Received: 12 October 2021

| Revised: 3 January 2022

| Accepted: 11 January 2022

DOI: 10.1002/ese3.1087

REVIEW

Strategies for improving photoelectrochemical water

splitting performance of Si-based electrodes

Caihong Cheng | Weiying Zhang | Xiaoming Chen | Shaoqin Peng | Yuexiang Li

Department of Chemistry, Key

Laboratory of Jiangxi Province for
Environment and Energy Catalysis,
Nanchang University, Nanchang, China
Correspondence
Yuexiang Li, Department of Chemistry,
Key Laboratory of Jiangxi Province for
Environment and Energy Catalysis,
Nanchang University, Nanchang,
330031, China.
Email: liyx@ncu.edu.cn
Funding information
National Key Research and
Development Program of China, Grant/
Award Number: 2018YFB1502004;
National Natural Science Foundation of
China, Grant/Award Number: 21962010
Abstract
Si, as a narrow bandgap semiconductor with a broadband absorption for sunlight,
is considered to be a very competitive photoelectrode material for solar-driven
photoelectrochemical (PEC) water splitting. However, there are major barriers
in construction of efficient and stable Si-based PEC cell, including low photovolt-
age, sluggish reaction kinetics, and poor stability in electrolytes. This review fo-
cuses on the strategies to solve these issues and summarizes recent progress. The
working principles of PEC water splitting are first introduced. Then the strategies
for improving Si-based photoelectrode performances are discussed, including (1)
the regulation of Si surface morphology for enhancing light harvesting, (2) band
structure engineering strategies to reduce recombination of photogenerated car-
riers, and (3) modification of protection layers for long stability and loading co-
catalysts on Si-based photoelectrodes for accelerating water splitting. Lastly, we
have presented some issues of Si-based photoelectrode materials, which should
be addressed in future research.

KEYWORDS
band structure engineering, cocatalyst for water splitting, morphology, protection layer, Silicon

1 | INTRODUCTION (PV)-electrocatalytic (EC),1-4 photocatalytic,5-12 and pho-

Along with the swift development in economy, the short-
age of energy and the environment pollution in the global
become more serious. Therefore, developing green and re-
newable energy is urgent to reduce fossil energy consump-
tion and realize environmental sustainability. Hydrogen,
due to its high energy density, storability, and clean prod-
uct (water), is becoming an ideal fuel to replace fossil fuels.
Solar energy-driven water splitting to produce hydrogen
is a promising and cost-effective approach. Conversion
of solar energy into hydrogen via water splitting can be
achieved through various ways such as photovoltaic
toelectrochemical/photoelectrocatalytic (PEC) water
splitting,.13-15 Since PEC water splitting technology is
technically and economically feasible, it stands out from
various technologies for sustainable hydrogen produc-
tion.16 When the energy conversion efficiency of solar to
hydrogen (STH) reaches 10%, and hydrogen production
cost reduces to ca. $2–$4 per kg, the commercial applica-
tion of PEC water splitting will become possible.17,18
A typical PEC water splitting cell consists of light-
harvesting semiconductor photoelectrodes and an
electrolyte solution. Between them, semiconductor pho-
toelectrodes are the crucial components. To realize high

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© 2022 The Authors. Energy Science & Engineering published by Society of Chemical Industry and John Wiley & Sons Ltd.

Energy
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Energy Sci Eng. 2022;10:1526–1543.
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2 |
CHENG et al.
efficiency and large-scale application of PEC water split-
ting, it is imperative to search efficient, low cost, abun-
dant, and nonhazardous semiconductor materials.
Silicon is one of the most earth-abundant elements,
and the production cost of Si semiconductor is relatively
low. It is a narrow band gap semiconductor (Eg =1.12 eV),
which can absorb most light of solar spectrum (300–
1200 nm).17 Thanks to technological progress, silicon PV
cell has achieved a high photoelectric conversion effi-
ciency, for example, the efficiency of 25% for commercial
Si TOPCon cell.19 Through connecting commercial Si PV
panels with a water electrolyzer to construct a PV-EC sys-
tem, efficient solar water splitting for hydrogen produc-
tion can be easily realized. However, the PV-EC system
is complicated and expensive for large-scale hydrogen
evolution. Loading electrocatalysts of water splitting on
Si photoelectrodes to build PEC electrodes and cells can
decrease greatly the cost for large-scale hydrogen produc-
tion.16,20 Nonetheless, a single Si photoelectrode without
any protection layer is unstable. The high recombination
of photogenerated carriers in Si bulk and at the interface
decreases greatly the generated photovoltage and photo-
electric conversion efficiency. Moreover, the Si surface re-
action kinetics is sluggish.21 Therefore, how to boost the
performance of hydrogen production and reinforce stabil-
ity is essential for Si-based photoelectrodes.
In this review, we focus on the manipulation of the
energy bands of semiconductor surfaces to facilitate the
charge separation and transfer for achieving high pho-
tovoltage and energy conversion efficiency. The other
strategies for high PEC efficiency and stability are also
summarized, including morphology control of Si sub-
strate to enhance light harvesting, and surface/interface
F I G U R E 1 Configurations of Si-based PEC water splitting and operating principle under illumination: (A) a photoanode for OER and
a counter cathode for HER; (B) a photocathode for HER and a counter anode for OER; (C) a dual photoelectrode for both HER and OER.
CB, energy of conduction band minimum; VB, energy of valence band maximum; EF, n and EF, p, quasi-Fermi level of semiconductor; Ebias,
external voltage
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CHENG et1527
al.
modification with protective layer and cocatalysts to sta-
bilize Si substrate and accelerate the surface water oxida-
tion/reduction reaction, respectively.
2 | PEC WATER SPLITT IN G AN D
SI- BASED PEC
2.1 | Configuration and working
principle of Si-based PEC cell
Configurations of Si-based PEC cell can be divided
into: (1) Si photoanode-counter electrode (CE) device
(Figure 1A); (2) Si photocathode-CE device (Figure 1B);
(3) a dual photoelectrodes device composed of photoan-
ode and photocathode (Figure 1C). An Si-based photo-
electrode consists of the Si substrate for light harvesting,
charge separation, and transport layers and cocatalyst
layer.18 Intrinsic Si semiconductor performs poor con-
ductivity. The conductivity of Si semiconductor can be
greatly improved by doping main group three (B and
Ga, p-type) and group five (P and As, n-type) elements.22
Generally, the n-Si is employed as photoanode for oxygen
evolution reaction (OER) and p-Si as photocathode for
hydrogen evolution reaction (HER).18 The open circuit
voltage (Voc) of a single Si PV cell is normally <0.7 V.23 A
single Si photoanode or photocathode cannot drive water
splitting and requires an external bias. However, the dual
photoelectrodes device (Figure 1C) could achieve PEC
water splitting without any bias. Another strategy for
achieving unassisted PEC water splitting is construction
of PV/PEC tandem cells, which readers can consult the
excellent article and review.24,25

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CHENG et al.
The operating principle of PEC water splitting cell is
shown in Figure 1A. When semiconductor photoelectrode
is illuminated with photons with energy equal to or greater
than the semiconductor band gap, electrons are excited
from the valence band into the conduction band, simulta-
neously leaving behind positive holes in the valence band
(Equation 1). The photoexcited electrons transfer to the
counter electrode (i.e., cathode) through the external cir-
cuit, and then participate in the water reduction reaction
to produce hydrogen (Equation 2 or 4). The holes remain-
ing in the valence band migrate to the photoanode surface
and subsequently oxidize the water to oxygen (Equation 3
or 5). In order to achieve water splitting, the VB must be
more positive than the O2/H2O redox potential and the CB
must be more negative than the H+/H2 redox potential.
The electrochemical potential of those photo-generated
electrons or holes can be described by a quasi-Fermi level
(namely, EF,n or EF,p). The potential difference between the
electron and hole quasi-Fermi levels is termed the photo-
voltage or the Voc.
Si + h𝜈 → e− + h+ (1)
In an acidic electrolyte cell, the photogenerated elec-
tron and hole undergo the two half reactions of PEC water
splitting on the cathode and anode, respectively, which are
expressed by following the two equations.18
( )
4H+ + 4e− → 2H2 E◦ H+ ∕H2 = 0.00 VNHE (2)
( )
2H2 O + 4h+ → 4H+ + O2 E◦ H2 O∕O2 = − 1.229 VNHE (3)
In an alkaline electrolyte cell, the corresponding two
half reactions are described similarly:
( )
4H2 O + 4e− → 2H2 + 4OH− E◦ H+ ∕H2 = − 0.828 VNHE (4)
( )
4OH− + 4h+ → 2H2 O + O2 E◦ H2 O∕O2 = + 0.401 VNHE (5)
The overall water splitting reaction is the same regard-
less of the pH value of the electrolytes:
2H2 O + 4h𝜈 → 2H2 + O2 (6)
The thermodynamic potential for water electrolysis
(Equation 6) is 1.23 V, which corresponds to a Gibbs free en-
ergy change of 237.2 kJ mol−1 for the decomposition of one
mole of H2O. What happens in practice is that hundreds of
millivolts overpotential (η) are needed to actuate the water
splitting, resulting in an electrolysis voltage greater than
1.23 V, as shown in Equation 7.26 The overpotentials are con-
sisted of three parts: OER overpotential, HER overpotential,
and overpotential induced by all the resistive losses.
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|
CHENG et al.3
VEC = 1.23 V + 𝜂 OER + 𝜂 HER + 𝜂 R (7)
Loading HER and OER catalysts on a photocathode
and photoanode, respectively, is an effective strategy to
lower ηOER and ηHER.
2.2 | Semiconductor band bending and
charge carriers separation
Photoexcited electrons and holes of a single semiconductor
are prone to recombination in the bulk and at the surface/
interface, resulting in a quite low energy conversion effi-
ciency.25 However, the construction of junctions, such as
p-n homojunctions by doping impurity elements and het-
erojunctions by fabricating semiconductor/semiconductor
or metal/semiconductor contact, can form an electric field
to promote the migration of photogenerated electrons and
holes. This electric field is formed in the space charge region
(SCR), which can induce the band bending of the semicon-
ductor. Here, we only take metal/semiconductor contact as
an example to introduce the band bending. There are other
conditions that can induce the band bending, which are dis-
cussed in detail by Yates et al.27
An ideal energy band bending diagram of metal and
n-type semiconductor contacts is illustrated in Figure 2,
W is the work function of contact material defined as the
energy difference between the EF and the vacuum level
(Evac).27 When the metal work function (Wm) is higher
than that of the semiconductor (Ws) (Figure 2A), the
electrons of the semiconductor continuously transfer to
the metal until the Fermi levels of both sides are aligned.
Under equilibrium, a positive charge layer (or depletion
layer) is formed near the surface of the semiconductor, and
a large number of electrons are accumulated on the metal
surface, thereby forming the SCR at the metal/semicon-
ductor interface. In the SCR, the VB and CB bend upward
toward the interface, which leads to an electron barrier
(i.e., Schottky barrier). When Wm < Ws (Figure 2B), the
electrons of the metal flow to the semiconductor surface,
resulting in the formation of electrons accumulation layer
near the surface of the semiconductor and the downward
band bending in the SCR, which leads to a hole barrier.
3 | STRATEGIES FOR
ENHANCING PEC PERFO RM AN CE
3.1 | Enhancing light harvesting
Production of electron-hole pairs via light harvest-
ing is the first step in PEC water splitting procedure.
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4 |
CHENG et al. CHENG et1529
al.

F I G U R E 2 Energy band diagrams of

metal and n-type semiconductor contacts.
(A) Wm > Ws, (B) Wm < Ws

F I G U R E 3 Different microstructures of bare Si. (A) and (B) the top-viewed and cross-sectional SEM images of n+p-Si micropyramid
arrays, (C) reflectance spectra of the as-prepared samples. Reprinted with permission from Ref. [28] Copyright 2019 Elsevier. (D) and (E)
the top-viewed and cross-sectional SEM images of bare Si microwires. (F) reflectance spectra of the as-prepared samples. Reprinted with
permission from Ref. [34] Copyright 2017 Elsevier

It is vital to improve the light harvesting efficiency of
a photoelectrode.24 Although Si semiconductor can
absorb almost the entire solar spectrum, the planar
Si displays strong light reflection. Therefore, it is nec-
essary to construct the specific surface structures
to enhance light absorption, such as Si microstruc-
tures (micropyramids,28-32 microwires,33-35 micropo-
rous Si36,37) and nanostructures (nanopyramids,38,39
nanowires,40-48 nanopillars,49-51 nanorods,52,53 nano-
spheres,54 etc.). Both the micro- and nano-structures

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CHENG et al.
can increase light harvesting via the multiple reflections
and scattering.55,56 Si microstructures such as micropyr-
amids are obtained by mature and simple chemical wet
etching technique, which has been applied on a large
scale in Si solar cell industry. In contrast, the prepa-
ration of Si nanostructures is expensive and compli-
cated, for example, metal-assisted wet chemical etching
(MACE) and deep reactive ion etching (DRIE, namely,
dry etching).57 On the other hand, for Si microstruc-
tures, the migration path of photogenerated carriers is
long, which easily leads to their secondary recombina-
tion and a low efficiency. In contrast, nanostructures
possess a shorter carrier migration path, which can en-
hance STH efficiency.58
3.1.1 | Microstructures
Wet chemical/electrochemical etching technique is
frequently applied to prepare microporous and micro-
pyramidal structure of Si substrate.28,30,32,36 Porous Si
material could shorten the collection pathway of carri-
ers and increase the active sites due to plenty of inter-
connected pores and large electrolyte accessible surface
area.59 Hossen et al. fabricated macro-porous Si by elec-
trochemical etching, and then deposited α-Fe2O3 on it.
The prepared heterostructure Fe2O3/porous Si showed
good performance in low bias region (<0.8 V vs. RHE).37
Zhang et al. prepared the n+p-Si micropyramid photo-
cathode with an omnidirectional broadband light har-
vesting ability of solar light, as shown in Figure 3A,B.28
Due to the unique micropyramid architectures, the n+p-
Si exhibits a very low reflectance in the wavelength of
400–1000 nm (Figure 3C). Yang et al. also reported the
micro-pyramidal textured silicon wafer for enhanced
high light absorption.32 Compared to upright pyramids,
Si-inverted pyramid arrays (SiIPs) can further reduce
the reflection. Zhao and Yuan et al. fabricated the SiIPs
via facile Cu-assisted chemical etching, which exhibit
a mean reflectivity of ~6.55% in the wavelength of
300–1100 nm.60
Liu and Wei et al. reported the high-quality, compact,
and uniformly one-dimensional structural Si microwire
arrays (MWs) constructed by photolithography and dry
etching preparation techniques, as shown in Figure 3D
and E.34 Compared with the planar structure, the Si MWs
provided a higher surface area of light-harvesting. In the
wavelength range of 450–900 nm, the reflectance of Si
MWs is very low (Figure 3F).
In addition, Wu and Li et al. verified the effects of silicon
wire array (Si WA) size on the performance of PEC hydro-
gen production.35 They found that the effects were possi-
bly different for Si photocathode with or without surface
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CHENG et al.5
passivation. As the length of the wire array increases, the
PEC hydrogen production performance of bare Si WA
photocathode is gradually getting worse, whereas a con-
trary trend is observed for Si WA photocathode passivated
through the deposition of metal oxides. The reflectance
spectra of these samples show that the overall reflectance
of Si WA extremely decreases compared to that of planar
Si.
3.1.2 | Nanostructures
During the past decade, Si nanostructures have played
an important role in optimizing Si photoelectrodes to
boost the conversion efficiency of solar energy to hy-
drogen, especially nanowires (NWs).56,61-67 These na-
noarrays have high aspect ratios, when incident light
travels into these nanoarrays, the multiple reflections
and scattering happen within the intervals. It follows
that the transmitting paths of light become longer in the
Si absorber and further increase the capability for cap-
turing photons.55,56 Peng et al. utilized a gold-sensitized
n-Si/n-ZnO core/shell NW array photoanode to achieve
unbiased water splitting.65 Wang and Chen et al. fabri-
cated n-Si NWs via metal-catalyzed electroless etching
(Figure 3A,B).68 Due to the improved light reflection,
scattering, and interference, the nanowires based on
Si core showed higher light absorptance compared to
the planar Si substrate, The length and diameter of n-Si
NWs prepared by metal-catalyzed electroless etching
are about 4 μm and 100 nm, respectively.
Si nanopillar arrays possess the strong light absorp-
tion properties as the same as nanowires. The rough
surface and high density of nanopillars can effectively
enhance the scattering and reduce the reflection.
Zhang et al. prepared a bamboo shoot-like nanopil-
lars structure vertically aligned on p-Si substrate via
the technique of cesium chloride lithography.49 These
nanopillars have the average length of about 1 µm and
the average diameter of 200 nm, which reduce the re-
flectance to below 10% in the wavelength range of 400–
1100 nm. After integrated with the amorphous NiCoSex
cocatalyst, the Si cathode performed a high photocur-
rent density of -−37.5 mA cm−2 at 0 V vs. RHE in 0.5 M
H2SO4 electrolyte. Iatsunskyi et al. synthesized Si nano-
pillars via metal-assisted chemical etching and nano-
sphere lithography, subsequently fabricated TiO2 onto it
(Figure 4C,D).51 They found that the reflectance of Si/
TiO2 core-shell nanopillar arrays fell below 6% in UV
and visible spectrum.
Si photoelectrodes with nanorods morphology can
also prolong the diffusion path of incident light and re-
duce the reflection of photons. And these nanostructures

6 |
CHENG et al.
can enlarge Si surface area and expose more action
sites as compared to planar Si, such as Si nanorods
(Figure 4E,F).52 Catalyzed by few-layer MoS2 flakes, the
p-Si nanorods achieved a high saturated photocurrent
density of 42.3 mA cm−2 in 0.5 M H2SO4 aqueous solu-
tion. Nordin et al. utilized waste-biomass sources (i.e.,
oil palm kernel shell), combined with a chemical vapor
deposition (CVD) technique to manufacture silicon na-
norods and nanowires with band gap energies of about
1.8 eV and 1.9 eV, which exhibit visible light absorption
capability.53 Such a tunable optical energy gap of Si ma-
terial makes it potential for PEC water splitting. Zhou
et al. successfully synthesized Ag-core Si-shell nano-
spheres (Ag@Si NSs) owned high surface area ratio and
large curvature.54 When coated with ultrathin MoS2
nanoflakes as a cocatalyst, the Ag@Si NSs exposed more
active sites to drive water reduction.
Besides the aforementioned NWs and nanorod arrays,
Si nanoparticles and porous silicon nanostructures can
also enhance light harvesting.57 Interestingly, Bang and
Lee et al. found the carrier concentration in tapered Si
nanoporous arrays to be less than that of planar Si, be-
cause the negatively charged ions and defects on the sur-
face of Si nanostructures are repulsive to electrons.69 As a
result, an electric field is created at the interface between
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CHENG et1531
al.
F I G U R E 4 SEM images of Si
substrate nanostructures. (A) and (B)
SEM cross-sectional image of n-Si NW/CN
photoanode. Reprinted with permission
from Ref. [68] Copyright 2018 Elsevier.
(C) SEM image of SiNP array, and (D)
tilted SEM image of SiNP/TiO2/ZnO.
Reprinted with permission from Ref. [51]
Copyright 2020 Elsevier. (E) cross-section
SEM image of p-SiNRs, and (F) the
vertically-standing, few-layer MoS2 flakes
on SiNRs. Reprinted with permission
from Ref. [52] Copyright 2021 Elsevier
crystalline mother Si and Si nanostructures. The electric
field can inhibit charge recombination and enhance the
photovoltage of the nanostructured Si electrode.
3.2 | Band structure engineering for
efficient charge separation and enhanced
photovoltage
During the generation processes of photoexcited charge
carriers of Si-based photoelectrodes, the electrons and
holes are peculiarly prone to recombine, which leads to
the losses of photovoltage and lowered STH conversion
efficiency.21 To suppress the recombination, reduction of
defects density present at the interface and construction
of Si homojunction and/or heterojunction are all effective
routes.22,23 With the aid of an electric field based on en-
ergy band engineering, the separation and transport of the
photogenerated carriers could be successfully achieved.
A high photovoltage can be obtained by engineering the
interface energetics based on the work function differ-
ence of the contact materials.14,22,70-72 In this part, vari-
ous surface/interface engineering strategies of Si-based
photoelectrodes are summarized and discussed in terms
of homojunction and heterojunction. Tables 1 and 2 list
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1532
CHENG et al. |
CHENG et al.7

some performances of Si photoelectrodes with different 3.2.2 | Construction of heterojunction

junctions in a three-electrode system in recent five years.
3.2.1 | Construction of homojunction
For monocrystal Si-based photoelectrode, construction
of a buried p-n homojunction is desirable method to pro-
mote the separation of photoexcited carriers and enhance
the photovoltage required for overall water splitting.28,87-89
Usually, the n+ and p+ emitter layers are prepared by
thermal diffusion of POCl3 and BCl3 precursor, respec-
tively.78,79 Both POCl3 and BCl3 are low-boiling liquids,
which can be carried with N2 as a carrier gas into a thermal
diffusion reactor. Shen et al. prepared a P-doping n+-p-Si
homojunction achieving a high photovoltage of ~0.6 V.80
Based on that, they constructed a dual-photoelectrode de-
vice consisting of an n+n-p+-Si photocathode and a p+p-
n+-Si photoanode. After coupling with Ni protection layer
and a bifunctional Ni-Mo catalyst, this device realized
water splitting under zero bias condition.90 Wu and Li
et al. introduced the “TOPCon” c-Si PV cell based on the
embedded p+-n-Si homojunction and the boron-doped p+
emitter. After integrating with α-Fe2O3 photoanode, they
realized the PEC/PV tandem system for solar-driven over-
all water splitting without bias.31
The advantages of constructing Si homojunction in-
clude simple preparation process, mature technology, and
low cost. It can also effectively promote the separation
of photogenerated carriers in the bulk. Nevertheless, the
high surface doping concentration would decrease the
photovoltage.
Compared with that of homojunction, construction of Si
heterojunction has a wider selection of materials, which
is conducive to the generation of higher voltage. The het-
erojunction of wide band gap semiconductor and Si can
effectively extend the light absorption of short wavelength
region.21 The fabrication techniques of Si heterojunc-
tions include atomic layer deposition,91 reactive radio
frequency magnetron sputtering,92 electron beam evapo-
rator,93 and molecular beam epitaxy.94 These technologies
possess high cost and complex equipment. In addition,
heterojunctions frequently induce high-density interface
defects as the recombination centers of photoexcited car-
riers. Therefore, the reduction or elimination of interface
defects is a key part to improving a photovoltage.
Semiconductor/semiconductor heterojunction
The semiconductor/semiconductor junction is induced
by two semiconductors contact with different band gaps,
which is often adopted in a tandem configuration cell.
Due to the presence of an electric field, photogenerated
carriers can quickly separate at the interface between two
semiconductors. Wide band gap semiconductor is often
chosen in Si-based photoelectrodes. Under illumination,
the top semiconductor with large band gap can absorb
the UV and a small portion of visible light, such as TiO2,95
while the rest photons are absorbed in the p-Si substrate.
Moreover, the introduction of TiO2 insertion layer not
only improves the carrier separation but also regulates the
interface mismatch between Si and cocatalyst layer.91 Kim
and Jang et al. coupled Si-based photocathode with TiO2

TABLE 1 PEC water splitting performances of Si-based photocathodes with different junctions

Onset
potential Photocurrent Published
Photocathode Type Electrolyte (pH) vs. RHE density at 0 VRHE Stability year [Ref.]
n+-n-p+-Si/MoS2 HOJ* 0.5 M H2SO4 (0.3) +0.5 V −36.33 mA cm−2 10 h at 0 VRHE 2019 [73]
HEJ*
n+p-Si/Ti/NiSxOy HOJ 1.0 M KOH (14.0) +0.5 V −26 mA cm−2 6 h at 10 mA cm−2 2019 [28]
HEJ
p-Si MWs@CoMoSx HEJ 0.5 M H2SO4 (0.3) +0.192 V −17.2 mA cm−2 500 min at 0 VRHE 2017 [34]
−2
p-Si/Ni(TEOA)2Cl2 HEJ 0.5 M H2SO4 (0.3) +0.11 V −5.57 mA cm 24 h at −0.4 VRHE 2018 [74]
−2
p-Si/Co2P HEJ 0.5 M H2SO4 (0.3) +0.38 V −35.2 mA cm 150 h at 0 VRHE 2019 [38]
ITO/Al2O3/n-Si/Ti/TiO2 HEJ 1.0 M HClO4 (0) +0.57 V −35.2 mA cm−2 300 h at 0 VREH 2020 [72]
−2
p-Si/MoS2 NRs HEJ 0.5 M H2SO4 (0.3) +0.72 V −42.3 mA cm 15 h at 0 VRHE 2021 [52]
−2
p-Si/CN/TiO2 NRs/NiCoP HEJ 1.0 M KOH (14.0) +0.24 V −19.87 mA cm 3 h at 0 VREH 2021 [75]
p-Si/graphene/MoP HEJ 0.5 M H2SO4 (0.3) +0.24 V −21.8 mA cm−2 10 h at 0 VREH 2021 [76]
−2
p-Si/TiO2/WP HEJ 1.0 M KOH (13.9) +0.27 V −15 mA cm 110 h at 0 VRHE 2021 [77]
Note: HEJ*, heterojunction; HOJ*, homojunction.
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8 |
CHENG et al. CHENG et1533
al.

TABLE 2 PEC water splitting performances of Si-based photoanodes with different junctions

Onset
potential Photocurrent density Published
Photoanode Type Electrolyte (pH) vs. RHE at 1.23 VRHE Stability year [Ref.]
np+-Si/SiOx/NiFe HOJ 1.0 M KOH (14.0) 0.89 V 30.7 mA cm−2 100 h at 1.80 VRHEa 2016 [78]
HEJ
n+-p-Si/SiOx/Ni/ HOJ 1.0 M KOH (13.6) 0.78 V 37 mA cm−2 68 h at 1.02 VRHE 2018 [79]
NiOx/NiFe-LDH HEJ
n+-p-Si/Ni/Ni-O HOJ 1.0 M NaOH (13.6) 0.93 V 39.7 mA cm−2 100 h at 1.02 VRHE 2019[80]
HEJ
n-Si/NiSe2 HEJ 1.0 M KOH (14.0) 0.7 V 5.8 mA cm−2 13 h at 1.23 VRHE 2016 [81]
n-Si/SiOx/Al2O3/ HEJ 1.0 M KOH (14.0) 0.997 V 19.2 mA cm−2 200 h at 1.70VRHE 2017 [82]
Pt/Ni/Ni(OH)2
n-Si/SiOx/Ni@ HEJ 1.0 M NaOH (14.0) 1.03 V 36.4 mA cm−2 300 h at 1.73 VRHEa 2017 [83]
Ni(OH)2
n-Si/SiOx/Al2O3/ HEJ 1.0 M KOH (14.0) 0.85 V 28 mA cm−2 80 h at 1.23 VRHE 2019 [71]
Ni/NiOx/
NiOOH
n-Si/Ni/NiOOH/ HEJ 1.0 M KOH (14.0) 1.0 V 25.2 mA cm−2 20 h at 1.23 VRHE 2020 [84]
NiFe
n-Si/SiOx/NiFe HEJ 1.0 M KOH (13.6) 0.96 V 29.5 mA cm−2 14 h at 1.5 VREH 2020 [85]
−2
n-Si MPs@Fe3O4 HEJ 0.5 M Na2SO4 (6.8) 0.27 V 0.10 mA cm 4 h at 1.23 VHRE 2021 [32]
n-Si/TiO2/In2O3 HEJ 1.0 M NaOH 0.6 V 27 mA cm−2 5 h at 1.6 VHRE 2021 [86]
a
The stability of the photoanode was tested in 1.0 M K-borate electrolyte.

F I G U R E 5 (A) SEM image of the

n-doped 3C-SiC layer deposited on
Si (100). (B) Energy-band diagram of
p-Si/n-type 3C-SiC heterojunction cell
under 1 sun illumination. (C) The setup
to characterize the photocathodes. (D)
J-V characterization of four samples: 3C-
SiC/p-Si, two types of Au NPs on 3C-SiC/
Si and Pt NPs on 3C-SiC/Si. Reprinted
with permission from Ref. [98] Copyright
2017 Elsevier

1534
CHENG et al.
F I G U R E 6 (A) Schematic diagram of the band bending using dendritic Ag/Si nanostructures as photoanode under illumination. (B)
Linear sweep voltammetry (LSV) curves of dendritic nanostructures under white light illumination of 50 mW cm−2 in natural water. (C)
Applied bias-photon-to-current conversion efficiency of dendritic nanostructures as a function of applied potential vs. Ag/AgCl. Reprinted
with permission from Ref. [44] Copyright 2018 Elsevier
(Eg =2.9 eV) nanorods and then modified with MoS2 na-
noplates to promote alkaline water splitting under zero
bias condition.93
Semiconductor/semiconductor heterojunctions can be
classified into the p-p heterojunction, n-n heterojunction,
and p-n heterojunction. They all induce band bending at
the contact interface, but the band bending degree of p-n
heterojunction is larger than that of the others because
the Fermi-level difference between p-type and n-type
semiconductors is the largest before contact.14 Thus, in
general, the photovoltage of p-n heterojunction is higher
than that of n-n heterojunction and p-p heterojunction.
The p-p heterojunction of c-Si/a-SiC photocathodes
for water splitting was constructed by Meija et al.92 In
this study, aluminum-doped amorphous SiC grown on
p-Si substrate was prepared by reactive Radio Frequency
Magnetron Co-sputtering technique. After the anneal-
ing treatment, the ohmic contacts were achieved, which
allowed the electrons to move easily through c-Si/a–SiC
interface. A saturated photocurrent of 17 mA cm−2 at
−1.75 V vs. Ag/AgCl electrode was achieved in 1.0 M of
H2SO4 electrolyte.
Krol et al. constructed a simple n-n heterojunction
photoanode of n-Si and n-type α-Fe2O3.96 Due to the lower
work function of Si, an upward band bending toward n-
type Fe2O3 is occurring while the band levels of n-type
Fe2O3 are also bending upward at the n-type Fe2O3/liquid
junction. Such two upward bands bending facilitated the
separation and transfer of photogenerated holes and elec-
trons. The prepared photoanode generated a photovoltage
of about 0.3 V. Shi et al prepared the n-Si/α-Fe2O3 n-n
heterojunction photoanode that generated a photocur-
rent density of 5.28 mA cm−2 at 1.23 V vs. RHE and a low
onset potential of 0.5 V vs. RHE in 1.0 M of NaOH solu-
tion.97 The InGaN/Si double-junction photocathodes con-
sisting of n+-InGaN/n+-Si heterojunction achieved ABPE
of ~9.5% at 0.4 V vs. RHE in 0.5 M of H2SO4 solution.94
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CHENG et al.9
Privitera et al. prepared an n-type 3C-SiC layer as a pro-
tective layer on p-Si substrate via chemical vapor deposi-
tion, as shown inFigure 5. 98 Such a p-Si/n-type 3C-SiC
heterojunction restrained effectively the photoexcited
holes injection into the SiC layer due to the upward band
bending toward p-Si, and protect the p-Si substrate from
photo-corrosion. The prepared photocathode performed a
saturated photocurrent of 30 mA cm−2 at −1.4 V vs. RHE
and the stability for 9 h with a current of 12 mA cm−2 in
1.0 M of KOH solution. Bao et al. reported a hierarchical p-
Si/n-ZnO@Au heterostructure exhibiting a superior per-
formance for PEC water splitting compared to the bare Si
and Si/ZnO NRs array.70 The vertically oriented ZnO NRs
array hydrothermally grown on Si substrate can not only
provide long scattering paths for enhanced light absorp-
tion but also expose large surface areas for active reaction
sites. But more than that, their high-quality conducting
channels can steer the collection of photoelectrons well.
Except for heterojunctions composed of Si and other
semiconductors, heterojunctions can also be constructed
with amorphous Si (a-Si), microcrystalline Si (μc-Si),
and crystalline Si (c-Si).99,100 A thin film of hydrogenated
a-Si (a-Si:H) is often used on the top of Si-based photo-
electrodes due to its efficient UV-light conversion.101 An
a-Si:H/μc-Si/c-Si heterojunction solar cell could generate
a high photovoltage (>1.9 V), which is enough for stand-
alone water splitting. Urbain et al. combined hematite
photoanodes with a-Si:H/a-Si:H/μc-Si:H heterojunction
photocathodes, achieving bias-free current density of
1.1 mA cm−2 in 1.0 M of NaOH electrolyte at 100 mW
cm−2 of illumination intensity.102
Metal–semiconductor heterojunction
Xing et al. investigated the effect of the insertion of metal
W between n-WO3 and p-Si.103 They confirmed that the
introduced W layer eliminated Si-O bands at the interface
and constructed n-WO3/W/p-Si electrode exhibited ten

10 |
CHENG et al.
F I G U R E 7 (A) The energy band alignment of n-Si/SiO2/Ni/NiOOH/NiFe photoanode for water oxidation. (B) Linear sweep
voltammetry (LSV) curves of various Si photoanodes in 1.0 M KOH electrolyte under illumination. (C) The chronoamperometric curves of
n-Si/SiO2/Ni/NiOOH and n-Si/SiO2/Ni/NiOOH/NiFe photoanodes in 1.0 M KOH electrolyte under illumination. Reprinted with permission
from Ref. [84] Copyright 2020 RSC Pub
times higher photocurrent density compared to n-WO3/
p-Si. A Schottky barrier induced by metal–semiconductor
contact exists in Ag/Si NW contact (Figure 6).44 Due to the
band bending and Ag dendritic nanostructures, the pho-
togenerated carriers were effectively separated and then
holes were quickly transferred to Ag/electrolyte interface
for participating OER. In natural water (pH 7), the Si NW
cooperated with Ag dendrites achieved a relatively high
ABPE of 4%.
Metal-insulator-semiconductor heterojunction
As for metal/semiconductor contact, it often shows a
deviation from the ideal contact due to Fermi-level pin-
ning.82,104 Atoms at the surface of a semiconductor pos-
sess plenty of unsaturated dangling bonds due to the
termination of lattice periodicity. These dangling bonds
cause surface states in the band gap at semiconductor
surface or interface between metal and semiconduc-
tor. Generally, the density of surface or interface states
is much larger than the bulk dopant states, the surface
Fermi level of the semiconductor is almost unaffected
by the bulk dopant concentration and is pinned by the
surface states, leading to Fermi-level pinning. Such
high density of surface states not only make heterojunc-
tion barrier completely irrelevant with the function of
semiconductor but also enhance the surface recombina-
tion of holes and electrons. To remove the pinning, the
metal/Si semiconductor interface should be modified by
introducing additional passivation layers, such as Al2O3,
SiO2, and TiO2. When an Al2O3 or SiO2 insulator layer is
introduced between metal and Si semiconductor, metal-
insulator-semiconductor junction (MIS junction) as a
passivation layer is formed. The passivation layer not
only removes most of the harmful surface states out of
the band gap region through the formation of chemical
bond but also avoids or reduces the electrochemical cor-
rosion of photoelectrodes. Hence, construction of MIS
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CHENG et1535
al.
junctions is an effective approach to regulate the inter-
face band structure of Si-based photoelectrodes.
Generally, there is a native SiO2 film on the bare-Si
surface in air. Thus, it is very common to employ the na-
tive SiO2 as the passivation layer for Si-based photoelec-
trodes.105,106 Ultrathin SiO2 layer allows photogenerated
carriers to pass through due to the tunneling effect.107
However, thicker SiO2 layer limits the carriers transfer at
the interface and decreases the photovoltage. Thus, it is vi-
able to first remove native oxides film through HF etching
and then refabricate controllable thin SiO2 layer.108 The
thin SiO2 layer can be grown by wet chemical method,82
atomic layer deposition (ALD),108 thermal oxidation,109
etc.
Based on MIS structure, Liu et al. fabricated an n-Si/
SiO2/Ni MIS photoanode.84 Then the prepared photoan-
ode was activated through cyclic voltammetry scans in
1.0 M of KOH electrolyte under illumination to generate
a highly active NiOOH shell around the Ni core. Due to
the increase of the work function of Ni (4.82 eV) upon ox-
idation to NiOOH (5.42 eV), the electron's barrier height
of n-Si/SiO2/Ni/NiOOH increases, that results in a high
photovoltage. Finally, an ultrathin NiFe nanolayer was de-
posited on the photoelectrode surface. The barrier height
of n-Si/SiO2/Ni/NiOOH/NiFe is eventually increased to
1.01 eV (Figure 7A). Such a significant barrier height can
effectively expedite the separation and transfer of holes.
The prepared photoanode exhibited a current density of
about 25.2 mA cm−2 at 1.23 V vs. RHE and run stably for
20 hours in 1.0 M of KOH electrolyte (Figure 7B,C).
To further reduce the Fermi-level pinning, the SiOx
coupled with tunnelling Al2O3 layer is also a valuable de-
sign for the optimization of MIS structure, such as n-Si/
SiOx/Al2O3/Pt/Ni photoanode.82 Gong et al. investigated
the effect of energy band structure engineering on PEC
water splitting performance of the n-Si/SiOx/Al2O3/Ni/
NiOx/NiOOH.71 Due to the passivation of tunnelling

1536
CHENG et al.
Al2O3 layer, the adverse defects at the interface of Si and
Ni film can be terminated, thereby reducing the recom-
bination of charges at the interface during the trans-
fer process. After depositing Ni thin film on n-Si/SiOx/
Al2O3 surface, the constructed MIS structure generated a
high photovoltage of 640 mV and the photocurrent den-
sity of 28 mA cm−2 at 1.23 V vs. RHE in 1.0 M of KOH
solution. Under the protection of Ni film, the n-Si/SiOx/
Al2O3/Ni/NiOx/NiOOH photoanode continuously pro-
duced oxygen for 80 hours at 1.23 V vs. RHE without any
degradation. They further investigated the effect of MIS
junction on Si photocathode.72 Figure 8A showed the
schematic energy band diagrams of ITO/Al2O3/n-Si MIS
junction, the band is bending upward toward ITO layer
due to its high work function and simultaneously form-
ing an electron barrier, allowing holes to flow through the
MIS to the counter electrode. Additionally, the transpar-
ent ITO can avoid the parasitic light absorption of metal in
MIS structure. As a result, the ITO/Al2O3/n-Si photocath-
ode generated a high photovoltage of 570 mV (Figure 8B).
Meanwhile, the catalysts were placed on the back side of
MIS junction to avoid the light-shielding problem. Such an
illumination-reaction decoupled ITO/Al2O3/n-Si/Ti/TiO2
photocathode exhibited a superior photocurrent density
of 35.2 mA cm−2 at 0 V vs. RHE. Furthermore, to illustrate
the practical application potential of the MIS photoca-
thode, they constructed a PEC tandem cell composed of
the ITO/Al2O3/n-Si/Ti/TiO2 photocathode and a BiVO4/
FeOOH/NiOOH photoanode to realize unassisted overall
F I G U R E 8 (A) Schematic energy
band diagrams of n-Si based photocathode
constructed from ITO/Al2O3/n-Si MIS
junction. (B) LSV curves of n-Si MIS
photocathode and n+-Si/Ti/TiO2/Pt
cathode. (C) LSV curves of n-Si MIS
photocathode and BiVO4/FeOOH/NiOOH
photoanode in a 3-electrode configuration,
respectively. (D) The I-t curve for two
electrodes cell under illumination.
Reprinted with permission from Ref. [72]
Copyright 2020 Oxford University Press
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CHENG et al.
11
water splitting. And through the intersection of the LSV
curves of the photoanode and photocathode tested in a
3-electrode configuration, a theoretical photocurrent den-
sity of 1.73 mA cm−2 was obtained (Figure 8C). Finally,
the actual unbiased photocurrent in the 2-electrode con-
figuration was 1.39 mA cm−2, and the calculated overall
STH efficiency is 1.71% (Figure 8D). The light harvesting-
catalytic reaction sites decoupled MIS photocathode are
potential to realize an unassisted overall water splitting.
In addition to the aforementioned heterojunctions, a
strong electric field induced by the semiconductor/liquid
junction is favorable to the charge separation as well.23,110
Due to the (electro)chemical corrosion of Si in an aque-
ous electrolyte, a bare Si photoelectrode cannot be di-
rectly used for water splitting. Modifying the Si surface
with molecular reagents (perylene-diimide derivative),
which could capture electrons from the p-Si surface and
subsequently transferred to the cocatalyst, can effectively
inhibit the corrosion.111 Moreover, depositing a protective
layer or cocatalyst on Si surface is a common strategy to
construct a favorable semiconductor/liquid junction.112,113
3.3 | Modification of protection
layers and cocatalysts
Long-term stability is a critical indicator in the practi-
cal application of Si-based photoelectrodes for PEC
water splitting, while Si is prone to electrochemical

12 |
CHENG et al.
and photochemical corrosion.21,114 However, the in-
stability can be solved by depositing a transparent pas-
sivation layer and/or stable electrocatalysts, such as
stable oxide (TiOx,77,115,116), corrosion-resistant electro-
catalyst overlayer (Co2P,38 CoS2,33 MoS2,52 NiOx,80,87,88a
nd Ni(OH)2,83), or MIS structure (Ni,71,84 Ti,72 NiFe,85
Cu,117). Thanks to the sluggish reaction kinetics (high
overpotential) or water splitting on the Si photo-
electrodes,118 loading HER or OER cocatalysts to reduce
the overpotential for water reduction or oxidation are
necessary to achieve high STH conversion efficiency. It
is worth noting that catalysts can not only be used to ac-
celerate the reaction, but also directly used as a protec-
tion layer because of their excellent chemical stability.72
3.3.1 | Modification of protection layers
Modification of protection layers for Si-based photo-
electrode depends on an electrolyte solution. In acidic
solution, a Ti layer is stable, which can protect Si sub-
strate.72 Whether in acidic or alkaline solutions, a TiO2
film is an excellent corrosion-resistant material. Shen
et al. demonstrated that n+np+-Si/TiO2/Pt photocathodes
exhibited an unprecedented hydrogen evolution perfor-
mance with a high half-cell STH efficiency of 11.5% and
stability of 168 h in 1.0 M of HClO4 solution, due to the
high active Pt catalyst and protective TiO2 layer.119 In an
alkaline solution, a TiO2 layer can also effectively pro-
tect Si from corrosion.77,115,116,120,121 Lee and Park et al.
prepared a nanocrystalline TiOx film protected p-Si via
ALD technology, which ran stably for 40 hours in 1.0 M
of KOH solution.122 Moreover, a dense Ni film is also a
good protection lay in alkaline solution.105 In fact, the Si/
semiconductor layers (Section 3.2.2.1) and metal/insula-
tor layers discussed in MIS structure (Section 3.2.2.3) can
also be used as a protection layer,83 as well as cocatalyst
layers (see below).
3.3.2 | Modification of HER cocatalysts
For the PEC water splitting, hydrogen production is fa-
vorable in an acidic electrolyte, so the HER catalysts/co-
catalysts should be stable in the acidic solution. As the
efficient cocatalysts, noble metals (Ru89 and Pt119) are
often used for electrocatalytic water splitting. Plus, the Ti
and/or TiO2 protection layer can prevent the electrolyte
penetrating into the semiconductor and enable the pho-
toelectrode to operate stably for a long time. Gong et al.
prepared the ITO/Al2O3/n-Si/Ti/TiO2/Pt photocathode
exhibited a high photocurrent of −35.2 mA cm−2 at 0 V
vs. RHE and an excellent stability of 300 h in 1.0 M of
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CHENG et1537
al.
HClO4 solution.72 By integrating Ru-MoS2 catalysts with
Si, the n+p-Si/Ti/Ru-MoS2 photocathode achieved a con-
siderably high half-cell STH efficiency of 7.28% at 0.2V vs.
RHE in 0.5 M H2SO4 electrolyte solution.89
Because of the rareness and preciousness, noble met-
als are restricted in large-scale applications. The cost-
effective and earth-abundant candidates to catalyze HER
have been developed, such as transition metal alloy (Ni-
Mo,90 Ni-Fe117), metal phosphides (Co2P,38 GaP,46 NiC
oP,75 MoP,76 WP,77), sulfides (MoS252,54,93,123), selenides
(NiCoSex49), and CuCo hybrid oxide.116 Most of them act
as both HER catalysts and protective layers for Si-based
photocathodes. Due to the conform and continuous Co2P
overlayer, p-Si/Co2P photocathode produced hydrogen
steadily and continuously for 150 h under high photocur-
rent density of 30 mA cm−2 in 0.5 M of H2SO4 solution.38
Zhang and Liu et al. coated the mesoporous tungsten
phosphide (WP) protective layer on p-Si/TiO2 photoca-
thode, which showed both a high photocurrent density
of −15 mA cm−2 and good stability of 110 h in 1.0 M of
KOH solution.77 Besides, cobalt dichalcogenide-covered
p-Si also passivated the silicon surface and made it wide
range pH-tolerable.33 Kim et al. reported the p-Si/TiO2 na-
norods/MoS2 nanoplates photocathode achieving an un-
assisted STH efficiency of 6.6% in alkaline solution, which
is the highest among p-Si photocathodes.93 Moreover,
MXene (two-dimension transition metal carbides and ni-
trides) are good HER electrocatalysts with high electronic
conductivity. Modification of them on Si photoelectrode
has been explored.124-126 Alshareef and He et al. incorpo-
rated MXene to Si photoelectrode successfully for PEC
water splitting.127 The as-prepared Ru-N-S-Ti3C2Tx/n+n-
p+-Si photocathode achieved a high photocurrent density
to 37.6 mA cm−2 in 0.5 M of H2SO4 electrolyte, indicating
that MXene may become a competitive candidate as a co-
catalyst for PEC water splitting in the future.
3.3.3 | Modification of OER cocatalysts
Because of the nature of four-electron steps in OER, it is
generally accepted that the OER is much tardier than the
HER. Thus, it is essential to enhance the catalytic per-
formance and durability of OER catalysts/cocatalysts.128
As can be seen from the volcano plot among catalysts,
the state-of-the-art electrocatalysts are noble metal ox-
ides (RuO2129 and IrO2130). Their energy barrier of each
step in OER is almost equalized, resulting in the smallest
total overpotential.131 Thus, n-Si/SiO2/RuO2 photoanodes
could perform high OER performance.132-134
In addition, non-noble metal and oxide/hydrox-
ide have made outstanding contributions to reduce
the overpotential of water oxidation and enhance the

1538
CHENG et al.
durability of Si-based photoanodes, including the bi-
functional Ni-Mo,90 Ni-Fe,84,85,117 Fe3O4,32 NiOx,88,122
Co3O4,135 NiMoO4,136 and NiOOH.71,84 And during the
OER process, the surface metals are prone to be oxidized
and then converted into higher active oxides/hydroxides.82
Lewis et al. fabricated the n-p+-Si photoanode, with a reac-
tively sputtered NiOx layer, that produced steadily oxygen
over 1200 h in 1.0 M of KOH aqueous solution without
notable degradation.87 Shen et al. fabricated the porous
Ni-O/Ni/Si photoanode by electrodepositing Ni-S on Ni/
Si and subsequently PEC activating, which achieved an
energy conversion efficiency of 3.2% and a stability above
100 h in 1.0 M of NaOH electrolyte.80
To lower the overpotential and enhance the stability of
Si-based photoelectrodes, a high-active and stable catalyst
is first considered. Secondly, considering the interface is-
sues, it is vital to employ a dense, ultrathin and stable in-
terlayer to passivate the Si interface and further reduce the
recombination loss of photogenerated carriers. Layered
double hydroxide (LDH)-based materials have attracted
widespread attention in various applications due to their
unique layered structure with high specific surface area
and unique electron distribution, resulting in a good
electrocatalytic performance. Moreover, the existence of
multiple metal cations invests a flexible tunability in the
host layers; the unique intercalation characteristics lead to
F I G U R E 9 Cross-sectional SEM image of n-Si/a-TiO2/NiFe LDH photoanode (the top left), Cyclic voltammetry curves of deposition
of a-TiO2 layer (the top right) and Schematic of n-Si/a-TiO2/NiFe LDH photoanode (below). Reprinted with permission from Ref. [137]
Copyright 2020 ACS Applied Energy Materials
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|
CHENG et al.
13
flexible ion exchange and exfoliation. Thus, their electro-
catalytic performance can be tuned by regulating the mor-
phology, composition, intercalation ion, and exfoliation.128
However, LDH cannot effectively protect Si substrate
from electrolyte corrosion because of the open-channeled
structure, and the existence of LDH weakens the adhesion
of the catalyst and substrate leading to delamination. Jang
and Shin et al constructed an amorphous TiO2 interlayer
between the n-Si and the NiFe LDH to solve these issues,
as shown inFigure 9. 137 The as-prepared n-Si/a-TiO2/NiFe
LDH photoanode without the buried junction showed a
high photocurrent density of 36 mA cm−2 at 1.23 V vs.
RHE, and operated more stably compared to n-Si/NiFe
LDH. Dabirian et al reported an Si photocathode func-
tionalized with Cu/NiFe-LDH electrocatalysts.117 Due to
the high catalytic activity of NiFe-LDH, the photocathode
achieved STH efficiency of 11.31% under no-bias condi-
tion and stability of about 33 h in 1.0 M NaOH electrolyte.
4 | CONCLUSIONS AND O U TLO O K
PEC water splitting is a practical and feasible method
for solar-driven hydrogen production. To realize effi-
cient, cost-effective, and stable PEC water splitting, Si-
based photoelectrode materials are a good candidate.

14 |
CHENG et al.
This review presents the three effective strategies and
the recent progress, including (1) regulation of Si sur-
face morphology for enhancing light harvesting, (2)
band structure engineering to reduce recombination of
photogenerated carriers, and (3) modification of protec-
tion layers for long stability and loading cocatalysts on
Si-based photoelectrodes for accelerating water split-
ting. However, there is still a long way to go to achieve
commercial PEC water splitting. We think that follow-
ing issues should be addressed in future research: (1)
Due to insufficient photovoltage of a single Si-based
photoelectrode for water splitting, the development
of efficient, stable, and low-cost PV-PEC tandem cells
of Si with other semiconductor such as perovskite and
coupling two efficient Si-based photoelectrodes (pho-
toanode and photocathode) are promising approaches;
(2) Owing to parasitic light absorption induced by
catalyst and protection layer as well as the produced
gas bubbles on the electrode surface, the development
of dense cocatalyst layer with both high catalytic and
protective function not only reduce the parasitic light
absorption but also simplify the structure of Si-based
photoelectrode, and thereby reducing the fabrication
cost. Furthermore, spatial decoupling for light absorp-
tion and reaction sites can keep the light absorption
away from the reaction sites and remove the influence
of gas bubbles on the photo absorption, which can also
enhance the light absorption. (3) The thin passivate
layer between Si substrate and cocatalyst is prepared
usually via vapor deposition method with expensive
equipment. The development of new and cheap solu-
tion preparation methods is desirable to reduce the
manufacture cost.
ACKNOWLEDGMENTS
This work was supported by the National Key Research
and Development Program of China (2018YFB1502004),
and the National Natural Science Foundation of China
(21962010).
CONFLICT OF INTEREST
There are no conflicts to declare.
ORCID
Yuexiang Li https://orcid.org/0000-0003-3104-1772
REFERENCES
1. Jia J, Seitz LC, Benck JD, et al. Solar water splitting by
photovoltaic-electrolysis with a solar-to-hydrogen efficiency
over 30. Nat Commun. 2016;7:13237.
2. Kim JH, Kaneko H, Minegishi T, et al. Overall photoelectro-
chemical water splitting using tandem cell under simulated
sunlight. Chemsuschem. 2016;9(1):61-66.
20500505, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ese3.1087 by INASP/HINARI - PAKISTAN, Wiley Online Library on [18/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHENG et1539
al.
3. Qiu YLW, Chen W, Zhou G. Efficient solar-driven water split-
ting by nanocone BiVO4-perovskite tandem cells. Science
Advances. 2016;2(6):e1501764.
4. Nadeem MA, Idriss H. Effect of pH, temperature, and low
light flux on the performance (16% STH) of coupled triple
junction solar cell to water electrolysis. J Power Sources.
2020;459:228074.
5. Cao S, Chen Y, Wang CJ, He P, Fu WF. Highly efficient pho-
tocatalytic hydrogen evolution by nickel phosphide nanopar-
ticles from aqueous solution. Chem Commun (Camb).
2014;50(72):10427-10429.
6. Zhang W, Li W, Li Y, Peng S, Xu Z. One-step synthesis of
nickel oxide/nickel carbide/graphene composite for efficient
dye-sensitized photocatalytic H2 evolution. Catal Today.
2019;335:326-332.
7. Zeng D, Ong W-J, Zheng H, et al. Ni12P5 nanoparticles em-
bedded into porous g-C3N4 nanosheets as a noble-metal-free
hetero-structure photocatalyst for efficient H2 production
under visible light. J Mater Chem A. 2017;5(31):16171-16178.
8. He F, Wang Z, Li Y, Peng S, Liu B. The nonmetal modula-
tion of composition and morphology of g-C3N4-based pho-
tocatalysts. Appl Catal B. 2020;269:118828. doi:10.1016/j.
apcatb.2020.118828
9. Li Y, He R, Han P, et al. A new concept: Volume photocatalysis
for efficient H2 generation – Using low polymeric carbon ni-
tride as an example. Appl Catal B. 2020;279:119379.
10. Xie C, Yan D, Li H, et al. Defect chemistry in heterogeneous
catalysis: recognition, understanding, and utilization. ACS
Catalysis. 2020;10(19):11082-11098.
11. Li Y, Zhang W, Li H, et al. Ni-B coupled with borate-intercalated
Ni(OH)2 for efficient and stable electrocatalytic and photocat-
alytic hydrogen evolution under low alkalinity. Chem Eng J.
2020;394:124928.
12. Wang C, Wang K, Feng Y, et al. Co and Pt dual-single-atoms
with oxygen-coordinated Co-O-Pt dimer sites for ultrahigh
photocatalytic hydrogen evolution efficiency. Adv Mater.
2021;33(13):e2003327.
13. Gan J, Lu X, Tong Y. Towards highly efficient photoanodes:
boosting sunlight-driven semiconductor nanomaterials for
water oxidation. Nanoscale. 2014;6(13):7142-7164.
14. Hu Y, Huang H, Feng J, et al. Material design and surface/in-
terface engineering of photoelectrodes for solar water splitting.
Sol. RRL. 2021;5(4):2100100.
15. Das PK, Poonchi Sivasankaran R, Arunachalam M, et al.
Highly efficient and stable g-C3N4 decorated Ta3N5 nanotube
on n-Si substrate for solar water oxidation. Appl Surf Sci.
2021;565:150456.
16. Pinaud BA, Benck JD, Seitz LC, et al. Technical and economic
feasibility of centralized facilities for solar hydrogen production
via photocatalysis and photoelectrochemistry. Energy Environ
Sci. 2013;6(7):1983.
17. Krol RVD, Schoonman J. Photo-electrochemical production
of hydrogen. In: K. H, R. VdK, A. L., eds. Sustainable Energy
Technologies. Springe; 2008:121-142.
18. Dias P, Mendes A. Hydrogen production from photoelectro-
chemical water splitting. In: Lipman T, Weber A, eds. Fuel Cells
and Hydrogen Production. Springer; 2018: 1003-1053.
19. ᖡᮑ. 椕⪉⸲をⓆ㠿TOPCon䟄㻯ᇬHJT䟄㻯ₘ欈㟗䘖₥䟛儹㇤,
2021. https://www.thepaper.cn/newsDetail_forward_12915022

1540
CHENG et al.
20. Dumortier M, Tembhurne S, Haussener S. Holistic de-
sign guidelines for solar hydrogen production by photo-
electrochemical routes. Energy Environ Sci. 2015;8(12):
3614-3628.
21. Zheng J, Zhou H, Zou Y, et al. Efficiency and stability of narrow-
gap semiconductor-based photoelectrodes. Energy Environ Sci.
2019;12(8):2345-2374.
22. Jiang C, Moniz SJA, Wang A, Zhang T, Tang J.
Photoelectrochemical devices for solar water splitting – mate-
rials and challenges. Chem Soc Rev. 2017;46(15):4645-4660.
23. Jaegermann W, Kaiser B, Ziegler J, Klett J. Interface engineer-
ing of semiconductor electrodes for photoelectrochemical
water splitting: application of surface characterization with
photoelectron spectroscopy. In: Giménez S, Bisquert J, eds.
Photoelectrochemical Solar Fuel Production. Springer; 2016:
199-280.
24. Gao J, Sahli F, Liu C, et al. Solar water splitting with perovskite/
silicon tandem cell and TiC-supported Pt nanocluster electro-
catalyst. Joule. 2019;3(12):2930-2941.
25. Luo Z, Wang T, Gong J. Single-crystal silicon-based electrodes
for unbiased solar water splitting: current status and prospects.
Chem Soc Rev. 2019;48(7):2158-2181.
26. Cox CR, Lee JZ, Nocera DG, Buonassisi T. Ten-percent solar-to-
fuel conversion with nonprecious materials. Proc Natl Acad Sci
USA. 2014;111(39):14057-14061.
27. Zhang Z, Yates JT. Band bending in semiconductors: chemical
and physical consequences at surfaces and interfaces. Chem
Rev. 2012;112(10):5520-5551.
28. Jia Q, Yu C, Liu W, et al. High performance n+p-Si/Ti/NiSxOy
photocathode for photoelectrochemical hydrogen evolution in
alkaline solution. J. Energy Chem. 2019;30:101-107.
29. Kawde A, Annamalai A, Sellstedt A, et al. A microstructured
p-Si photocathode outcompetes Pt as a counter electrode to he-
matite in photoelectrochemical water splitting. Dalton Trans.
2019;48(4):1166-1170.
30. Li X, Li Y, Wang HJ, et al. Fabrication of a three-dimensional
bionic Si/TiO2/MoS2 photoelectrode for efficient solar water
splitting. ACS Appl. Energy Mater. 2021;4(1):730-736.
31. Xiao C, Zhou Z, Li L, et al. Direct growth of hematite film on
p+n-silicon micro-pyramid arrays for low-bias water splitting.
Sol Energy Mater Sol Cells. 2021;224:110987.
32. Zhang L, Chen W, Cheng L, et al. Integration of Fe3O4 nano-
spheres and micropyramidal textured silicon wafer with im-
proved photoelectrochemical performance. J Mater Sci Mater
Electron. 2021;32(4):5176-5185.
33. Chen CJ, Yang KC, Basu M, et al. Wide range pH-tolerable
Silicon@Pyrite cobalt dichalcogenide microwire array pho-
toelectrodes for solar hydrogen evolution. ACS Appl Mater
Interfaces. 2016;8(8):5400-5407.
34. Chen C-J, Yang K- C, Liu C-W, et al. Silicon microwire ar-
rays decorated with amorphous heterometal-doped molyb-
denum sulfide for water photoelectrolysis. Nano Energy.
2017;32:422-432.
35. Li L, Wu S, Zhou Z, Guo P, Li X. Size-dependent performances
in homogeneous, controllable, and large-area silicon wire array
photocathode. J Power Sources. 2020;473:228580.
36. Ismail ABM, Hossen MF. Porous silicon: A material of choice
in solar energy harvesting. In International Conference on
Advances in Electrical, Electronic and System Engineering, 2016.
IEEE. Putrajaya, Malaysia.
20500505, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ese3.1087 by INASP/HINARI - PAKISTAN, Wiley Online Library on [18/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
|
CHENG et al.
15
37. Hossen MF, Ismail ABM. Investigation on Fe2O3/por-Si photo-
catalyst for low-bias water-splitting. J Mater Sci Mater Electron.
2018;29(18):15480-15485.
38. Thalluri SM, Wei B, Welter K, et al. Inverted pyramid tex-
tured p-Silicon covered with Co2P as an efficient and stable
solar hydrogen evolution photocathode. ACS Energy Letters.
2019;4(7):1755-1762.
39. Park M-J, Heo J, Jee H, et al. Enhancement of the oxygen
evolution using a 21-μm-Thin c-Si photoanode with a nano-
pyramid texture. J Electrochem Soc. 2017;164(14):H1129
-H1132.
40. Shi MM, Pan XW, Qiu WM, et al. Si/ZnO core-shell nanowire
arrays for photoelectrochemical water splitting. Int. J. Hydrog.
Energy. 2011;36(23):15153-15159.
41. Ji JY, Zhang WH, Zhang HQ, et al. High density Si/ZnO core/
shell nanowire arrays for photoelectrochemical water splitting.
J Mater Sci Mater Electron. 2013;24(9):3474-3480.
42. Kargar A, Kim SJ, Allameh P, et al. p-Si/SnO2/Fe2O3 Core/
Shell/Shell nanowire photocathodes for neutral pH water split-
ting. Adv Funct Mater. 2015;25(17):2609-2615.
43. Chen Z, Ning MH, Ma G, et al. Effective silicon nanowire ar-
rays/WO3 core/shell photoelectrode for neutral pH water split-
ting. Nanotechnology. 2017;28(27):275401.
44. Dadwal U, Ali D, Singh R. Silicon-silver dendritic nanostruc-
tures for the enhanced photoelectrochemical splitting of natu-
ral water. Int. J. Hydrog. Energy. 2018;43(51):22815-22826.
45. Yang R, Ji Y, Li Q, et al. Ultrafine Si nanowires/Sn3O4
nanosheets 3D hierarchical heterostructured array as a photo-
anode with high-efficient photoelectrocatalytic performance.
Appl Catalysis B Environ. 2019;256:117798.
46. Xie GC, Jan SU, Dong ZJ, et al. GaP/GaPN core/shell nanowire
array on silicon for enhanced photoelectrochemical hydrogen
production. Chinese J. Catal. 2020;41(1):2-8.
47. Chen H, Wang P, Wang X, et al. 3D InGaN nanowire arrays on
oblique pyramid-textured Si (311) for light trapping and solar
water splitting enhancement. Nano Energy. 2021;83:105768.
48. Sheng WJ, Shi TL, Sun B, Jiang T, Liao GL. Fabrication of hier-
archical ZnO/Si nanowire structure for photoelectrochemical
cells. J Nanosci Nanotechnol. 2015;15(2):1331-1337.
49. Zhang H, Ding Q, He D, et al. A p-Si/NiCoSex core/shell nanopil-
lar array photocathode for enhanced photoelectrochemical hy-
drogen production. Energy Environ Sci. 2016;9(10):3113-3119.
50. Pavlenko M, Siuzdak K, Coy E, et al. Silicon/TiO2 core-shell
nanopillar photoanodes for enhanced photoelectrochem-
ical water oxidation. Int. J. Hydrog. Energy. 2017;42(51):
30076-30085.
51. Pavlenko M, Siuzdak K, Coy E, et al. Enhanced solar-driven
water splitting of 1D core-shell Si/TiO2/ZnO nanopillars. Int. J.
Hydrog. Energy. 2020;45(50):26426-26433.
52. Dang TC, Dang VT, Nguyen TD, et al. MoS2 hydrogen evolution
catalysis on p-Si nanorod photocathodes. Mater Sci Semicond
Process. 2021;121:105308.
53. Nordin FN, Alizadeh M, Nakajima H, et al. Photoelectrochemical
behavior of Si nanostructures grown by chemical vapor depo-
sition using waste-biomass sources. J Solid State Chem.
2021;300:122254.
54. Zhou QW, Su SQ, Hu D, et al. Ultrathin MoS2-coated Ag@
Si nanosphere arrays as an efficient and stable photocath-
ode for solar-driven hydrogen production. Nanotechnology.
2018;29(10):105402.

16 |
CHENG et al.
55. Kargar A, Sun KE, Jing YI, et al. Tailoring n-ZnO/p-Si
branched nanowire heterostructures for selective photo-
electrochemical water oxidation or reduction. Nano Lett.
2013;13(7):3017-3022.
56. Feng B, Deng J, Lu B, et al. Nanofabrication of silicon nanowires
with high aspect ratio for photo-electron sensing. Microelectron
Eng. 2018;195:139-144.
57. Liu D, Ma J, Long R, Gao C, Xiong Y. Silicon nanostructures for
solar-driven catalytic applications. Nano Today. 2017;17:96-116.
58. Oh I, Kye J, Hwang S. Enhanced photoelectrochemical hydro-
gen production from silicon nanowire array photocathode.
Nano Lett. 2012;12(1):298-302.
59. Li Z, Feng J, Yan S, Zou Z. Solar fuel production: Strategies
and new opportunities with nanostructures. Nano Today.
2015;10(4):468-486.
60. Zhao S, Yuan G, Wang QI, et al. Quasi-hydrophilic black silicon
photocathodes with inverted pyramid arrays for enhanced hy-
drogen generation. Nanoscale. 2020;12(1):316-325.
61. Mayer MT, Du C, Wang DW. Hematite/Si nanowire
dual-absorber system for photoelectrochemical water
splitting at low applied potentials. J Am Chem Soc.
2012;134(30):12406-12409.
62. Liu Q, Wu F, Cao F, et al. A multijunction of ZnIn2S4 nanosheet/
TiO2 film/Si nanowire for significant performance enhance-
ment of water splitting. Nano Res. 2015;8(11):3524-3534.
63. Li W, Guan ZJ, Gao YP, Ji JY. Simple fabrication of Si/ZnO core/
shell nanowire arrays for photoelectrochemical electrodes.
Chem Phys Lett. 2017;688:79-83.
64. Zhang SY, She GW, Li SY, Mu LX, Shi WS. Si-H induced synthe-
sis of Si/Cu2O nanowire arrays for photoelectrochemical water
splitting. Nanotechnology. 2018;29(3):35601.
65. Zhang FQ, Hu Y, Sun RN, Fu HX, Peng KQ. Gold-sensitized
silicon/ZnO core/shell nanowire array for solar water splitting.
Front Chem. 2019;7:206.
66. Chen H, Wang P, Ye H, et al. Vertically aligned InGaN nanowire
arrays on pyramid textured Si (100): A 3D arrayed light trapping
structure for photoelectrocatalytic water splitting. Chem Eng J.
2021;406:126757.
67. Kim SY, Sivasankaran R, Arunachalam M, et al. Mo2C cocata-
lysts supported Si nanowire photoanode for solar water oxida-
tion. J Electrochem Soc. 2021;168(6):066519.
68. Ning MH, Chen Z, Li L, et al. Modified Si nanowire/graphite-
like carbon nitride core-shell photoanodes for solar water split-
ting. Electrochem Commun. 2018;87:13-17.
69. Jung J-Y, Choi MJ, Zhou K, et al. Photoelectrochemical water
splitting employing a tapered silicon nanohole array. J Mater
Chem A. 2014;2(3):833-842.
70. Bao ZJ, Xu XY, Zhou G, Hu JG. Constructing n-ZnO@Au hetero-
geneous nanorod arrays on p-Si substrate as efficient photoca-
thode for water splitting. Nanotechnology. 2016;27(30):305403.
71. Luo Z, Liu B, Li H, et al. Multifunctional nickel film pro-
tected n-type silicon photoanode with high photovoltage for
efficient and stable oxygen evolution reaction. Small Methods.
2019;3(10):1900212.
72. Wang S, Wang T, Liu B, Li H, Feng S, Gong J. Spatial decoupling
of light absorption and reaction sites in n-Si photocathodes for
solar water splitting. Natl. Sci. Rev. 2020;8:nwaa293.
73. Alarawi A, Ramalingam V, Fu HC, et al. Enhanced photoelec-
trochemical hydrogen production efficiency of MoS2-Si hetero-
junction. Opt Express. 2019;27(8):A352-A363.
20500505, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ese3.1087 by INASP/HINARI - PAKISTAN, Wiley Online Library on [18/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHENG et1541
al.
74. Zhou W, Niu F, Mao SS, Shen S. Nickel complex engineered in-
terface energetics for efficient photoelectrochemical hydrogen
evolution over p-Si. Appl Catal B. 2018;220:362-366.
75. Sun XR, Liu C, Zhang PL, Gong LL, Wang M. Interface-
engineered silicon photocathodes with a NiCoP catalyst-
modified TiO2 nanorod array outlayer for photoelectrochemical
hydrogen production in alkaline solution. J Power Sources.
2021;484:229272.
76. Jun SE, Choi S, Choi S, et al. Direct Synthesis of molybdenum
phosphide nanorods on silicon using graphene at the hetero-
interface for efficient photoelectrochemical water reduction.
Nanomicro Lett. 2021;13(1):81.
77. Li F, Yuan Y, Feng X, et al. Coating of phosphide catalysts on p-
silicon by a necking strategy for improved photoelectrochemi-
cal characteristics in alkaline media. ACS Appl Mater Interfaces.
2021;13(17):20185-20193.
78. Yu X, Yang P, Chen S, Zhang M, Shi G. NiFe alloy protected sili-
con photoanode for efficient water splitting. Adv. Energy Mater.
2016;7(6):1601805.
79. Guo B, Batool A, Xie G, et al. Facile integration between Si and
catalyst for high-performance photoanodes by a multifunc-
tional bridging layer. Nano Lett. 2018;18(2):1516-1521.
80. Huang G, Fan R, Zhou X, et al. A porous Ni-O/Ni/Si photoan-
ode for stable and efficient photoelectrochemical water split-
ting. Chem Commun (Camb). 2019;55(3):377-380.
81. Kwak IH, Im HS, Jang DM, et al. CoSe(2) and NiSe(2) nano-
crystals as superior bifunctional catalysts for electrochemical
and photoelectrochemical water splitting. ACS Appl Mater
Interfaces. 2016;8(8):5327-5334.
82. Digdaya IA, Adhyaksa GWP, Trzesniewski BJ, Garnett
EC, Smith WA. Interfacial engineering of metal-insulator-
semiconductor junctions for efficient and stable photoelectro-
chemical water oxidation. Nat Commun. 2017;8:15968.
83. Xu G, Xu Z, Shi Z, et al. Silicon photoanodes partially covered
by Ni@Ni(OH)2 core-shell particles for photoelectrochemical
water oxidation. Chemsuschem. 2017;10(14):2897-2903.
84. Cai Q, Hong W, Jian C, Liu W. A high-performance sili-
con photoanode enabled by oxygen vacancy modulation
on NiOOH electrocatalyst for water oxidation. Nanoscale.
2020;12(14):7550-7556.
85. Liu Z, Li C, Xiao Y, et al. Tailored NiFe catalyst on silicon pho-
toanode for efficient photoelectrochemical water oxidation. J
Phys Chem C. 2020;124(5):2844-2850.
86. Yan G, Dong Y, Wu T, Xing S, Wang X. Mesoporous ultrathin
In2O3 nanosheet cocatalysts on a silicon nanowire photoanode
for efficient photoelectrochemical water splitting. ACS Appl
Mater Interfaces. 2021;13(44):52912-52920.
87. Sun K, Mcdowell MT, Nielander AC, et al. Stable solar-driven
water oxidation to O2(g) by Ni-oxide-coated silicon photoan-
odes. J Phys Chem Lett. 2015;6(4):592-598.
88. Lee Y, Gupta B, Tan HH, et al. Thin silicon via crack-assisted
layer exfoliation for photoelectrochemical water splitting.
iScience. 2021;24(8):102921. doi:10.1016/j.isci.2021.102921
89. Zhang F, Yu X, Hu J, et al. Coupling Ru-MoS2 heterostructure
with silicon for efficient photoelectrocatalytic water splitting.
Chem Eng J. 2021;423:130231.
90. Fan R, Cheng S, Huang G, et al. Unassisted solar water splitting
with 9.8% efficiency and over 100 h stability based on Si solar
cells and photoelectrodes catalyzed by bifunctional Ni–Mo/Ni.
J Mater Chem A. 2019;7(5):2200-2209.

1542
CHENG et al.
91. Chen Z, Li Y, Wang L, Bu Y, Ao J-P. Development of a bi-
compound heterogeneous cocatalyst modified p-Si photoca-
thode for boosting the photoelectrochemical water splitting
performance. J Mater Chem A. 2021;9(14):9157-9164.
92. Mejia MDC, Sánchez LF, Kurniawan M, et al. Analysis of the
physical and photoelectrochemical properties of c-Si(p)/a-
SiC:H(p) photocathodes for solar water splitting. J Phys D: Appl
Phys. 2021;54(19):195101.
93. Jun SE, Hong SP, Choi S, et al. Boosting unassisted alkaline
solar water splitting using silicon photocathode with TiO2
nanorods decorated by edge-rich MoS2 nanoplates. Small.
2021;17:e2103457.
94. Navid IA, Vanka S, Awni RA, et al. On the design and perfor-
mance of InGaN/Si double-junction photocathodes. Appl Phys
Lett. 2021;118(24):243906.
95. Gong L, Zhang P, Liu G, Shan Y, Wang M. A silicon-based hy-
brid photocathode modified with an N5-chelated nickel catalyst
in a noble-metal-free biomimetic photoelectrochemical cell for
solar-driven unbiased overall water splitting. J Mater Chem A.
2021;9(20):12140-12151.
96. Van De Krol R, Liang Y. An n-Si/n-Fe2O3 heterojunction tan-
dem photoanode for solar water splitting. Chimia (Aarau).
2013;67(3):168-171.
97. Qi X, She G, Huang X, et al. High-performance n-Si/alpha-Fe2O3
core/shell nanowire array photoanode towards photoelectro-
chemical water splitting. Nanoscale. 2014;6(6):3182-3189.
98. Han T, Privitera S, Milazzo RG, et al. Photo-electrochemical
water splitting in silicon based photocathodes enhanced
by plasmonic/catalytic nanostructures. Mater Sci Eng, B.
2017;225:128-133.
99. Perez-Rodriguez P, Digdaya I, Raventos AM, et al. Solar
fuel production by using PV PEC junctions based on earth-
abundant materials. In 2016 IEEE 43RD Photovoltaic Specialists
Conference (PVSC). IEEE, Portland, OR; 2016:3620-3624.
100. Perez-Rodriguez P, Vijselaar W, Huskens J, et al. Designing
a hybrid thin-film/wafer silicon triple photovoltaic junc-
tion for solar water splitting. Prog Photovoltaics Res Appl.
2019;27(3):245-254.
101. Kirner S, Sarajan H, Azarpira A, et al. Wafer surface tuning for
a-Si:H/μc-Si:H/c-Si triple junction solar cells for application in
water splitting. Energy Procedia. 2016;102:126-135.
102. Urbain F, Tang P, Smirnov V, et al. Multilayered hematite
nanowires with thin-film silicon photovoltaics in an all-earth-
abundant hybrid tandem device for solar water splitting.
Chemsuschem. 2019;12(7):1428-1436.
103. Xing Z, Shen S, Wang M, et al. Efficient enhancement of solar-
water-splitting by modified “Z-scheme” structural WO3-W-Si
photoelectrodes. Appl Phys Lett. 2014;105(14):143902.
104. Gorji MS, Cheong KY. Embedded nanoparticles in schottky
and ohmic contacts: a review. Crit Rev Solid State Mater Sci.
2015;40(4):197-222.
105. Kenney MJ, Gong M, Li Y, et al. High-performance silicon pho-
toanodes passivated with ultrathin nickel films for water oxida-
tion. Science. 2013;342(6160):836-840.
106. Zhao Y, Brocks G, Genuit H, et al. Boosting the performance
of WO3 /n-Si heterostructures for photo-electrochemical water
splitting from the role of Si to interface engineering. Adv. Energy
Mater. 2019;9(26):1900940.
107. Matsuo N, Takami Y, Kitagawa Y. Modeling of direct tun-
neling for thin SiO2 film on n-type Si(100) by WKB method
20500505, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ese3.1087 by INASP/HINARI - PAKISTAN, Wiley Online Library on [18/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
|
CHENG et al.
17
considering the quantum effect in the accumulation layer.
Solid-State Electron. 2002;46:577-579.
108. Satterthwaite PF, Scheuermann AG, Hurley PK, Chidsey
CE, Mcintyre PC. Engineering interfacial silicon dioxide for
improved metal-insulator-semiconductor silicon photoan-
ode water splitting performance. ACS Appl Mater Interfaces.
2016;8(20):13140-13149.
109. Kaushik N, Karmakar D, Nipane A, Karande S, Lodha S.
Interfacial n-Doping using an ultrathin TiO2 layer for con-
tact resistance reduction in MoS2. ACS Appl Mater Interfaces.
2016;8(1):256-263.
110. Tan MX, Laibinis PE, Nguyen ST, et al. Principles and appli-
cations of semiconductor photoelectrochemistry. Prog Inorg
Chem. 1994;21-144.
111. Shan B, Brennaman MK, Troian-Gautier L, et al. A silicon-
based heterojunction integrated with a molecular excited
state in a water-splitting tandem cell. J Am Chem Soc.
2019;141(26):10390-10398.
112. Feng J, Huang H, Yan S, et al. Non-oxide semiconductors for
artificial photosynthesis: Progress on photoelectrochemical
water splitting and carbon dioxide reduction. Nano Today.
2020;30:100830.
113. Zhang Y, Bu Y, Wang L, Ao J-P. Regulation of the photogenerated
carrier transfer process during photoelectrochemical water
splitting: a review. Green Energy Environ. 2021;6(4):479-495.
114. Chen S, Wang L-W. Thermodynamic oxidation and reduction
potentials of photocatalytic semiconductors in aqueous solu-
tion. Chem Mater. 2012;24(18):3659-3666.
115. Hu S, Shaner MR, Beardslee JA, et al. Amorphous TiO2 coat-
ings stabilize Si GaAs and GaP photoanodes for efficient water
oxidation. Science. 2014;45(34):1005-1009.
116. Wang Y, Tian W, Cao F, et al. Boosting PEC performance of Si
photoelectrodes by coupling bifunctional CuCo hybrid oxide
cocatalysts. Nanotechnology. 2018;29(42):425703.
117. Eftekharinia B, Pezeshki H, Dabirian A. Unassisted water split-
ting using standard silicon solar cells stabilized with copper and
bifunctional NiFe electrocatalysts. ACS Appl Mater Interfaces.
2020;12(15):17424-17435.
118. Yang W, Prabhakar RR, Tan J, Tilley SD, Moon J. Strategies for
enhancing the photocurrent, photovoltage, and stability of pho-
toelectrodes for photoelectrochemical water splitting. Chem
Soc Rev. 2019;48(19):4979-5015.
119. Yin Z, Fan R, Huang G, Shen M. 11.5% efficiency of TiO2 pro-
tected and Pt catalyzed n+np+-Si photocathodes for photoelec-
trochemical water splitting: manipulating the Pt distribution
and Pt/Si contact. Chem Commun (Camb). 2018;54(5):543-546.
120. Ziegler J, Yang F, Wagner S, et al. Interface engineering of tita-
nium oxide protected a-Si:H/a-Si: H photoelectrodes for light
induced water splitting. Appl Surf Sci. 2016;389:73-79.
121. Yao T, Chen R, Li J, et al. Manipulating the interfacial energet-
ics of n-type silicon photoanode for efficient water oxidation. J
Am Chem Soc. 2016;138(41):13664-13672.
122. Jung J-Y, Kim DW, Park TJ, Lee J-H. Design guidelines of insu-
lator for improving stability and performance of nanoelectro-
catalyst/insulator/semiconductor photoelectrochemical cells.
ACS Appl. Energy Mater. 2020;3(1):1046-1053.
123. Mallikarjuna K, Tekalgne MA, Hasani A, et al. C-doped SnO2
nanostructure/MoS2/p-Si electrodes for visible light-driven
photoelectrochemical hydrogen evolution reaction. Int J Energy
Res. 2021;45(12):18201-18211.

18 |
CHENG et al.
124. Vahidmohammadi A, Rosen J, Gogotsi Y. The world of
two-dimensional carbides and nitrides (MXenes). Science.
2021;372(6547):eabf1581.
125. Yu M, Wang Z, Liu J, et al. A hierarchically porous and hydro-
philic 3D nickel–iron/MXene electrode for accelerating oxygen
and hydrogen evolution at high current densities. Nano Energy.
2019;63:103880.
126. Lin J, Yu Y, Zhang Z, et al. A novel approach for achieving
high-efficiency photoelectrochemical water oxidation in
InGaN Nanorods grown on Si system: MXene nanosheets
as multifunctional interfacial modifier. Adv Funct Mater.
2020;30(13):1910479.
127. Ramalingam V, Varadhan P, Fu H-C, et al. Heteroatom-
mediated interactions between ruthenium single atoms and
an MXene support for efficient hydrogen evolution. Adv Mater.
2019;31(48):e1903841.
128. Wang Y, Yan D, El Hankari S, Zou Y, Wang S. Recent progress
on layered double hydroxides and their derivatives for electro-
catalytic water splitting. Adv Sci (Weinh). 2018;5(8):1800064.
129. Licht S, Wang B, Mukerji S, et al. Efficient solar water splitting,
exemplified by RuO2-catalyzed AlGaAs/Si photoelectrolysis. J
Phys Chem B. 2000;104:8920-8924.
130. Over H. Fundamental studies of planar single-crystalline oxide
model electrodes (RuO2, IrO2) for acidic water splitting. ACS
Catalysis. 2021;11(14):8848-8871.
131. Wang Y, Qiu W, Song E, et al. Adsorption-energy-based activity
descriptors for electrocatalysts in energy storage applications.
Natl. Sci. Rev. 2018;5(3):327-341.
132. Hendricks OL, Scheuermann AG, Schmidt M, et al. Isolating
the photovoltaic junction: atomic layer deposited TiO2-RuO2
20500505, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ese3.1087 by INASP/HINARI - PAKISTAN, Wiley Online Library on [18/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHENG et1543
al.
alloy schottky contacts for silicon photoanodes. ACS Appl
Mater Interfaces. 2016;8(36):23763-23773.
133. Mikolasek M, Frohlich K, Husekova K, et al. Silicon based MIS
photoanode for water oxidation: a comparison of RuO2 and Ni
Schottky contacts. Appl Surf Sci. 2018;461:48-53.
134. Sahoo PP, Mikolášek M, Hušeková K, et al. Si-based metal–
insulator–semiconductor structures with RuO2–(IrO2) films
for photoelectrochemical water oxidation. ACS Appl. Energy
Mater. 2021;4(10):11162-11172.
135. Tang R, Zhou SJ, Yuan ZM, Yin LW. Metal-organic framework
derived Co3O4/TiO2/Si heterostructured nanorod array photo-
anodes for efficient photoelectrochemical water oxidation. Adv
Funct Mater. 2017;27(37):1701102.
136. Wu FL, Liao QL, Cao FR, Li L, Zhang Y. Non-noble bimetallic
NiMoO4 nanosheets integrated Si photoanodes for highly effi-
cient and stable solar water splitting. Nano Energy. 2017;34:8-14.
137. Choi S, Lee SA, Yang H, et al. Stabilization of NiFe layered
double hydroxides on n-Si by an activated TiO2 interlayer
for efficient solar water oxidation. ACS Appl. Energy Mater.
2020;3(12):12298-12307.
How to cite this article: Cheng C, Zhang W,
Chen X, Peng S, Li Y. Strategies for improving
photoelectrochemical water splitting performance
of Si-based electrodes. Energy Sci Eng. 2022;10:
2022;00:1–
1526–1543. doi:10.1002/ese3.1087
18. doi:10.1002/ese3.1087