864 Q. CHEN ET AL.

1. Introduction
Photoelectrochemical (PEC) water splitting is an important strategy for con-
verting sunlight into a chemical fuel in the form of hydrogen, and has been
widely studied for decades [1–5]. Many p-type semiconductors, such as GaP [6],
InP [7], GaInP2 [8–10], Si [11–14], SiC [15], WS2 [16], Cu(In,Ga)Se2 [17],
Cu2O [18], CuYO2 [19], CaFe2O4 [20], and Mg-doped Fe2O3 [21], have been
reported as photocathode materials for water reduction. Some of these photo-
cathodes exhibit considerable solar-to-hydrogen (STH) efficiency. Compared to
the two-electron reaction of water reduction, water oxidation involves a four-
electron reaction, which makes it the rate-determining step for water splitting.
The lack of efficient and stable photoelectrode materials for water oxidation has
restricted the application of solar water splitting. Many efforts have been devoted
to the investigation of photoelectrode materials. In addition to TiO2 [22–24],
WO3 [25] and α-Fe2O3 [26], other oxides, such as BiVO4 [27], ZnFe2O4 [28], β-
Fe2O3 [29], and YFeO3 [30], have been found to act as photoanode materials for
water oxidation. Recently, (oxy)nitride photoanode materials with a visible-light
response, such as Ta3N5 [31–35], TaON [32,36,37], LaTaON2
[38], LaTiO2N [39,40], and SrTaO2N [40,42], have also attracted much attention
due to their theoretical STH efficiency, although they exhibit poorer durability
than many oxide photoanode materials.
However, a single photoelectrode (whether a photoanode or a photocathode)
has exhibited many elusive problems for efficient overall water splitting, due to
the challenge of driving this multi-electron process with a high yield at low
overpotentials [43]. From the point of view of thermodynamics, the band gap of
a single photoelectrode should straddle the O2/H2O and H+/H2 standard elec-
trode potential for overall water splitting, and the band gap of semiconductor
materials should reach 1.23 eV. Considering ohmic losses and a kinetic loss due
to the overpotentials for oxygen or hydrogen production, the band gap of a
semiconductor photoelectrode should be larger than 2.03 eV, corresponding to
the light absorption edge of 610 nm [44]. This large gap means that photons
with long wavelengths cannot be absorbed and wide band gap semiconductor
materials are required. Nevertheless, narrow band-gap semiconductor materials
are indispensable to improve the utilization of the solar spectrum. In addition,
an STH efficiency above 10% is needed for reaching a viable level for commer-
cialization, which is a fundamental requirement [45,46]. Therefore, achieving
this efficiency is very critical for individual photoelectrode materials.
To overcome the issue of a large external bias for the overall water splitting of
a traditional single photoelectrode, some practical approaches to achieve effi-
cient PEC water splitting without an external bias have been developed. The
configuration of dual-absorber tandem systems has been increasingly more
attractive for unassisted overall water splitting [47]. Dual-absorber PEC tandem
devices can be accomplished by photoanode/photocathode (PEC/PEC) systems
 ADVANCES IN PHYSICS: X 865

or photoelectrode/photovoltaic (PEC/PV) coupled devices [47–49]. Therefore,

dual-absorber tandem devices can generate a sufficient driving force for self-
driven solar water splitting while simultaneously maximizing the fraction of
solar energy collected.
Very recently, a photovoltaic-electrolysis (PV-EL) system, which is
another type of cell devices for solar water splitting, has attracted much
attention [50]. The water oxidation and water reduction reactions at the
electrodes are driven by the electric energy, which is supported by solar
cells. Only a p/n junction, instead of the semiconductor-electrolyte junc-
tion, is required in PV/EL cells. This type of cell is different from the PEC-
based cells, which have a semiconductor–electrolyte junction.
Here, tandem PEC cells for water splitting are discussed including
PEC/PEC and PEC/PV systems.

2. Concept of tandem PEC water splitting cells

2.1 Concept of the PEC/PEC cells

One approach for overall water splitting is to use a photocathode and a

photoanode connected in series to form a PEC/PEC tandem cell, in which
the sunlight can pass through the n-type semiconductor and then the
p-type semiconductor. On the surface of the n-type semiconductor,
water is oxidized to produce oxygen, and reduction reactions on the sur-
face of the p-type semiconductor produce hydrogen.
More specifically, in this configuration, photons with the shorter wave-
lengths of the solar spectrum are absorbed by the top electrode (the photo-
anode). The remaining photons with longer wavelengths are transmitted and

Figure 1. Simplified illustration of the PEC/PEC tandem cell configuration.

866 Q. CHEN ET AL.

captured by the bottom electrode (the photocathode). Thus, after two or

more steps of sunlight absorption, more solar photons can be utilized. From
the point of view of thermodynamics, the two semiconductors with smaller
band gaps can be chosen compared with the single photoelectrode, because
each photoelectrode only needs to provide part of the potential for overall
water splitting. As shown in Figure 1, the band gap of each photoelectrode
should cover the O2/H2O or the H+/H2 standard electrode potential, and the
conduction band of the photoanode is more negative than valence band of
the photocathode. The smaller the band gap in the semiconductor material,
the more photons can be absorbed, and the larger STH efficiency may be
achieved [51].
In summary, when choosing semiconductor materials, it should be
guaranteed that the energy necessary for water splitting is gathered
entirely from the light source. In this system, the water splitting poten-
tial is generated directly at the semiconductor–electrolyte interfaces for
water redox.

2.2 Concept of the PEC/PV cells

Another feasible pathway for unassisted overall water splitting is to combine
the photoelectrodes with the photovoltaic cells to form a PEC/PV tandem
cell. This tandem cell is a PEC device that is voltage-biased with an inte-
grated PV device [9]. For the part of the PEC photoelectrodes in this
configuration, it is invariable that the minority carriers of the semiconductor
material participate in the water redox reaction and the reaction occurs at

Figure 2. Simplified illustration of the PEC/PV tandem cell configuration (taking the photo-
anode/PV as an example).
 ADVANCES IN PHYSICS: X 867

the semiconductor–electrolyte junction. Taking the n-type semiconductor

materials as an example, the majority carriers (electrons) generated in the
photoanode are recombined in the PV cell through the external circuit.
Hydrogen is generated at the metal counter electrode, which is connected
with the PV cell, as shown in Figure 2.
Solar cells can support an operation when the power generated by the
minority carriers is not enough. With the help of the bias generated by the
solar cell, it is more flexible when choosing the photoelectrode materials and
the PV cells because there is no request for the matching energy levels. For
the whole system, light is also the only energy input, which is the same as in
the PEC/PEC configuration.

3. PEC/PEC tandem cells

In 1975, Yoneyama and coworkers presented a PEC cell, which consisted of a
TiO2 photoanode and a p-GaP photocathode [52]. The n-TiO2/p-GaP tandem
cell was found to generate both hydrogen and oxygen with no external bias.
According to the previous work, Nozik presented an energy analysis in 1976
and established the general theory for connecting photoanodes and photo-
cathodes to form tandem cells [53]. Only a 0.25% of energy conversion
efficiency for water splitting was achieved, partly due to the high internal
resistance of the n-TiO2/p-GaP cell [52].
After Yoneyama’s pioneering demonstration, very little attention has
been paid to constructing photoanode/photocathode tandem cells, due to
the difficulty in improving the PEC performance of the oxide photoanodes
and developing inexpensive and stable photocathodes. There are many
problems for reaching a high STH efficiency, such as lower saturation
photocurrents and less overlap area between two photoelectrodes. If the
onset potential of the photoanode negatively shifts enough to overlap the
onset potential of the photocathode in a wider range, then the tandem cell
will be more efficient. In addition, the long-term durability of the photo-
electrodes should be considered.

3.1 BiVO4-based PEC/PEC tandem cells

With the development of BiVO4 semiconductor materials, BiVO4 has fre-

quently been utilized in PEC/PEC tandem cells because BiVO4 (band gap,
~2.4 eV) absorbs a substantial portion of the visible spectrum and has a well-
suited band structure for potential use in solar water splitting [54–56]. A
tandem cell connecting the NiO photocathode with the BiVO4 photoanode
was fabricated by Mozer’s group. The BiVO4/NiO tandem cell was stable over
several hours, and the corresponding faradaic efficiency of hydrogen genera-
tion was 80% [57]. As a photocathode, NiO has a wide band gap of 3.6–4.0 eV;
868 Q. CHEN ET AL.

Figure 3. The operating point estimated by intersecting the J–V curves for the
BiVO4 photoanodes with and without the photodeposited catalyst (corresponding solid lines
and dashed lines, respectively) and the J−V curves for the Cu2O photocathode (dotted lines,
filtered by the BiVO4 photoanode) [58].

therefore, NiO may not be a perfect photocathode for a PEC tandem cell.
Therefore, the STH efficiency of such a BiVO4/NiO tandem cell is very low.
Compared to NiO, Cu2O as a photocathode has a much smaller band
gap (2.0 eV), which can absorb wavelengths <600 nm. In 2014, Sivula’s
group presented a BiVO4/Cu2O tandem cell for overall unassisted solar
water splitting, and the corresponding STH efficiency was ca. 0.5%. In
Sivula’s report, the expected tandem cell operating point was estimated by
the individual J–V curves of the respective photoelectrodes (3-electrode).
The operating point is where the J–V curves for the photoanode and
photocathode intersect, as shown in Figure 3. Nevertheless, the perfor-
mance was found to decay during the operation because of the detachment
of the Co–Pi catalyst [58].
As the Si photocathode exhibits a band gap of 1.1 eV, it acts as an
important candidate for the tandem PEC cells for solar water splitting.
However, this photocathode exhibits a poor onset potential for water
reduction. Compared with a planar Si photocathode film, p-type Si
nanoarrays often have a larger onset potential for water reduction due to
the decrease in the transfer distance of the photoinduced electrons from
the bulk to the surface. The p-type Si nanoarrays with a preferred geometry
then were chosen to construct the tandem cell. Xu et al. designed a PEC
tandem cell consisting of a BiVO4 photoanode and Si nanoarray photo-
cathode, and an STH efficiency of 0.57% (corresponding photocurrent
 ADVANCES IN PHYSICS: X 869

Figure 4. (a) Simplified energy diagram of the BiVO4/Si nanoarray tandem cell. (b) Intersection
point of the J−V curves of the BiVO4 and Si nanoarray photoelectrodes [59].

density of 0.46 mA cm−2) was achieved in this system. As shown in

Figure 4(b), according to the operating point, an unassisted photocurrent
of 0.6 mA cm−2 is possible to achieve. The two-electrode system connect-
ing Co-Pi/Mo:BiVO4 with the Pt/p-Si nanoarray reached a stable photo-
current density of 0.12 mA cm−2 after 3.5 h, which is slightly lower than
the expected operating point. This density suggests that a noticeable loss
occurs or an instability exists. A series resistance of the whole circuit may
lead to the decline. The pH gradient that developed near the electrodes
may cause extra loss, and the dissolution of the Co–Pi catalyst decreased
the actual conversion efficiency of the device [59].
Composited photocathodes have also been used in constructing the tandem
cells. In 2016, Lee’s group demonstrated a tandem device of a Pt/CdS/CuGa3Se5/
(Ag,Cu)GaSe2 photocathode and a NiOOH/FeOOH/Mo:BiVO4 photoanode,
which achieved an STH efficiency of 0.67% over 2 h without degradation. The
Pt/CdS/CGS/ACGSe photocathode exhibited an onset potential of 0.9 VRHE and
a 4.6 mA cm−2 photocurrent filtered by the BiVO4 photoanode. The excellent
properties of the photocathode enhanced the tandem cell efficiency with a
NiOOH/FeOOH/Mo:BiVO4 photoanode with a 3.4 mA cm−2 photocurrent at
1.23 VRHE. The preferable performance of the Pt/CdS/CGS/ACGSe photo-
cathode may be attributed to the proper contacts between similar crystal
structures [60]. Although the limitation still lies in the photocurrent of the
photoanode, utilizing a photocathode with preferable properties is equally
important. In 2018, new strategies for a surface reaction and interface optimiza-
tion were employed to improve the performance of the Cu(In,Ga)Se2 (CIGS)
photocathode by Gong’s group. The spatial dispersion and particle size of the Pt
catalyst can be controlled by a two-step platinization strategy (sputtering + PED,
S-P), while the defects at the CdS/TiO2 interface can be passivated by an
Al2O3 insertion layer. Then, the improved CIGS/CdS/Al2O3/TiO2/S-P-
870 Q. CHEN ET AL.

Pt photocathode was connected with BiVO4 to construct a tandem cell, which

reached an STH efficiency of 1.01% [61]. The fabrication strategy requires an
upgrade to obtain higher performance of the photoelectrodes, not only n-type
but also p-type semiconductors, and then the tandem cells can be advanced.

3.2 Other PEC/PEC tandem cells

Hematite (α-Fe2O3) is also a prototypical material as a photoanode for tandem

cells because of its potential performance [62,63]. A Mg- and Si-doped
Fe2O3 tandem device was demonstrated in 1982, and the power conversion
efficiency was approximately 0.05% in a 0.1 M Na2SO4 solution (pH 6) [64].
With an enhancement in the preparation technology, a self-driven tandem
p/n-Fe2O3 device for photoelectrochemical water splitting was fabricated by
Khan’s group in 2006, and the STH efficiency was calculated to be 0.11%. The
p-type Fe2O3 material favours H2 generation because of the band-edge mod-
ification by zinc [65]. However, there are still many problems to solve to improve
the magnitude of the photocurrent and the stability in aqueous solutions.
Following the advances in oxide photoanode performance, increasingly more
demonstrations of p/n tandem cells have appeared. In 2008, Turner’s group
reported two p/n combinations. The n-Fe2O3 nanorod thin films and a
WO3 film were both connected with p-GaInP2. For the case of WO3
/GaInP2, the photocurrent of water splitting can achieve 20 μA cm−2 under an
illumination of 1 W cm−2. The device did not work at below 0.2 W cm−2
illumination intensities because of an insufficient potential difference. For the
case of the Fe2O3/GaInP2 tandem device, a very low current density was
observed, even at 10 sun illumination (1 W cm−2). The low photocurrent of
Fe2O3 is the limiting photoelectrode for the two-photoelectrode combination
system due to the low electron mobility, high recombination losses and short
hole diffusion lengths of Fe2O3 [66]. Two years later, Turner’s group found that
the mismatch of the conduction band minimum of the hematite film with the
valence band maximum of p-GaInP2 was the main reason for the low perfor-
mance [67]. In 2015, Jang et al. reported a device that can achieve an STH
efficiency of 0.91%. The Si photocathode was used to connect with a hematite
photoanode in this device. The turn-on photovoltages of the Fe2O3 photoanode
was improved, and finally 0.45 V was obtained due to the improved preparation
strategy, which reduced the surface disorders [68]. The onset potential of the
photoanode is the main challenge to improve the final efficiency of the whole
system at all times. To achieve a standout performance, how to achieve higher
photovoltages generated by the photoanodes may be the primary focus.
 ADVANCES IN PHYSICS: X 871

Table 1. Obtained impressed examples of the PEC/PEC tandem water splitting cells.
Main photoelectrodes
(n-type materials) Connected p-type materials STH efficiency Year References
BiVO4 Cu(In,Ga)Se2 1.01% 2018 [61]
Fe2O3 Si 0.91% 2015 [66]
BiVO4 (Ag,Cu)GaSe2 0.67% 2016 [60]
BiVO4 Si 0.57% 2016 [59]
BiVO4 Cu2O 0.5% 2014 [58]
Fe2O3 Fe2O3 0.11% 2006 [65]
BiVO4 SrTiO3 <0.1% 2012 [69]
BiVO4 Si <0.1% 2014 [70]
BiVO4 (CuGa)1−xZnxS2 <0.1% 2015 [71]

3.3 Current situation of the PEC/PEC cells

Some typical examples of the PEC/PEC cells are shown in Table 1. Fe2O3 and
BiVO4 are widely applied in PEC/PEC system. For the PEC/PEC system, the
band gap of each photoelectrode should cover the O2/H2O or H+/H2 standard
electrode potential and demonstrate an overlay region.
Actually, the PEC/PEC tandem device could theoretically achieve a
maximum STH efficiency of approximately 29.7% [72]. However, in prac-
tical applications, there are many problems that may cause the low effi-
ciency of the whole system. The more the region of the onset potential of
the two photoelectrodes overlap, the higher efficiency could be achieved.
One of the photoelectrodes with a lower photocurrent may limit the
performance of the whole tandem device. The high internal resistance
loss of the PEC/PEC configuration should also be considered as the reason
for the low efficiency. In addition, the electrolyte is difficult to choose when
considering the corrosion and stability problem of both photoelectrodes.
Although the PEC/PEC system has a high theoretical STH efficiency,
realizing large-scale utilization may still be a long way off.

4. PEC/PV tandem cells

There are two main kinds of PEC/PV tandem cells: one is an external device
and the other is an immersed device. One alternative approach is that the
solid-state PV is not directly in contact with the electrolyte but is connected to
the electrolyser through external wiring. This configuration is the external
device. As the PEC absorbers need to be immersed in the electrolyte to form
the semiconductor–electrolyte junction, another alternative configuration
employs a PV cell that is immersed and connected to the photoelectrodes
without external wiring. The immersed device may decrease the cost of the
whole system, but electrolyte stability and light scattering through bubbles
need to be considered [73]. The two kinds of devices have their own advan-
tages and disadvantages, which need further research.
872 Q. CHEN ET AL.

Figure 5. (a) Schematic diagram of the tandem device with the BiVO4 photoanode and Si solar
cell. (b) The intersection point of the J−V curves of the BiVO4 (two-electrode) with either one
of 2-jn a-Si (black) or 1-jn a-Si (red) curves indicates the operating situation of the tandem
device [79].

To establish a photoanode/PV tandem cell, a stable transition metal oxide is

a frequently used material for the photoanode; this photoanode is accompa-
nied by an excellent PV device. These materials have enticed many research
groups to investigate various systems, such as TiO2 photoanodes in tandem
with a thin film PV device based on Cu(In,Ga)Se2/CdS [74] and
Fe2O3 photoanodes in tandem with a-Si:Ge PV [75].

4.1 BiVO4-based PEC/PV tandem cells

With the development of BiVO4 semiconductor materials, BiVO4 has also
frequently been utilized in PEC/PV tandem cells because it has relatively
smaller band gap energy and strong light absorption properties [56,76–78].
In 2013, Krol’s group made a great progress in PEC/PV tandem cell develop-
ment for water splitting. A gradient-doped BiVO4 was combined with a 1-
junction (1-jn) or 2-junction (2-jn) Si solar cell, as shown in Figure 5a. The use
of a gradient dopant concentration in the metal oxide film could solve the
problem of poor charge carrier separation. Consequently, a photocurrent of
4 mA cm−2 was obtained by the tandem cell using a double-junction Si solar
cell, corresponding to an STH efficiency of 4.9%. The expected operation
point of the cell, Jop, was estimated by means of the intersection method, as
shown in Figure 5(Fb) [79]. The intersection method was put forward in 1984
by Weber and coworkers. They predicted the operation conditions by over-
lapping the current-voltage curves of the photoelectrode and PV cell under
actual illumination conditions, as the quantity obtained by the intersection
point must be equal at both interfaces [80]. The point can reveal the ideal
photocurrent (Jop), and the STH efficiency is given by the Jop.
Notably, the curve of the photoanode should be measured by the two-
electrode system to match the practical operation situation, and the solar
 ADVANCES IN PHYSICS: X 873

cell should be placed behind the photoanode to obtain the curve when
overlapping the J–V curves. In 2014, Kamat’s group and Smets’ group
reported BiVO4-based PEC/PV tandem cells with an STH efficiency of
2.5% and 5.2%, respectively [81,82]. A CoPi/BiVO4 photoanode and a
CH3NH3PbI3 solar cell were chosen to constitute an all solution-processed
tandem cell in Kamat’s research, while Smets presented a cell consisting of
a gradient-doped BiVO4 photoanode and a silicon solar cell. Kamat’s work
established a foundation for exploring available photoanode–perovskite PV
combinations. However, a slight decline in photocurrent appeared follow-
ing the initial response, which is attributed to the partial dissolution of the
CoPi catalyst [81,83]. The enhanced performance showed in Smets’
research could be attributed to the increased performance of the
BiVO4 photoanode, as well as better spectral matching between the
BiVO4 photoanode and the silicon solar cell [82].
In 2015 and 2016, Kim et al. reported two studies regarding tandem cells
based on the BiVO4 photoanode and different PV materials, and two
different architectures were presented [84,85]. A CH3NH3PbI3 perovskite
single junction solar cell and parallel-connected Si solar cells were applied
into the tandem system. In the former work, dual-doped BiVO4 with a
cobalt carbonate (Co–Ci) catalyst was fabricated as the photoanode material.
The Co–Ci catalysts were compared with the frequently used cobalt phos-
phate (Co–Pi) catalysts; similar photocurrents were obtained but the Co–Ci
catalysts realized an increase in the stability. This research provided a
solution for the previously mentioned Co–Pi catalysts dissolution problem.
BiVO4 was combined with the perovskite solar cell in a well-designed
tandem artificial-leaf-type device, and eventually an STH efficiency of 4.3%
was produced [84]. In 2016, Kim et al. designed an unassisted solar water
splitting system consisting of hetero-type dual photoanodes and parallel-
connected Si solar cells, as shown in Figure 6. The modified BiVO4 and

Figure 6. (a) Scheme of an unassisted solar water splitting tandem cell with a hetero-type
dual photoelectrode (BiVO4||Fe2O3) and parallel-positioned Si solar cells. (b) Practical picture of
the monolithic tandem cell in operation under the illumination of real sunlight [85].
874 Q. CHEN ET AL.

Figure 7. Schematic illustration of the tandem device with the embedded structured WO3/
BiVO4 photoanode [86].

α-Fe2O3 electrodes were chosen to consist of dual photoelectrodes, which

were connected in parallel for extended light harvesting, and visible light up
to 610 nm can be utilized.
The tandem cell showed an excellent STH efficiency of 7.7%. The hetero-
type dual photoanodes were regarded as a new strategy for unassisted water
splitting and supported the blueprint of the tandem cells composed of the
dual photoanodes. This work could facilitate the process of reaching an STH
efficiency of above 10% for practical applications by further reducing the
onset potential of the hetero-type dual photoanodes because the saturated
photocurrent is already over 8.3 mA cm−2. For portion of Fe2O3, increasing
the bulk charge separation efficiency could be eventually beneficial for the
performance of the whole tandem cell [85].
Park’s group also published an article regarding progress in WO3
/BiVO4 heterojunction-based tandem devices in 2015. After coating the
mesoporous WO3 nanoparticle network with a thin BiVO4 layer, a larger
contact area between the two components were provided and the electron
transport ability was well maintained. This kind of structure is called a
core/shell structure and can be applied to other photoelectrode systems.
Combined with a single dye-sensitized solar cell (DSSC), as shown in
Figure 7, the WO3/BiVO4 heterojunction-based tandem devices showed
an extraordinarily STH efficiency of 5.7% [86].
Based on former work, Park’s group increased the STH efficiency to 7.1%,
as shown in Figure 8. To overcome the contradiction between high transpar-
ency and high photocurrent density of the front photoelectrode in a tandem
device, a photon-recycling hybrid conductive distributed Bragg reflector
 ADVANCES IN PHYSICS: X 875

Figure 8. Schematic diagram of the tandem cell with the photon-recycling hybrid cDBRs [87].

(cDBR) on the back side of the transparent conducting substrate was incor-
porated. The cDBR structure reflects short wavelength light (λ < 500 nm) for
enhancing photocurrent generation of the front photoelectrochemical elec-
trode, while transmitting longer-wavelength light (λ > 500 nm) for the rear
solar cell. The hybrid cDBR can serve as not only as an optical filter but also as
a counter electrode for the solar cell. The eventually an STH efficiency of 7.1%
with no external potential reveals a great step towards an STH efficiency above
10% for commercialization [87].

4.2 Cu2O-based PEC/PV tandem cells

A variety of studies regarding other photoanode or photocathode materials

with various photovoltaic cells have been applied in tandem devices. For
example, in 2015, Dias et al. turned their attention to a photocathode/PV
system. A tandem cell for water splitting was constructed using a
Cu2O photocathode and a hybrid perovskite photovoltaic, as shown in
Figure 9. In this tandem configuration, the flat anode electrode was positioned
parallel to the path of light. The problem of the counter electrode areas was
mentioned, which may be increased, as long as its placement is out of the
illumination path in the tandem configuration. In addition, the increased area
means more abundant and desirable employed catalyst materials. The final
876 Q. CHEN ET AL.

Figure 9. Schematic illustration of the Cu2O–perovskite–IrO2 tandem cell [88].

tandem cell using a Cu2O photocathode with a hybrid perovskite photovoltaic

achieved an STH efficiency of 2.5%. The performance could be enhanced in
the future by the development of the Cu2O materials [88].

4.3 Fe2O3-based PEC/PV tandem cells

In addition to BiVO4, another popular photoanode material used in
tandem cells is hematite due to its favourable band gap (~2.1 eV),
good stability, abundance, nontoxicity and economic viability [89,90].
In 2010, Brillet et al. combined a Fe2O3 photoanode with dye-sensi-
tized solar cells. Three possible architectures for constructing the
tandem cell were demonstrated: two side-by-side dye cells behind a
Fe2O3 photoanode, two side-by-side dye-sensitized solar cells (DSCs)
in front of the Fe2O3, and a trilevel Fe2O3/DSC/DSC architecture. The
highest expected STH efficiency of 1.36% was obtained by the trilevel
tandem architecture. The trilevel architectures can harvest more
photons and decrease the photon energy loss [91]. This architecture
of the photovoltaic cell behind the photoelectrode has been commonly
adopted by researchers as the prepositive photoelectrode can capture
more photons to reach higher photocurrents.
In 2015, Gurudayal et al. demonstrated a stable and simple water splitting
tandem cell by combining a Mn-doped Fe2O3 photoanode with a single
perovskite solar cell, and finally realized an overall unassisted water splitting
with an STH efficiency of 2.4%. The performance of the tandem system
could be limited by the low photocurrents generated by the photoanode(the
 ADVANCES IN PHYSICS: X 877

Figure 10. Illustration of an IMM photocathode configured for water splitting [73].

thin Fe2O3); thus, the indicated operating situation of the system is far below
the maximum performance of the solar cell [92].
In 2017, Gurudayal et al. improved the fabrication of hematite, and then
combined it with a CH3NH3PbI3 perovskite solar cell to form a tandem
cell. The STH efficiency of the device was 3.4% for overall unassisted water
splitting. The preparation of Fe2O3 was based on an atomic layer deposi-
tion treatment approach. Because of an enhancement in the technology,
the performance of the photoanode was also enhanced, which brings the
increased STH efficiency of the whole tandem device [93].

4.4 Immersed configuration for the PEC/PV tandem cells

In addition to the aforementioned external device, there are other exam-

ples of the immersed device. The most impressive photoelectrode/PV
device is an integrated design developed by Turner in 1998 with a GaAs
p–n junction connected to a GaInP2 photocathode [9]. Even though the
hydrogen production efficiency of this system could reach 12.4%, the
GaInP2 photocathode quickly corroded when in contact with the aqueous
electrolyte [10]. In addition, the chosen materials are expensive and poi-
sonous and are not suitable for large-scale applications.
Another immersed configuration was demonstrated by Deutsch’s group
in 2017 by using a buried p–n junction. With GaInP/GaInAs tandem
absorbers, an STH efficiency of over 16% was obtained. Photons with
energies higher than 1.8 eV are absorbed by GaInP, while those less than
878 Q. CHEN ET AL.

Table 2. Obtained impressed examples of the PEC/PV tandem water splitting cells.
Main PV cells Connected photoelectrodes STH efficiency Year References
GaInAs GaInP 16.2% 2017 [73]
Si Cell BiVO4||Fe2O3* 7.7% 2016 [85]
DSSC WO3/BiVO4# 7.1% 2016 [87]
DSSC WO3/BiVO4# 5.7% 2015 [86]
Si Cell BiVO4 5.2% 2014 [82]
Si Cell BiVO4 4.9% 2013 [79]
CH3NH3PbI3 BiVO4 4.3% 2015 [84]
CH3NH3PbI3 Fe2O3 3.4% 2017 [93]
Hybrid Perovskite Cu2O 2.5% 2015 [88]
CH3NH3PbI3 BiVO4 2.5% 2015 [81]
CH3NH3PbI3 Fe2O3 2.4% 2015 [92]
DSSC Fe2O3 1.36% 2010 [91]
* Hetero-type dual photoelectrode BiVO4||Fe2O3
# Heterojunction WO3/BiVO4

1.8 eV pass through to the bottom GaInAs junction, as shown in Figure 10.
When the device is illuminated, photogenerated electron and hole pairs
appear. Then, electrons in the conduction band of GaInP are transferred to
the electrolyte to produce H2, while the holes in the GaInAs valence band
are transferred through the Au back contact and a wire to a metal counter
electrode to produce O2. The GaInP and GaInAs are connected in series
through the transparent tunnel junction where holes in the valence band of
GaInP can recombine with electrons in the conduction band of GaInAs.
The immersed devices could minimize external wiring, which may lead to
lower-cost tandem device, because other solid-state solar cells are not
immersed and must be connected to the electrolyser through external
wiring. The device with GaInP/GaInAs tandem absorbers is called an
inverted metamorphic multi-junction (IMM) device. A flexible platform
then can be provided for realizing tandem band gap combinations to reach
higher a STH efficiency [73].

4.4 Current situation of the PEC/PV tandem cells

Table 2 shows several typical examples of PEC/PV tandem cells.
Compared to the PEC/PEC system, the choices of the photoelectrode
materials and the PV cells are more flexible. Although the best design for
unassisted solar water splitting is uncertain, the potential space for the
development of PEC/PV tandem cells is wide, and to date a fairish
efficiency for unassisted solar water splitting is easier to reach. The limita-
tion lies in the photocurrent of the sand-alone semiconductor material,
and the cost for the large-scale application of the PV cells should also be
considered. In summary, this system has relatively vast potential for future
development.
 ADVANCES IN PHYSICS: X 879

5. Conclusion and outlook

Here, the motivation and practical applied examples for the PEC water-
splitting tandem cell were illustrated. Using a single semiconductor
material, it is difficult to realize highly efficient unassisted overall water
splitting. Researchers must turn their attention to PEC-based tandem
cells. The high conversion efficiency for water splitting is proportional
to the photocurrent of the whole system, and the photocurrent can be
optimized by the appropriate selection of semiconductor materials and
optimized configuration.
For the PEC/PEC tandem system, the fabrication cost is relatively low, while
the poor energy conversion efficiency restrains the commercial application of
the PEC/PEC tandem system. Compared to the PEC/PV system, the PEC/PEC
configuration does not have complex electrical connections. However, the limit
of the tandem PEC system is the restrictive matching of the band gap between
two semiconductors. The stable and large photocurrents of the photoelectrode
materials are urgent needs for the future. In addition, the onset potentials of the
two photoelectrodes should have more overlay areas, and enhancing the onset
potentials of photoanodes is more urgent at present.
On one hand, to increase the efficiency of the PEC/PEC system, more
studies should be carried out to improve the existing photoanode perfor-
mance, and we should pay more attention to the onset potential and
improving the photocurrent at a low external bias. On the other hand,
new photoanodes with suitable band gaps and band edge potentials are
required. With the rapid development of computational capabilities and
theoretical methods, computational screening of possible photoanodes is a
promising solution towards finding new materials [94].
For the PEC/PV system, the efficiency is relatively high, but the drawback of
PEC/PV system is the high cost. However, this system is more flexible when
choosing the photoelectrode materials and the PV cells. However, with the rapid
declining costs of the PV cells, the PEC/PV system is a competitive candidate for
the future commercial application of water splitting. Specifically, the recent
organic–inorganic perovskite solar cell offers low-cost, easy-fabrication solar
energy utilization solutions. In addition, the replacement of noble metals with
earth abundant elements in the PEC/PV system is another important issue, and
many strategies, such as the alloys of noble metals, are promising solutions for
reducing noble metal consumption. Up to now, it is easier to obtain a higher
efficiency using the PEC/PV system.
Long-term durability, low cost and high performance are prerequisites for a
practical water-splitting tandem cell. The durability of PEC cells may be
prompted by the conformal coating of protective layers, which can isolate the
photoelectrodes from the electrolytes [3,95]. From the viewpoint of cost, per-
ovskite solar cells may be a candidate PV for tandem cells because of their high
880 Q. CHEN ET AL.

performance and low cost. From the viewpoint of performance, photoanodes

with a more negative onset potential for water oxidation and photocathodes
with a more positive onset potential for water reduction should be considered,
and the interface between the photoanode surface and the electrolyte deserves
more attention [96]. To decrease the onset potential of the photoanodes,
improving the preparation method and employing more effective catalysts
may be useful. In addition, applying new materials can bring hope to tandem
cell. A Cu2ZnSnS4 photocathode has been recently reported for its excellent
performance. A stable photocurrent density of 11.1 mA cm−2 at 0 VRHE has been
obtained. Cu2ZnSnS4 may be a very promising absorber for solar driven photo-
voltaics and water splitting applications [97].
The most important aspects in the future are to continue the research for
improving the performance of existing materials [98] and to find new materials,
coupled with an optimized configuration. Lastly, it is reasonable to believe that
an efficient, inexpensive and stable tandem device for the unassisted overall
water splitting will someday be realized.

Disclosure statement
No potential conflict of interest was reported by the authors.

Funding
This work was supported by National Key Research and Development Program of China
[No 2018YFA0209303], National Natural Science Foundation of China [U1663228 and
21473090] and a Project Funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions.

ORCID
Zhaosheng Li http://orcid.org/0000-0001-8114-0432

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