REVIEWS

Semiconducting materials for

photoelectrochemical energy
conversion
Kevin Sivula1 and Roel van de Krol2
Abstract | To achieve a sustainable society with an energy mix primarily based on solar energy,
we need methods of storing energy from sunlight as chemical fuels. Photoelectrochemical (PEC)
devices offer the promise of solar fuel production through artificial photosynthesis. Although
the idea of a carbon-neutral energy economy powered by such artificial leaves is intriguing,
viable PEC energy conversion on a global scale requires the development of devices that are
highly efficient, stable and simple in design. In this Review, recently developed semiconductor
materials for the direct conversion of light into fuels are scrutinized with respect to their atomic
constitution, electronic structure and potential for practical performance as photoelectrodes in
PEC cells. The processes of light absorption, charge separation and transport, and suitable
energetics for energy conversion in PEC devices are emphasized. Both the advantageous and
unfavourable aspects of multinary oxides, oxynitrides, chalcogenides, classic semiconductors
and carbon-based semiconductors are critically considered on the basis of their experimentally
demonstrated performance and predicted properties.

1
Institut des Sciences et
Ingnierie Chimiques, cole
Polytechnique Fdrale de
Lausanne (EPFL), Station 6,
1015 Lausanne, Switzerland.
2
Helmholtz-Zentrum Berlin fr
Materialien und Energie
GmbH, Institute for Solar
Fuels, Hahn-Meitner-Platz 1,
14109 Berlin, Germany.
Correspondence to K.S.
kevin.sivula@epfl.ch
Article number: 15010
doi:10.1038/natrevmats.2015.10
Published online 20 Jan 2016
Engineering artificial photosynthetic systems to afford
the efficient and economical conversion of abundant
solar energy into chemical fuel on a scale in accordance
with global energy demand (tens of terawatts) is an
important step towards the realization of a sustainable
carbon-neutral society 1. At the heart of any system for
harvesting solar energy is the semiconductor material,
which transforms absorbed solar photons into excited
electronic states (both electrons and holes). Oppositely
charged excited states can be separated to generate an
electronic potential (that is, a photopotential) suita-
ble to drive the electrochemical production of simple
fuels, such as molecular hydrogen from the reduction of
water or methanol from the reduction of carbon dioxide.
Hydrogen production can be accomplished in a straight-
forward manner using traditional photovoltaic devices
together with standard electrolysers (splitting water into
H2 and O2). However, this route is not economically
competitive with traditional methods using fossil fuels
(for example, the steam reforming of natural gas or coal
gasification). Although cost estimates vary, hydrogen
produced from fossil fuels is less expensive (by a fac-
tor of two to five) than using photovoltaics combined
with electrolysis24. Thus, the development of alterna-
tive, economically competitive strategies to produce
solar fuels is of strong interest. Semiconductor-based
solar fuel production can also be accomplished with a
photoelectrochemical (PEC) device, which contains
a direct-semiconductor/liquid interface5. However, to
enable practical PEC solar fuel production, low-cost,
robust and high-performance semiconductor materials
are needed. The past 5years have seen a surge in the
development of promising semiconductor materials,
owing, in part, to the rational engineering of classic
semiconducting materials.
In this Review, we aim to give readers a brief overview
of the basics of PEC technology while focusing on the
light-harvesting materials. We present a critical analy-
sis of both the advantageous and detrimental aspects of
classic and recently developed semiconductors for direct
solar fuel production to give insight into the potential for
viable performance in PEC cells. Advances with ternary
oxide semiconductors beyond the well-known binary
transition metal oxides are examined in the context of
their optoelectronic properties and intrinsic stability.
Tuning the optoelectronics by adding nitrogen yields
oxynitrides, a new and emerging class of PEC materi-
als. Replacing the oxygen atom with a chalcogen (S or
Se) can offer improved light absorption, and suitable
charge transport can be achieved using transition-metal
dichalcogenides and multinary compounds, such as
CZTS (copper zinc tin sulfide, Cu2ZnSnS4) and CIGS

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a e b
Photoanode Membrane Photocathode
CB WRC CB
H2 e

C
EQF R
0 EH+/H2
e H+
Eg,2
e 1.23 V e
EF
+1
EH2O/O2
Eg,1 H2O h+
O
A
+2 EQF
H+
O2
h+
E(VRHE)
VB WOC VB
Photocathode
Membrane
Photoanode
Nature Reviews | Materials

Figure 1 | Photoelectrochemical cell basics. a | Schematic of a wired-type tandem cell for water splitting with incident
solar illumination striking the photoanode and transmitting to the photocathode. b|Working principle of the tandem
cell for water splitting using a photoanode with bandgap energy Eg,1, and a photocathode with Eg,2 (where Eg,1 > Eg,2).
Briefly, on absorption of a solar photon, an electron (e) from the valence band (VB) is promoted to the conduction band
(CB) leaving the corresponding electron hole (h+). The electric field in the depletion layer physically separates these
charges and, in the photocathode, the electrons in the CB drift to the semiconductorliquid junction, increasing the
quasi-Fermi energy of the cathode, ECQF, to drive the reduction of H+ to H2 at a water reduction catalysis (WRC) site.
Analogously, in the photoanode, electron holes in the VB drift to the semiconductorliquid junction, increasing the
photoanodes quasi-Fermi energy, EAQF, sufficiently to surmount the overpotential for oxidation (O) and oxidize water to
O2 at a water oxidation catalysis (WOC) site. Photogenerated electrons in the CB of the photoanode travel through the
external circuit to recombine with the holes in the VB of the photocathode. EF, Fermi energy; E(VRHE), electronic potential
with respect to the reversible hydrogen electrode; R, overpotential for reduction.

(copper indium gallium selenide, CuIn xGa(1x)Se2).
These materials, as well as the traditional high-perfor-
mance semiconductors used in photovoltaic devices, are
typically not stable in a direct-semiconductor/electrolyte
junction configuration but can be encapsulated and opti-
mized for high-performance PEC application. The recent
emergence of carbon- and carbon-nitride-based semi-
conductors for the direct PEC splitting of water is also
discussed. In the final section, based on the development
of the above-mentioned materials, we present a realistic
outlook on device performance in terms of the goal of
cost-effective PEC solar-to-chemical energy conversion.
Solar-to-chemical using semiconductors
PEC solar fuel production conceivably offers a more
straightforward route towards renewable solar-to-
chemical energy conversion compared with conven-
tional photovoltaic technology coupled with standard
devices that produce electrochemical fuel (for example,
electrolysers)6. This is partly because of the simplicity of
the PEC device, which requires only a few elements to
integrate the light-absorbing and electrocatalytic func-
tions. Similar to a traditional electrochemical device,
a PEC cell requires two electrodes (an anode for the
oxidation reaction and a cathode for the reduction
reaction) and a membrane to separate the products
of the two half-cell reactions. However, in contrast to
electrolysis, in a PEC cell, at least one of the electrodes
is a semiconductor, which absorbs solar photons with
energy greater than the semiconductor bandgap energy,
Eg. The photopotential generated by the subsequent sep-
aration of the photogenerated charges can directly drive
an electrochemical solar-fuel-production reaction.
Although it is possible to envisage a PEC cell with
one semiconductor photoelectrode and one standard
metallic (dark) electrode, identifying a single semicon-
ductor material that can both develop sufficient pho-
topotential for solar fuel production (approximately
1.51.8 V for water splitting) and also harvest a signif-
icant portion of the solar spectrum is an ongoing and
difficult challenge. However, because semiconductors
can also transmit photons with energy less than their
Eg, a PEC cell can be constructed with semiconductors
used for both electrodes (that is, an n-type photoanode
and a p-type photocathode) in a tandem configuration
to increase both the photopotential and the amount of
light harvested by the device7.
Many distinct tandem cell configurations are possi-
ble and have been discussed recently8. A schematic is
presented in FIG.1a of a common and representative
example, in which a large-bandgap photoanode absorbs
the high-energy portion of the incoming solar irradia-
tion and transmits the remainder to the photocathode.
The two photoelectrodes are electrically connected by

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an external wire in the wired type of device shown in
FIG.1a, and an electrolyte fills the cavity between the
two photoelectrodes. This configuration is preferred
over wireless cell designs (in which the photoanode
and photocathode are directly adjoined back-to-back),
as it minimizes the distance for ions to travel in the
(electronically more resistive) electrolyte9.
A defining characteristic of a PEC cell is the direct
interface between the semiconductor (or semiconduc-
tors) and the liquid electrolyte. At the semiconductor
liquid junction (SCLJ), the equilibration of the chemical
potential of the electrons in the semiconductor (that is,
the Fermi level, EF) and the oxidationreduction poten-
tial in the electrolyte causes the transfer of electrons
across the SCLJ. Ideally, this process results in a PEC
diode7 owing to the Schottky-type electronic junction
formed as a result of the development of a region in the
semiconductor that is depleted of free charge carriers. In
this depletion layer, only fixed, ionized donor or accep-
tor ions remain, forming a space charge, which gener-
ates an electric field10. This manifests in the upward
bending of the conduction and valence energy bands
at the SCLJ in the n-type photoanode and downward
bending of the bands in the p-type photocathode. The
electrochemistry is depicted schematically in FIG.1b, in
which a cross-section of the PEC tandem cell is shown.
The electronic potential is defined in volts with respect
to the reversible hydrogen electrode, VRHE, where, at pH
0, electrons at 0 VRHE have an energy of 4.5eV relative
to vacuum. The electric field that is present in the deple-
tion layer owing to the Schottky-type junction is crucial
for charge separation and the operating principle of the
PEC cell (see the FIG.1 legend for further details).
For the common case of solar water splitting (as
shown in FIG.1b), protons, H+, in the electrolyte are
reduced to H2 at the photocathode effectively storing
the energy of the photons as hydrogen fuel. For carbon
dioxide, the catalytic reduction of CO2 to CO, HCO2
or CH3OH is possible11. In both cases, a corresponding
oxidation reaction must occur. Most conveniently, this
is the oxidation of water the planets most abundant
electron donor which results in the formation of O2
at the photoanode. When the solar fuel is later used
in a fuel cell or in a combustion process, this O2 will
be consumed to reform H2O or CO2 and complete the
cycle. The electrochemical reactions at the photoanode
and photocathode are generally complex, multistep,
proton-coupled electron transfer processes, which phys-
ically transpire on catalytic surface sites at the SCLJ (at
the water oxidation catalysis and water reduction catal-
ysis sites indicated in FIG.1b). These sites can originate
from the surface of the semiconductor itself or from
catalysts deposited to reduce the kinetic overpotential
for oxidation (O) or reduction reactions (R). Complete
solar-to-fuel conversion can be achieved if the total
photopotential developed by the PEC cell (defined as
the potential difference between the quasi-Fermi energy
of the holes in the photoanode, EAQF, and of the electrons
in the photocathode, ECQF) is greater than the difference
between the redox levels of the oxidation and reduc-
tion reaction (1.23 V at 20 C for water splitting) plus
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the kinetic overpotentials, O and R, and any resistive
(ohmic) losses that may occur in the system. Because
the electrochemical reactions occur directly at the semi-
conductor surfaces, the current densities in PEC cells
are about two orders of magnitude smaller than those in
commercial electrolyser systems (that is, 1020 mA cm2
compared with 12 A cm2). This greatly reduces the
requirement for very high catalytic activity and may even
allow the use of low-cost, Earth-abundant catalysts in
acidic environments; the development of these for water
oxidation represents a major ongoing challenge12.
Reasonable theoretical limits to the performance of
a single photoelectrode or a photoanodephotocathode
tandem cell configuration for solar hydrogen produc-
tion by water splitting were first estimated by Bolton13.
These studies suggest that solar-to-hydrogen (STH)
energy conversion efficiencies of more than 20% are
feasible using semiconductor bandgaps of approxi-
mately 1.7 and 1.2 eV for the first and second absorbers,
respectively, even with realistic assumptions regard-
ing unavoidable losses14,15. Use of a single electrode or
placement of two photoelectrodes side by side (instead
of in tandem) are feasible approaches but lead to lower
maximum theoretical STH efficiencies (11% and 14%,
respectively). A techno-economic analysis suggests that
the cost of hydrogen produced using the PEC-cell con-
cept could be competitive with that produced from fos-
sil fuels (even after considering the added engineering
problems of electrolyte and gas handling) if a PEC cell
with a STH efficiency of 15% could be developed with
a device lifetime of 10years and a cost of less than US
$200 per square metre of device (including the semi-
conductors, substrates, housing and membranes) 16.
Although the development of PEC technology remains
at an early stage and the ultimate economic viability
remains unknown and dependent on the performance
of the materials developed, in a recent report it is spec-
ulated that PEC technology could be competitive with
photovoltaics combined with electrolysis3.
Material requirements
Although the simple device structure and operation
of the PEC tandem cell is advantageous in terms of
economic viability, this places constraints on the semi-
conductor materials used. In addition to the bandgap
requirements for high conversion efficiency, the photo-
electrodes must consist of widely available and low-cost
component atoms, be inexpensive to fabricate into their
final form and importantly be robust enough to
withstand continuous and long-term PEC operation in
the presence of water and oxygen. The classic binary
transition-metal-oxide semiconductor photoelectrodes,
such as TiO2 (Eg = 3.03.2 eV) and WO3 (Eg = 2.7 eV),
are easy to prepare and are remarkably stable under
PEC operation. Accordingly, these materials have gar-
nered an enormous amount of attention for decades17,18.
However, the bandgaps of these classic oxides are too
large to absorb a sufficient fraction of the available solar
spectrum. By contrast, STH efficiencies of more than
10% under standard conditions have been demonstrated
with devices based on high-efficiency photovoltaic
 Box 1 | Photocurrent density and conversion efficiency as device performance metrics

a Measurement of photocurrent density b Measurement of quantum eciency c Measurement of solar-to-chemical eciency

Potentiostat Potentiostat Ammeter
H2
O2

Reference
electrode

Counter
electrode

Photoanode Photocathode

100
Illuminated E3app Light on
Dark E2app

JOP
E1app
Current density ( J)

J(Eapp)
IPCE or APCE (%)

Total current passed

Total gas evolved

H2
0
O2
on
EH2O/O2
Eapp
Eon

0
0
Potential, E Photon wavelength, Time

For PEC devices, different performance metrics are used to assess
solar-to-fuel energy conversion. The most common method (panel a in
the figure) is to measure the photocurrent density, Jph, produced by a
photoelectrode in an electrolyte as a function of the applied potential,
E, using a potentiostat. The potential E is reported relative to a reference
electrode, and the current flows between the photoelectrode and the
counter-electrode during testing. The onset potential, Eon, for the
photocurrent can be defined from the plot, and Jph at a particular applied
potential (Eapp) can be used to calculate the applied-bias photon-to-current
which photon energies contribute to the solar photocurrent. These
metrics are measured at a fixed applied potential, E1app (panel b in the
figure) by varying the wavelength, , of the monochromatic incident
illumination. The photocurrent density Jph is measured at each wave-
length, and from the respective incident power density, P, the IPCE
is calculated as follows:
hc
IPCE = Jph, P e (2)

efficiency (ABPCE)163. Assuming PEC water splitting and a photoanode for
water oxidation
Jph (EH2O/O2 Eapp)
ABPCE =
Pin
where EH2O/O2 is the standard potential for water oxidation (+1.23 V versus
the reversible hydrogen electrode, VRHE) and Pin is the incident
illumination power density. Note that the chemical products are not
directly measured. When the photoelectrode is at a specific Eapp, called
the flat-band potential (EFB), the applied potential cancels the
band-bending in the space-charge layer. The bands of the semiconductor
thus become flat, indicating that there is no longer an electric field
present to assist with the separation of the photogenerated electrons
and holes. Determining EFB is useful for estimating the positions of the
conduction and valence bands with respect to the redox energy levels
in the electrolyte, which, in turn, allows estimation of the maximum
photovoltage and photocurrent onset potential (Eon) that can be
produced by the junction. Ideally, EFB = Eon; however, the kinetic over-
potentials typically make this a poor estimation. Thus, EFB is usually
measured using other techniques such as electrochemical impedance
spectroscopy164 or electroreflectance.
Quantum-efficiency metrics, such as the incident (or absorbed)
photon-to-current efficiency, IPCE (or APCE), are useful for determining
where hc/e is equal to 1,240 Vnm. The APCE can be determined by
simply dividing the IPCE by the fraction of photons absorbed by the
photoelectrode at each wavelength. The IPCE plot shows how the IPCE
(1) can vary with Eapp. The onset wavelength, on, is closely related to the
semiconductor bandgap, and we note that the IPCE multiplied by the
spectral distribution of standard solar illumination (AM 1.5G,
100 mW cm2) can be integrated to give an estimate of the expected Jph
under solar illumination.
Reliable measurements of the true solar-to-chemical conversion
efficiency cannot be made in a three-electrode configuration, but instead
require a two-electrode configuration, as shown in panel c of the figure
(note that for every H2 molecule, two electrons flow in the external
circuit). Measuring the operating photocurrent density, Jop, with an
ammeter as a function of time gives an indication of the stability of the
device. The integrated Jop gives the total charge passed, which can be
compared with the total amount of gas evolved (accounting for the
reaction stoichiometry) to give the faradaic efficiency, F. For the
water-splitting reaction, the overall solar-to-hydrogen conversion
efficiency (STH) is calculated as
F (3)
STH = Jop (1.23 V)
Pin
where 1.23 V corresponds to the Gibbs free energy (G) of the reaction.

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 a
2 Ti 4p
O 2p Ca 5s Bi 6p
Nb 5p Fe 4p Ta 6p La 4f
O 2p O 2p* O 2p Conduction
Bi 6p Zn 4s O 2p O 2p O 2p O 2p* band
1
W 6p W 6p W 6p O 2p*
O 2p O 2p O 2p Fe 3d Cu 3d Ta 5d
Nb 5d Fe 3d Ti 3d
Ti 3d
V 3d Fe 3d
Potential (VRHE)

0 Fe 3d EH+/H2
W 5d W 5d
3.2 eV

2.8 eV

2.0 eV

2.4 eV

2.1 eV

2.0 eV

1.9 eV

1.8 eV

2.0 eV

1.5 eV

2.4 eV

2.0 eV
+1
EH2O/O2
Cu 3d
Fe 3d
Bi 6s Cu3d
+2
Fe 3d N 2p N 2p
Fe 3d
Bi 6s Cu 3d O 2p Valence
+3 O 2p O 2p O 2p band

O 2p O 2p O 2p O 2p O 2p O 2p O 2p O 2p

TiO2 WO3 Fe2O3 BiVO4 CuWO4 ZnFe2O4 CaFe2O4 CuBi2O4 CuNbO4 CuFeO2 TaON LaTiO2N

b BiVO4 c CuFeO2 d LaTiO2N

Figure 2 | Bandgap structure and selected crystal structures of oxide and oxynitride semiconductors for PEC
applications. a|Contribution of metal cation and oxygen anion states to the conduction and valence bands. The bandgap
energy (red for n-type, black for p-type) is shown with respect to the reversible hydrogen electrode and the water redox
energy levels (assuming Nernstian behaviour for the band-edge energies with respect to electrolyte pH). b|Crystal
structure of the monoclinic scheelite polymorph of BiVO4. Here, the blue Bi3+ cations are coordinated to the red oxygen
anions of the VO43 tetrahedra (in a pentagonal bipyramidal structure). c|Delafossite crystal structure of CuFeO2 showing
the light blue Cu+ cations forming layers between face-sharing FeO6 octahedra. d|LaTiO2N adopts a triclinic perovskite
structure where the large La cations (green) occupy the A site between two distinct types of Ti(O4N2) octahedra.

materials (for example, IIIV semiconductors, such as
GaAs and GaInP)19. However, because these materials
corrode or oxidize when they are in direct contact with
an aqueous electrode, greater complexity is required.
Typically, thin and conformal overlayers of stable
oxides such as TiO2 are deposited by atomic layer depo-
sition to bury the junction and protect the unstable sem-
iconductor. Alternatively, the semiconductor junction
can be completely removed from the harsh conditions
of direct contact with the aqueous electrolyte and placed
outside the liquid cell2023. However, as these devices do
not derive an electronhole charge-separating junction
from the direct semiconductorliquid contact, they
are termed photovoltaic-biased electrosynthetic cells
or integrated photovoltaicelectrolysis cells (REF.24).
Although the development of these devices drives inno-
vation in PEC-cell design, the complexity and cost of
these devices25 make scaling up to the required mag-
nitude very difficult. As a result, achieving solar fuel
production at a cost significantly less than (or even
equivalent to) photovoltaics combined with electrolysis
will be challenging 26. Indeed, an analogy with technol-
ogy for solar electricity production can be drawn here:
the most prolific photovoltaic technology is not based
on the devices with the highest performance, as these
are far too expensive. Thus, a clear challenge on the way

NATURE REVIEWS | MATERIALS VOLUME 1 | FEBRUARY 2016 | 5

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 to economically viable PEC solar fuel production is to
develop inexpensive semiconductor materials that can
deliver high solar-to-fuel conversion efficiency with
a direct SCLJ while operating stably on a timescale of
years. It is likely that the viability of PEC technology rests
on meeting this challenge.
In the next section of this Review, we address recent
advances in the development of semiconducting PEC
materials. Although other aspects (for example, the
membrane27, and the oxidation and reduction catalysts12)
are also important factors that determine the conversion
efficiency and the longevity of a PEC cell, these are not
emphasized here. Systems engineering, including gas
and liquid handling equipment, which is critical for the
overall PEC solar fuel production and costs16, is also not
considered further. In addition, it is important to note
that although a complete PEC cell for solar fuel produc-
tion is likely to use a photoanode and a photocathode, the
development of photoelectrode materials in the labora-
tory does not necessitate the construction of a complete
PEC cell. Typically, a single electrode material is meas-
ured, and its performance is quantified by the standard
techniques described in BOX1.
Emerging PEC semiconductor materials
Beyond binary oxides. The field of PEC solar fuel pro-
duction began with the observation28,29 of water photo-
oxidation on semiconducting TiO2. Semiconducting
transition metal oxides are attractive photoanodes for
water oxidation, as the relatively high electronegativity
of oxygen results in the formation of stable compounds
based on O2 anions. As photoanodes transfer photo-
generated holes from their valence band to oxidize water,
understanding and controlling the valence-band level is
of interest.
The main factor leading to differences in the valence-
band energy in oxides is the occupancy of the metal
d band 30. Transition metal oxides based on empty
dbands (that is, with d 0 cations such as Ti4+, V5+, Nb5+
and W6+) have valence-band energy levels dictated
strongly by the O 2p levels (for example, TiO2, as shown
in FIG.2a), making the valence band low in energy and
stable towards oxidation under PEC operation. Their
high ionic character ensures a large separation between
the band edges, and typically these materials possess
bandgaps that are too large for efficient solar energy har-
vesting. A vast amount of effort has centred on trying to
overcome this challenge for the classic d 0 oxides (TiO2
and WO3) by increasing light absorption through dop-
ing or adding mid-gap defect states (for example, oxygen
deficiencies). As the energy levels formed by the dopants
or impurities are spatially isolated at typical dopant sol-
ubility limits (12% for metal oxides), the transport of
the photogenerated holes to the SCLJ will be slow, and
high rates of recombination are inevitable. Thus, these
efforts have not been particularly successful at creating
highly active PEC photoanodes.
Oxides based on transition-metal cations with dn elec-
tronic configurations often have smaller bandgaps and
good chemical stability. Examples are Fe2O3 and Co3O4,
the bandgaps of which (2.1 and 1.3 eV, respectively)
6 | FEBRUARY 2016 | VOLUME 1
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are strongly influenced by dd transitions. However,
carrier transport and photogenerated charge separa-
tion are problematic in this class of oxides because of
the low polaron conductivity 30. Considerable effort has
been focused on Fe2O3 in particular, given its favourable
abundance and stability in basic electrolytes. Solar water
oxidation photocurrents up to approximately 4 mA cm2
have been achieved for Fe2O3 (REFS31,32), but this is con-
siderably lower than the theoretical maximum photo-
current of 12 mA cm2 at standard irradiation of 1 sun
(100 mW cm2 at AM 1.5G). The poor semiconducting
properties of Fe2O3 render the efficient extraction of
photogenerated charges an unsolved and ongoing chal-
lenge33. The limitations of binary oxides have prompted
focus to shift recently to ternary and more complex mul-
tinary oxides. With ~50 candidate metals in the peri-
odic table, there are about 19,000 possible ternary metal
oxides, and more than 220,000 quaternary oxides34.
Clearly, a strategy is needed to identify promising can-
didates. Rationally engineering the bandgap in a ternary
or multinary oxide through the judicious combination
of metal cations is one possibility. Indeed, in many cases,
the bandgaps of complex oxides can be predicted by a
stoichiometrically weighted addition of the bandgaps
of the parent binary oxides35,36. Although this simple
approximation can often be used to rationalize the
experimental results, the added complexity stemming
from crystal-field splitting, electronelectron repulsion
and JahnTeller effects typically leads to significant
deviations. Sophisticated computational methods allow
more precise predictions for promising oxide systems37;
however, these approaches still suffer from limitations
in accurately predicting the experimental bandgap and
carrier-transport dynamics. Combinatorial guess-and-
check approaches also help to identify potential complex
oxide candidates34; however, these approaches are lim-
ited in their ability to identify active crystal polymorphs
or doping and preparation techniques that can improve
carrier transport.
Another key challenge is to control the nature and
concentration of defects in these materials. High-
temperature crystal growth and purification methods,
such as those used for growing Si wafers, are inherently
expensive. Moreover, even though wafer-based silicon
accounted for as much as 92% of global photovoltaic
production in 2014 (REF.38), there is a practical limit
to the production capacity of high-purity wafer-based
materials. This means that candidate materials should
be defect-tolerant to avoid recombination. Alternatively,
one must either develop optimized growth methods or
design effective counter-doping strategies to suppress
killer defect recombination centres.
One strategy to identify promising ternary metal
oxides is to rationally engineer the bandgap through
cation combination (FIG. 2a). Mixing s2 cations (for
example, Sn2+ and Bi3+) with d0 cations (for example,
V5+, Ti4+ and Nb5+) creates a coupling between the s and
the O2p that forces an upward dispersion of the valence
band, whereas the coupling between the d bands from
the d0 cation and the p band from the s2 cation keeps the
conduction-band minimumlow 39.
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 By far the most successful ternary metal-oxide
photoanode to emerge with this structure is BiVO4. The
monoclinic polymorph of this material (FIG.2b) derives
its low bandgap of 2.4 eV from a valence band, the high-
est energy levels of which are composed of a mixture
of unhybridized O2p and Bi6s states40, as shown in
FIG.2a. Although initial theoretical studies predicted
a direct bandgap for BiVO4 (REF.39), the bandgap was
later predicted40,41 and recently experimentally con-
firmed to be indirect 42. The photocatalytic properties
of BiVO4 were first reported by Kudo etal.43 in 1998,
but it was not until 2006 that the first appreciable photo-
currents and quantum efficiencies were demonstrated
by Sayama and colleagues44. Later studies revealed that
poor electron transport due to limited overlap between
V3dV3d and V3dBi6p orbitals in the conduction
band limits the photocurrent 40,45.
Doping BiVO4 with Mo6+ or W6+ at the V5+ sites was
found to be effective in increasing the electronic con-
ductivity and thus carrier collection efficiencies4548.
Slow reaction kinetics at the SCLJ are another bottle-
neck that needs to be addressed, and co-catalysts such
as cobalt phosphate4850 and dual-layer Fe and Ni oxy-
hydroxides51,52 have been found to greatly improve the
performance of BiVO4 photoanodes. Intriguingly, the
role of these co-catalysts is not yet fully understood.
They may accelerate catalysis of the water oxidation
reaction, but could also reduce surface recombination
by preventing back-electron transfer or by chemically
passivating surface traps53. The exact mechanism is the
subject of an ongoing debate that was sparked initially
by work on modified Fe2O3 photoanodes54,55. Surface
recombination seems to be a major loss mechanism56,
but modification with suitable overlayers can almost
completely suppress this48,57.
The remaining challenge for BiVO4 is to optimize
the carrier collection efficiency, which is not trivial
for a highly doped semiconductor. One possibility
is to introduce a gradient in the dopant concentra-
tion across the film, thus creating a distributed n+n
homojunction with a corresponding electric field that
enhances charge separation within the film58. Another
approach is to fabricate a typeII heterojunction (for
example, with WO3) that improves the carrier sepa-
ration59. Heterojunctions have been nanostructured
to ensure that the film thickness does not exceed the
carrier diffusion length (70200 nm)48,60,61 while still
absorbing enough light. This approach has resulted
in some of the highest photocurrents reported for any
metal-oxide photoanode51,62, with a recent record value
of 6.72 mA cm2 measured at 1.23 VRHE under 1-sun
illumination63. This corresponds to ~90% of the theo-
retical current density for BiVO4, which illustrates that
even small-polaron semiconductors64,65 can achieve
performance levels close to their theoretical maximum.
Various demonstrations of complete bias-free
water-splitting devices based on BiVO4 have been
reported using photovoltaic cells in tandem with STH
efficiencies of 5.2%, 5.7% and 8.1% for devices with
double-junction amorphous silicon58,66, dye-sensitized
solar cells52 and GaAsInGaAsP cells63, respectively.
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As the record photocurrent density for BiVO4 now
approaches the theoretical maximum of 7.5 mA cm2,
further efforts should aim at improving the fill factor
to allow such high current densities to be reached at
lower applied potentials. This may be possible by fur-
ther reducing surface recombination, the mechanism of
which is still poorly understood. One should, however,
keep in mind that STH efficiencies of 10% and higher
can only be obtained with materials that have a smaller
bandgap thanBiVO4.
Another example of bandgap engineering by com-
bining metal cations to form a ternary oxide is copper
tungsten oxide. This material was considered for PEC
application decades ago but was dismissed because it
was thought to have a valence band that was purely
atomic O2p in character 67. The results of recent experi-
mental and theoretical investigations, however, suggest
that the valence band has a strong Cu3d character 68,69.
Thus, the valence-band structure of this material can
be considered to a first approximation as WO3
raised by the Cu3d states (FIG.2a). With a bandgap
of 2.02.25 eV and a flat-band potential similar to
WO3, it is suitable for application as a photoanode.
Recent studies have shown encouraging results with
electrodes prepared with simple solgel68 or electro-
deposition techniques70, with solar Jph values of approx-
imately 0.2 mA cm2 at the oxygen evolution potential
(+1.23 VRHE) and an incident photon-to-current effi-
ciency (IPCE) exceeding 20% for photon wavelengths
shorter than 400 nm. Oxygen evolution has clearly been
shown to occur with high stability (tens of hours) and is
mediated by mid-gap surface states stemming from the
Cu 3d levels71,72. However, the low light absorption coef-
ficient resulting from the indirect bandgap and the high
charge-transport resistivity in the bulk, probably caused
by low polaron charge transport, have been identified as
factors that limit the performance. Although these have
been addressed using light-harvesting strategies73 and
doping 74, achieving high IPCE and solar photocurrents
with this material remains a challenge, similar to that
faced for Fe2O3, as previously described.
Another drawback of Fe2O3 as a photoanode is its
relatively positive flat-band potential, which in part
leads to its high experimental onset potential (Eon) for
the photocurrent. The spinel ferrites MFe2O4 (M = Zn2+,
Mg 2+ and Ca2+) exhibit many of the same desired prop-
erties (photochemical stability and visible light absorp-
tion) as Fe2O3, but their conduction- and valence-band
levels can potentially be tuned via band hybridization
with the M2+ states. In particular, ZnFe2O4 exhibits a
similar bandgap to Fe 2O 3 (E g2 eV); however, its
conduction- and valence-band edges are shifted in the
negative direction by approximately 200 mV owing to
strong hybridization with the Zn3d states75. This sug-
gests that it should be possible to bring the flat-band
potential closer to the hydrogen evolution potential
and that a lower onset voltage for water oxidation is
required. Unfortunately, recent studies motivated by
this possibility have not shown a significantly lower
flat-band potential in ZnFe2O4, and the onset potential
is similar to that of Fe2O3 (REFS.76,77).
VOLUME 1 | FEBRUARY 2016 | 7
a b 2 c

x = 0.6 x = 0.75 x = 1.0

1 y = 0.4 y = 0.25 y = 0.0

Potential (VRHE)
0 EH+/H2

1.8 eV

1.7 eV

1.5 eV

1.0 eV

1.5 eV

1.2 eV

2.4 eV

3.2 eV
+1 EH2O/O2

+2
CuInxGasyS2 CuInSe2 CZTS WSe2 CdS TiO2

Figure 3 | Promising semiconductor chalcogenides for photoelectrochemical energy conversion. a|Chalcopyrite

structure adopted by CuInS2 and related compounds, which is closely related to the diamond structure. Each
chalcogenide anion (green) is tetrahedrally coordinated to two Cu+ cations (blue) and two In3+ cations (grey).
b|Bandgaps of selected chalcogenides with respect to the reversible hydrogen electrode, RHE (pH 7), with the
exception of WSe2 which is given at pH 0 because the EFB exhibits a strong variation with pH and is below the water
reduction potential at pH 7 (REF.130). c|Layered transition-metal chalcogenide structure (2H phase) of semiconducting
WSe2. The W4+ cations occupy a trigonal prismatic coordination sphere (blue), which is bound to six chalcogenide
ligands (red). The trigonal prisms are layered, sandwiching W atoms between layers of weakly bonded Se atoms.

To overcome the relatively poor charge-transport As the development of stable photocathodes is of

properties and improve the photocurrent of ZnFe2O4,
heterojunctions76,78,79 and nanostructuring 77 have been
used. Recently, 1D nanorod arrays were prepared by a
hybrid microwave annealing technique, which led to
improved crystallinity, removal of surface states and
an increased photocurrent compared with the control
films80. Although the photocurrent was only approxi-
mately 100 A cm2, this reliable synthetic technique to
prepare phase-pure and photoactive ZnFe2O4 may serve
as a platform for further development. Further studies
on the charge-carrier dynamics to better quantify the
factors limiting the photocurrent areneeded.
Hybridization in ferrites with high-energy Ca 3d
energy states raises the conduction and valence bands
of CaFe2O4, and renders it useful as a p-type photoca-
thode for water reduction81. This material has a slightly
lower bandgap of 1.9 eV and requires high temperatures
(1,1001,200 C) to form the photoactive spinel phase.
Recently, heating a pre-prepared powder on a Pt substrate
to an optimum temperature was reported to result in an
(hk0)-oriented CaFe2O4 film, which exhibited a cathodic
photocurrent of approximately 200 A cm2 (REF.82).
Subsequently, various metal-doped p-type CaFe2O4 pho-
tocathodes were prepared in an attempt to improve the
low quantum efficiency 83. Although Ag doping improved
the performance greatly compared with a control, the
maximum IPCE values of the best electrodes (approxi-
mately 4%) were similar to previous results. Analogous to
the Zn ferrite, CaFe2O4 has been used in heterojunction
photoelectrodes. Charge-separating np heterojunctions
have been demonstrated with Fe2O3 (REF.84), BiVO4
(REF.85), TaON (REF.86) and ZnFe2O4 (REF.87). Although
these materials form good electronic interfaces in gen-
eral, fundamental studies of ferrite materials are required
to determine whether their fundamental limitations of
high charge recombination can be overcome.
strong interest, much effort has been focused on devel-
oping robust p-type oxides other than CaFe2O4. One
approach is to use analogues of binary Cu2O, which
possess a favourable bandgap and band energy levels
for hydrogen evolution (because of the Cu3d levels);
however, these are not stable under aqueous condi-
tions88. A combinatorial screening method was recently
used to optimize the performance of CuBi2O4 (REF.89),
which is known to be a stable electrode material in basic
pH but has poor PEC performance90; including Ag as
a dopant was found to increase the performance. In
contrast to the high-temperature conditions needed to
prepare ferrites, photoactive CuBi2O4 (which has a rel-
atively complex ditetragonal-dipyramidal crystal form)
has been prepared at low temperature (80 C) with
hydrothermal methods91 and by electrodeposition92.
Although heterojunctions have been employed with
this material (using CuO)93, and despite the favourable
bandgap (1.51.8 eV) and stability for hydrogen evolu-
tion, a route to overcome the poor charge extraction is
needed to advance the performance of this promising
material.
The copper niobium oxides CuNbO3 and CuNb3O8
have recently been developed as p-type photocathodes.
For CuNbO3 (Eg = 2.0 eV), stable photocurrent density,
IPCE values of up to 5% at 350 nm, and resistance to
photocorrosion were noted94. Electronic structure cal-
culations based on density functional theory suggested
that the bandgap originates from a nearly direct band-
gap transition primarily based on copper-to-niobium
(d 10-to-d 2) excitations. The same group increased the
optical absorption by increasing the Nb5+:Cu+ ratio
using CuNb3O8 (REF.95); however, although the mate-
rial showed a high hole mobility (145 cm2 V1 s1) and a
conduction-band edge less than the hydrogen evolution
potential, the IPCE values did not exceed 7%.

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2016 Macmillan Publishers Limited. All rights reserved

 Copper-based ternary oxides (p-type) that crystal-
lize in the delafossite phase, CuFeO2 (REFS96,97) and
CuRhO2 (REF.98), have been recently investigated as
potential photocathodes. Of these, CuFeO2 (FIG.2c) is
particularly attractive, as it is composed of widely avail-
able elements. Using a simple solgel route, the thick-
ness of this material has been optimized, and an oxygen
intercalation treatment can address the poor majority
carrier conductivity, leading to sacrificial photocurrent
densities of up to 1.5 mA cm2 at +0.35 VRHE (O2 reduc-
tion)97. Photocurrent densities of up to 0.4 mA cm2 for
H+ reduction at 0 VRHE have been reported when added
overlayers for charge extraction and water reduction
catalysts were used. The bare CuFeO2 surface is a poor
catalyst for water reduction but is active for CO2 reduc-
tion99,100. The bandgap of CuFeO 2 (1.5 eV) is lower
than that of the parent binary oxide (Cu2O) despite
the valence and conduction bands being mostly Cu3d
in character in both cases (the Fe3d bands lower the
conduction band). Moreover, in stark contrast to Cu2O,
CuFeO2 is remarkably stable under PEC operation in
basic electrolytes, operating without a decrease in pho-
tocurrent for days, which makes it a highly promising
photocathode material if the charge separation and
catalytic activity can be further improved.
Oxynitrides. In addition to tuning the bandgap of
oxides using metal-cation orbitals, substituting a
nitrogen atom for oxygen will decrease the bandgap
by introducing higher-lying N2p states (FIG.2a). For
example, the wide bandgap of tantalum oxide can be
reduced with high-temperature treatment under NH3 to
formTaOxNy (REF.101). Electrodes can also be prepared
at room temperature without NH3 using reactive sput-
tering 102. Although colouration of the material owing to
an N2p -to-Ta3d transition occurs readily upon treat-
ment, the films do not show any visible-light PEC activ-
ity until the nitrogen concentration is high enough to
form a continuous N2p impurity band103. Stoichiometric
TaON possesses a bandgap of 2.5 eV, whereas that of the
fully nitrated version, Ta3N5, is 2.1 eV. High electron
mobility 104 and a suitable valence-band level for water
oxidation make TaOxNy a potential photoanode material.
However, (oxy)nitrides are not thermodynamically sta-
ble for this application, as oxidizing the semiconductor is
more favourable than oxidizing water at the SCLJ. There
is some indication that if holes can be scavenged by a
charge-extracting water oxidation catalyst layer, stable
operation can be maintained for at least several hours105.
Impressive short-term performance was observed
in initial reports, with IPCEs approaching 80% at
400-nm illumination106, and photocurrents of the order
of 45 mA cm2 for water oxidation can be obtained
through optimization by doping (with Ba) or by further
aiding charge extraction using heterojunctions86,107,108.
Additional candidates such as LaTiO2N (Eg = 2.1 eV)
109112
, SrNbO 2 N (E g = 1.8 eV) 113 and BaTaO 2 N
(Eg = 1.8 eV)114, all of which adopt the common per-
ovskite structure (FIG.2d), have also recently emerged
as promising materials, with the latter behaving in a
similar manner to Ba-doped TaON with an impressive
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2016 Macmillan Publishers Limited. All rights reserved
photocurrent density of 4.2 mA cm2 at +1.2 VRHE and
approximately 100% faradaic efficiency for water oxi-
dation for 6hours. In general, the best performance
has been observed with materials prepared under harsh
conditions (>900 C with NH3) that are not compatible
with typical glass-based transparent-conducting-oxide
substrates. Thus, processing of oxynitride powder into
electrodes or the direct preparation of semi-transparent
films is a challenge. Moreover, we note that identifying
material preparation routes for these materials that lead
to high performance and also avoid high temperatures
and harsh conditions, which may not be economically
viable, is a point of interest for future development.
Metal chalcogenides. Sulfur and selenium have higher-
lying p-band energy levels than oxygen and can there-
fore be used to achieve smaller bandgaps compared
with oxides. Although the classic binary sulfides, such
as FeS2 and CuS, have intrinsic limitations that prevent
them from achieving high conversion efficiencies for
solar energy, the chalcopyrite-type semiconductors
(the crystal structure of which is shown in FIG.3a),
CuInxGa(1x)S(Se)2, and kesterite-type semiconductors,
Cu2ZnSnS(Se)4, have received considerable attention for
photovoltaic energy conversion because of their high
extinction coefficients, acceptable charge-transport
characteristics and tunable bandgaps (1.02.4 eV). These
materials generally do not exhibit a proper valence-band
energy or stability for water oxidation, but the well-po-
sitioned conduction-band edge for water photoreduc-
tion (FIG.3b) has inspired recent investigations into their
use as photocathodes in PEC cells. CuInS2 (Eg = 1.5 eV)
was reported with an onset potential at +0.6 VRHE and
photocurrent density of about 15 mA cm2 at 0 VRHE
(REF.115). Increasing the bandgap by adding up to 40%
Ga (CuInxGa1xS2) affords a positive shift in the onset
potential to about +0.8 VRHE (REF.116), which could be
of benefit in tandem cell configurations (together with a
low-bandgap photoanode).
Selenide chalcopyrite photocathodes ((Ag,Cu)
GaSe 2, Cu(In,Ga)Se 2)) 117121 with lower bandgaps
show good photocurrents but poor onset potentials.
Burying the junction and optimizing the electrolyte
conditions was reported to give an impressive applied-
bias photon-to-current efficiency of 8.5% at +0.38 VRHE
(REF.122). In efforts to make photocathodes from Earth-
abundant atoms, Cu2ZnSnS4 (Eg = 1.5 eV) has also been
used123,124, giving a photocurrent density of 1.0 mA cm2
at 0 VRHE and an onset of +0.2 VRHE for sustained water
reduction. It must be noted that n-type overlayers
(commonly CdS, similar to photovoltaic cells) are
used for chalcopyrite and kesterite materials, as the
resulting pn junction enhances the otherwise poor
charge separation. The long-term stability of the bare
CdSelectrolyte junction is one point for further inves-
tigation, but thin protective layers of TiO2 deposited
by sputtering or atomic layer deposition in addition to
the CdS have also been reported to improve the overall
performance124,125.
Semiconducting transition-metal dichalcogenides,
MoX2 and WX2 (X = S or Se), with a layered crystal
VOLUME 1 | FEBRUARY 2016 | 9
 a g-C3N4 TMP PMPDI
O OH
P
O
N N
O O
N N N N

N N N N N N NH N O
N N N N N N N
N HN OH
N N N N

N N N N N N
O N O
N N N N N N N
O
P
O OH
b
2

1 LUMO
Potential (VRHE, pH 7)

0 EH+/H2
2.7 eV

1.7 eV

1.8 eV

3.2 eV
+1
EH2O/O2

+2
HOMO

+3 g-C3N4 TMP PMPDI TiO2

Figure 4 | Emerging carbon-based semiconductors for photoelectrochemical devices. a|Chemical Nature Reviews | Materials
structures of
graphitic carbon nitride (g-C3N4); 5-(4-carboxyphenyl)-10,15,20-tris(2,4,6-trimethylphenyl)porphyrin (TMP); and
N,N-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI). b|Approximate highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO) locations of the semiconductors in water at pH 7. RHE,
reversible hydrogen electrode.

structure (as shown in FIG.3c) have recently attracted
widespread attention in the materials science commu-
nity owing to their ability to be exfoliated into atomically
thin 2D sheets, which results in high extinction coeffi-
cients and allows the bandgap to be tuned according to
the number of atomic layers126,127. In particular, WSe2 has
been identified as a promising material for PEC appli-
cations. Although not stable for water oxidation, initial
efforts with non-exfoliated (bulk) WSe2 showed its high
performance as an n-type photoanode for PEC oxidation
reactions128,129. More recently, Lewis and co-workers130
reported PEC water reduction with p-type (Nb-doped)
WSe2 bulk single crystals as photocathodes. Although
bare WSe2 electrodes exhibited negligible photocurrents,
significant hydrogen evolution was observed from a cat-
alyst (PtRu)-coated WSe2 electrode in acidic electrolyte
with a (1-sun) photocurrent density of 24.5 mA cm2 at
0 VRHE. As WSe2 can be exfoliated in 2D nanosheets and
solution-processed into thin films, it could be possible
to produce ultracheap roll-to-roll fabricated photoelec-
trodes131. In addition, as a critical advantage over other
chalcogenide-based materials, no charge extraction or
protection layers are needed on WSe2. Further develop-
ment of this family of semiconductors is warranted in
light of these recent encouraging results.
Silicon and IIIV semiconductors. The outstanding per-
formance of the classic semiconductors used in photo-
voltaic energy conversion has not been ignored by the
PEC community. Although silicon is unstable under
direct PEC water oxidation or reduction reactions, pho-
toanode or photocathode operation can be made possi-
ble with conformal protecting layers of TiO2 deposited
by atomic layer deposition. The Si and TiO2 band align-
ment is suitable for conduction-band electron transfer
from the Si to the TiO2, and subsequent water reduction
occurs with high photocurrent densities (16 mA cm2 at
+0.2 VRHE)132. Misalignment of the valence-band levels,
however, typically requires that ultrathin tunnel junc-
tions be used133. Recently, a breakthrough in the prepa-
ration of leaky TiO2, in which hole transport can occur
by hopping through mid-gap states, has enabled the use
of n-type silicon (n-Si) and IIIV semiconductors as
stable photoanodes for water oxidation134. Multijunction
amorphous silicon (a-Si), which has a tunable bandgap,
was investigated in early solar fuel research on photo-
voltaic-biased electrosynthetic cells25 and has recently
also been used as a photocathode with a protective layer
created by atomic layer deposition135.
The IIIV class of semiconductors (GaP (REFS136,137),
GaInP2 (REFS138,139) and InP (REFS140,141)) also offers

10 | FEBRUARY 2016 | VOLUME 1 www.nature.com/natrevmats

2016 Macmillan Publishers Limited. All rights reserved

 tunability and exceptional charge-transport character-
istics that lead to excellent performance as photoelec-
trodes for H2 evolution and CO2 reduction142. Recently,
May etal.143 demonstrated a new performance bench-
mark for STH conversion efficiency under illumination
of 1 sun using an absorber consisting of a GaInP np
top cell with a bandgap of 1.78 eV and an nip GaInAs
bottom cell (Eg = 1.26 eV). The device structure also con-
tained cap layers and an AlInP window layer for electron
collection. The combined chemical surface transfor-
mation of the tandem structure together with catalyst
deposition resulted in a STH efficiency (AM 1.5G) of
14%. The photocurrent density was found to decrease
continuously, saturating at half of its original value after
35hours of operation, thus indicating the requirement of
additional protecting layers. Overall, the scalability and
price of this class of semiconductors, especially with the
requisite protecting layers, will make it difficult to reach
the target of US $200 per square metre of device at the
terawattscale.
Carbon-based semiconductors. Conjugated (sp2) carbon
-based semiconductors offer tunable energy levels,
respectable solid-state charge-transport characteristics
and facile solution processability in many common sol-
vents. These promising aspects have motivated intense
investigation for economical roll-to-roll organic photo-
voltaic devices. However, owing to their generally low
stability under operation in aqueous conditions, and
the need to split coulombically bound excited states
(excitons) at typeII (np) heterojunctions, they have
generally not been pursued as photoelectrodes for
direct solar water splitting 144.
Encapsulated organic photovoltaics have recently
been demonstrated in photovoltaic-biased photo-
electrosynthetic cells for solar water splitting 145; how-
ever, the lack of intrinsic material stability limits their
application in this configuration. By contrast, robust
polymeric carbon-nitride-based materials146,147 and
conjugated microporous network polymers 148 have
recently shown visible-light hydrogen evolution and
stability for more than 20hours as p-type photocata-
lysts for direct solar water splitting; this suggests that
conjugated carbon-based materials may be suitable for
PEC application. Photoelectrodes of a graphitic carbon
nitride (g-C3N4) (see chemical structure in FIG.4a) pre-
pared by polymerizing dicyandiamide showed a band-
gap of 2.32.7 V, n-type behaviour with a flat-band
potential of 0.73 VRHE (suggesting that the conduc-
tion band is more negative than the water reduction
potential) and a photocurrent density of approximately
5 A cm2 (REF.149). The n-type behaviour was rational-
ized as coming from the donor quality of the N atoms
and inspired its subsequent application in heterojunc-
tions150. Indeed, g-C3N4 has been combined with CuInS2
to give a heterojunction photocathode with an onset
potential of +0.36 VRHE an improvement of about
0.15 V over the bare electrode151.
Despite the harsh conditions of PEC water oxidation,
small-molecule metalorganic and all-organic dyes have
also recently been demonstrated to have highest occu-
pied molecular orbital (HOMO) levels suitable for water
oxidation. Splitting the photogenerated exciton can be
accomplished with a heterojunction with TiO2 in the
architecture of a dye-sensitized PEC cell152,153. In this
case, a photogenerated electron in the lowest unoccupied

Table 1 | Overview of emerging n-type semiconductors for photoelectrochemical application

Material Eg (eV) EFB (VRHE)* Performance summary for water Limitations Satisfies selection Refs
oxidation criteria
BiVO4 2.4 ~0 High IPCE (~90%) with co-catalyst Carrier collection efficiency; surface Yes, for maximum 51,62,63
and 6.7 mA cm2 at 1.23 VRHE under recombination; bandgap limits AM 10% STH conversion
1-sun illumination. 1.5G solar photocurrent to ~7 mA cm efficiency
2

CuWO4 2.02.2 0.3 ~0.2 mA cm2 at 1.23 VRHE under 1-sun Indirect bandgap and high resistivity Unlikely 7072
illumination and IPCEs over 20%
ZnFe2O4 2.0 0.40.6 0.25 mA cm2 at 1.23 VRHE under 1-sun Poor minority carrier LD; bulk and Unlikely 77,80,165
illumination and IPCEs up to 15% surface recombination
TaOxNy 2.12.5 0.1 5 mA cm2 at +1.23 VRHE under 1-sun Low stability (can be addressed with Potentially yes 105,106
illumination and IPCEs up to 76% co-catalyst coating in the short term)
LaTiO2N 2.1 0.1 3.5 mA cm2 at +1.23 VRHE under 1-sun Faradaic efficiency for water Potentially yes 109111
illumination and (sacrificial) IPCEs oxidation of 76%; long-term stability
up to 40% unknown
BaTaO2N 1.8 0.2 4.2 mA cm2 at 1.2 VRHE under 1-sun Long-term stability unknown Potentially yes 114
illumination and IPCEs up to 25%,
ABPCE of 0.7% at 1.0 VRHE
g-C3N4 2.32.7 0.73 Small anodic photocurrents of Poor charge separation; long-term Unlikely 149,150
~5 A cm2 stability unknown
TMP 1.9 NA Small anodic photocurrents of Requires TiO2 scaffold; stable Unlikely 153
~100 A cm2 and an IPCE of 0.028% photocurrent not observed
PMPDI 1.75 0.3 150 A cm2 at +1.6 VRHE IPCEs of ~1% Stable photocurrent not observed Unlikely 154
ABPCE, applied-bias photon-to-current efficiency; EFB(VRHE), flat-band potential with respect to the reversible hydrogen electrode; Eg, bandgap energy; IPCE,
incident photon-to-current efficiency; LD, diffusion length; NA, not applicable; PMPDI, N,N-bis(phosphonomethyl)-3,4,9,10-perylenediimide; STH,
solar-to-hydrogen; TMP, 5-(4-carboxyphenyl)-10,15,20-tris(2,4,6-trimethylphenyl)porphyrin. *For the bare material in contact with aqueous electrolyte.

NATURE REVIEWS | MATERIALS VOLUME 1 | FEBRUARY 2016 | 11

2016 Macmillan Publishers Limited. All rights reserved

 molecular orbital (LUMO) of the dye injects into the
conduction band of TiO2, and the remaining hole is
transferred to a catalyst to oxidizewater.
Recently, a family of metal-free porphyrin-based
dyes (representative structure coded as TMP in FIG.4a)
anchored to TiO2 was demonstrated by Mallouk and
co-workers153 to drive PEC water oxidation under solar
illumination in the presence of an IrO2 water oxidation
catalyst. The LUMO levels were suitable for electron
injection into TiO2 (FIG.4b), and high photovoltages
were observed (in excess of 1 V); however, the IPCEs
were of the order of 0.1% at best, and the photoelec-
trode lifetime was on the timescale of seconds. A func-
tionalized perylene diimide (coded PMPDI; see FIG.4a)
thin-film electrode without TiO2 also oxidized water
in the presence of a water oxidation catalyst 154. A solar
photocurrent density of 150 A cm2 at +1.6 VRHE and
faradaic efficiency of 80% were obtained but, again, the
stability was poor. Overall, this class of semiconductors
offers an entirely new and exciting path of exploration
given the demonstrated tunability of these materials. A
strategy for further advancement could be to use rigid
core materials to reduce the possibility of instability.
Nanostructuring and functionalization
Among all of the materials discussed above, one impor-
tant theme emerges regarding the development of sem-
iconductor photoelectrodes: engineering the SCLJ via
nanostructuring 155 or chemical functionalization156.
These can be powerful tools to gain material insight and
improve photoelectrode performance. With respect to
chemical modification, many different surface-specific
effects arise, which can be categorized156 as protection of
the surface against photocorrosion; passivation of dele-
terious surface states; tuning of the band-edge positions
or band bending; or selective extraction of carriers and
improved catalytic activity. Several chemical modifi-
cation strategies are available that afford one or more
of these beneficial effects. For example, the passivation
of surface states using the deposition of thin overlay-
ers157,158 or using surface reconstruction159 can both
reduce charge-carrier recombination and increase the
photovoltage. Moreover, attaching dipolar molecules
can afford a relative shift in the semiconductor band-
edge positions (and flat-band potential)139. In ferroe-
lectric electrode materials, an additional built-in field
can be created by using a poling technique160, with the
increased field strength aiding the extraction of carri-
ers. Overall, the ability to tune the semiconductor sur-
face represents an important distinction between PEC
devices and photovoltaics combined with electrolysis.
We point readers to a recent comprehensive perspective
article on this topic for further information156.
Nanostructuring is now widely used to overcome
the trade-off between optical absorption and minori-
ty-carrier diffusion lengths, and to increase the catalytic

Table 2 | Overview of emerging p-type semiconductors for photoelectrochemical application

Material Eg (eV) EFB (VRHE)* Performance summary for water Limitations Satisfies Refs
reduction selection criteria
Cu2O 2.0 0.8 6 mA cm2 at 0 VRHE under 1-sun Low stability Yes 88
illumination and IPCEs up to 60%
CaFeO2 1.9 1.3 ~1 mA cm2 at +0.4 VRHE under Poor charge-carrier mobility Unlikely 82,83
concentrated illumination and IPCEs
up to 5%
CuNb3O8 1.3 0.35 0.2 mA cm2 at 0 VRHE under visible Poor minority-carrier LD Unlikely 95
( 420 nm) illumination and IPCEs
up to 7%
CuFeO2 1.5 1.0 0.4 mA cm2 at 0 VRHE under 1-sun Poor interface with water reduction Potentially yes 96,97
illumination for H2 production and catalysis and minority-carrier LD
(sacrificial) Jph up to 1.5 mA cm2 with
IPCEs up to 15%
Cu(In,Ga)S2 1.51.8 ~1.0 15 mA cm2 at 0 VRHE under 1-sun Charge separation and stability (CdS Potentially yes 116
illumination and IPCEs up to 60%, extraction and TiO2 overlayers required)
ABPCE of 2% at 0.25 VRHE
(Ag,Cu) 1.61.7 0.61.0 7.3 mA cm2 at 0 VRHE under 1-sun Charge separation and stability (CdS Potentially yes 117120
(In,Ga)Se2 illumination and IPCEs up to 50% extraction and TiO2 overlayers required)
Cu2ZnSnS4 1.5 0.6 1.0 mA cm2 at 0 VRHE under 1-sun Charge separation and stability (CdS Potentially yes 116,117
illumination extraction and TiO2 overlayers required)
WSe2 1.2 0.8 (pH 15 mA cm2 at 0 VRHE under 1-sun Long-term stability of unprotected Yes 130,131
2.3) illumination and IPCEs up to 60%, electrodes unknown
ABPCE of 7%
GaInP2 1.8 0.5 (pH 0) ~3 mA cm2 at 0 VRHE under 0.2-sun Low stability Yes 138,139
illumination
InP 1.35 0.8 ~35 mA cm2 at 0 VRHE under 1-sun Low stability (TiO2 overlayers required) Yes 140,141
illumination and IPCEs up to 60%,
ABPCE of 14%
ABPCE, applied-bias photon-to-current efficiency; Eg, bandgap energy; EFB(VRHE), flat-band potential with resepct to the reversible hydrogen electrode; IPCEs, incident
photon-to-current efficiencies; Jph, photocurrent density; LD, diffusion length. *For the bare material in contact with aqueous electrolyte.

12 | FEBRUARY 2016 | VOLUME 1 www.nature.com/natrevmats

2016 Macmillan Publishers Limited. All rights reserved

 activity through an increased surface area. For Fe2O3
photoanodes, nanostructuring has afforded an increase
in performance by a factor of 10 from the single-crys-
tal case. The best-performing metal-oxide photoanodes
reported so far are the nanostructured WO3BiVO4
heterojunctions mentioned earlier. In general, however,
the higher surface area leads to lower intrinsic photo-
voltage and increased surface recombination, which are
both important loss mechanisms. To minimize surface
recombination, it may be sufficient to nanostructure
only the co-catalyst, especially if the system is limited
by surface reaction kinetics. A large number of Earth-
abundant nanostructured catalysts are now available
with water oxidation overpotentials as low as 0.30.4 V
at 10 mA cm2 in alkaline solutions12. Some foam-based
structures even reach this current density at a mere
0.24-V overpotential23, and it seems unlikely that much
lower values can be reached. Further improvements are
thus likely to come from increasing the photovoltage of
the semiconductor, for which nanostructuring should
be avoided this is something that the photovoltaics
community has long been aware of. Moreover, nano-
structuring is not imperative for all semiconductors,
because it only benefits materials for which the carrier
diffusion length falls short of the optical absorption
depth. These properties should thus be well established
before any attempts at nanostructuring a particular
semiconductor aremade.
Realizing PEC technology
From just a few key materials a decade ago namely,
the binary oxides TiO2, WO3 and Fe2O3 the field of
PEC technology has expanded to incorporate a huge
number of potential semiconductors. Moreover, the
almost endless number of untested atomic combina-
tions gives hope that ideal materials are still waiting to
be discovered. An overview of the materials discussed
in this Review is given in TABLES1,2. Many of these
show small but encouraging photocurrents. It is neces-
sary to develop selection criteria to identify candidates
that warrant further in-depth and time-consuming
studies. We now briefly discuss three main criteria
that, when fulfilled, give a reasonable basis for further
scrutiny of a material. The main criterion that has been
used in the field is the bandgap energy, and decades
of effort on TiO2 have shown that this criterion still
stands; attempts to decrease the bandgap by doping
have invariably been unsuccessful, owing to increased
recombination. To reach efficiencies of 10%, 15% or
20%, the intrinsic bandgap of the top absorber should
be smaller than 2.35, 2.11 or 1.93 eV, respectively, and
this assumes that all incident photons with energy
greater than the bandgap can participate (that is, with
zero loss).
A second useful criterion is the carrier diffu-
sion length, L D, which can be calculated from the
carrier lifetime, , and the mobility, , as follows:
L D = (kT/e) 0.5. The lifetime and mobility can be
measured relatively quickly and conveniently in a
contactless fashion with time-resolved microwave
conductivity 60. If the signal is too small to measure, or
NATURE REVIEWS | MATERIALS
2016 Macmillan Publishers Limited. All rights reserved
if LD is only a few nanometres, it is likely that the mate-
rial is an intrinsically poor semiconductor or that it is
susceptible to the formation of recombination centres
(killer defects).
The third criterion is given by the band-edge posi-
tions in relation to the redox potentials of the desired
half-reaction (that is, the built-in potential), as these
determine the photovoltage that the other light absorb-
ers in the system need to generate. However, the band
edges can be shifted with surface functionalization by
the dipole layers; thus, this criterion is less strict than
the previous two. Another arguably soft criterion is the
stability of the semiconductor when it is in direct con-
tact with the electrolyte; however, this is only required
if it is not possible to make perfectly conformal and
stable protection layers in a scalable and cost-effective
manner. At present this is not clear, but the fact of the
matter is that very few of the more promising semi-
conductors are intrinsically stable (with the exception
of some oxides), and protection layers (coupled to cat-
alysts) may be necessary. In TABLES 1,2 an assessment
of each semiconductor material is given with respect
to the above criteria. If the material does not currently
meet the criteria because of a lack of sufficient study,
we offer a speculation as to whether a material could
possibly meet the criteria, or whether this is unlikely
given the known material limitations.
The next step is to incorporate these materials in
real solar fuel devices. Although several laboratory-
scale demonstrations have been reported20, we are yet
to realize a device that can produce solar fuels at a
cost competitive with the traditional photovoltaics
combined with electrolysis. Interfacial engineering
may enhance the performance of the conventional
and emerging materials discussed above; however,
above all, these materials and the processes used
must be inexpensive. To assist in the development
of a viable PEC device, guidelines should be defined
that direct efforts in the field. Such a roadmap should
not only include materials development but also take
into account the chemical engineering challenges
that need to be addressed. Indeed, the complexity
of a solar fuel device far exceeds that of a photovol-
taic cell because of the added demands associated
with gas handling and ion transport in the electro-
lyte. The need to efficiently combine these demands
with light harvesting presents an additional challenge
over (dark) electrolyser designs. The first important
advances in PEC device design and modelling have
recently been achieved161,162, and the current top-per-
forming materials are very useful in the experimen-
tal validation of these studies. For this reason, these
materials warrant further study even though they
may fall short of our ultimate performance goals. The
field has now reached a stage at which all aspects of
PEC technology materials development, device
modelling and simulations, life-cycle and techno-
economic analysis have to be considered to guide
our efforts. Only then can we avoid dead ends, make
rapid progress and develop the basic science into a
viable technology.
VOLUME 1 | FEBRUARY 2016 | 13
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Competing interests statement
The authors declare no competing interests.
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 CORRECTION

ERRATUM

Semiconducting materials for photoelectrochemical energy conversion

Kevin Sivula and Roel van de Krol
Nature Reviews Materials 1, 15010 (2016)
In the originally published version of this article, the values of the band gaps marked in Figure 4 for g-C3N4, TMP and PMPDI
were incorrect. This has been corrected in both the HTML and PDF versions. We apologize to the readers for this error.

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