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Meeting the growing global energy demand is one of the important challenges of the 21st century.
Currently over 80% of the worlds energy requirements are supplied by the combustion of fossil fuels,
which promotes global warming and has deleterious eects on our environment. Moreover, fossil fuels
are non-renewable energy and will eventually be exhausted due to the high consumption rate. A new type
of alternative energy that is clean, renewable and inexpensive is urgently needed. Several candidates are
currently available such as hydraulic power, wind force and nuclear power. Solar energy is particularly
attractive because it is essentially clean and inexhaustible. A years worth of sunlight would provide
more than 100 times the energy of the worlds entire known fossil fuel reserves. Photocatalysis and
photovoltaics are two of the most important routes for the utilization of solar energy. However,
environmental protection is also critical to realize a sustainable future, and water pollution is a serious
problem of current society. Photocatalysis is also an essential route for the degradation of organic dyes
in wastewater. A type of compound with the defined structure of perovskite (ABX3) was observed to play
important roles in photocatalysis and photovoltaics. These materials can be used as photocatalysts for
water splitting reaction for hydrogen production and photo-degradation of organic dyes in wastewater
as well as for photoanodes in dye-sensitized solar cells and light absorbers in perovskite-based solar
cells for electricity generation. In this review paper, the recent progress of perovskites for applications in
these fields is comprehensively summarized. A description of the basic principles of the water splitting
reaction, photo-degradation of organic dyes and solar cells as well as the requirements for ecient
photocatalysts is first provided. Then, emphasis is placed on the designation and strategies for perovskite
Received 5th February 2015 catalysts to improve their photocatalytic activity and/or light adsorption capability. Comments on current
DOI: 10.1039/c5cs00113g and future challenges are also provided. The main purpose of this review paper is to provide a current
summary of recent progress in perovskite materials for use in these important areas and to provide
www.rsc.org/chemsocrev some useful guidelines for future development in these hot research areas.
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electricity, has attracted considerable and increasing attention.15 efficiency (Z) is 31% for single-crystalline Si cells, as predicted
However, to date, humans consume only 539 EJ globally per year, by a thermodynamic calculation performed by Shockley and
which is only approximately 0.014% of the total solar energy Queisser (SQ).18 Although exhibiting a relatively high efficiency,
reaching the Earth. It is thus necessary to develop new approaches these materials suffer from high manufacturing and installation
that can utilize solar energy directly with improved efficiency. costs. The second generation of solar cells included the use
However, organic waste pollution has become a serious problem of amorphous silicon, polycrystalline silicon or microcrystalline
because many organic wastes are toxic and have a deleterious silicon, cadmium telluride or copper (gallium) indium selenide/
effect on the ecological environment. The conversion of wastewater sulfide. These solar cells were significantly less expensive than
to harmless and readily disposable water is of significant impor- single-crystalline solar cells due to the reduced materials and
tance for a sustainable future. processing costs and increased manufacturing throughput. The
Photocatalysis and photovoltaics are two of the most important efficiencies of these cells were generally lower than those of the
first-generation solar cells.2,19 The third generation of solar cells,
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catalysts, such as TiO2 and UV or visible light, has demon- In the absence of electron scavengers, the photoexcited electron
strated promising results for the degradation of organic dyes recombines with the VB hole in nanoseconds (ns) with the
and produces more biologically degradable and less toxic simultaneous dissipation of heat energy, as shown in eqn (4).4
substances. Tremendous efforts have been devoted to the use The recombination of the electron and hole must be prevented
of photocatalysis in the removal of dyes from wastewaters.4246 as much as possible for a photocatalyzed reaction to be favored.
The photocatalytic oxidation process is activated by the The ultimate goal of the process is to have a reaction between
absorption of a photon with sucient energy (equal or greater the activated electrons with an oxidant to produce a reduced
to Ebg of the semiconductor catalyst), and charge separation product and a reaction between the generated holes with a
then occurs due to the promotion of an electron (e) from the reductant to produce an oxidized product. Thus, the presence
VB of the semiconductor catalyst to the CB. Thus, a hole (h+) in of electron scavengers is vital for prolonging the recombination
the VB is generated.4 In this reaction, h+ and e are powerful and successful functioning of photocatalysis. In the degradation
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oxidizing and reducing agents, respectively. The positive hole of organic pollutants, the hydroxyl radical, which is generated
oxidizes either the pollutant directly or water to produce OH from the oxidation of adsorbed water, where it is adsorbed as
radicals and the electron in the CB reduces the oxygen adsorbed OH, is the primary oxidant; the presence of oxygen can prevent
on the photocatalyst.4 The activation of a semiconductor by the recombination of an electronhole pair while allowing the
light can be represented in the following steps, as proposed formation of a superoxide radical (O2 ), as indicated in eqn (5).4
by Chong et al.:4 This O2 radical can be further protonated to form the hydro-
Photoexcitation: peroxyl radical (HO2 ), and subsequently H2O2, as shown in
eqn (9) and (10), respectively.4 The HO2 radical formed was also
photocatalyst + hn - e+h+ (1)
reported to exhibit scavenging properties. Thus, the co-existence
Charge-carrier trapping of e: of these radical species can doubly prolong the recombination
time of the hTR+ in the entire photocatalysis reaction.4 Although
eCB - eTR (2) the hTR+ has been widely studied for its ability to oxidize organic
Charge-carrier trapping of h+: species directly, this possibility has remained inconclusive. In
the photocatalytic degradation of pollutants, when the reduction
hVB+ - hTR+ (3) process of oxygen and the oxidation of pollutants do not advance
Electronhole recombination: simultaneously, an electron would accumulate in the CB, which
causes an increase in the rate of recombination of e and h+.
eTR + hVB+(hTR+) - eCB + heat (4) Thus, to obtain the photo-catalyzed reaction, the eh+ recom-
Photoexcited e scavenging: bination must be prevented as much as possible.
2.1.3 Solar cells. Photovoltaics or solar cells are devices that
(O2)ads + e - O2 (5) directly convert the solar energy into electric power. Ecient
solar devices rely on matching their light absorption spectrum to
Oxidation of hydroxyls:
the AM 1.5G spectrum irradiated on the earth surface. AM 1.5G
OH + h+ - OH (6) is defined by a broadband solar spectrum, spanning from
280 nm in the UV region to 2500 nm in the mid-infrared region.
Photodegradation of organic by OH :
The power conversion eciency (PCE) Z of these devices can
organic + OH - CO2 + H2O (7) be given by
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been argued that perovskite structures are not stable, even in the detailed investigation of perovskite design based on above
the most favorable range of 0.8 o t o 0.9.58 It has been strategies for water splitting reaction and degradation of
indicated that perovskite stability cannot be predicted solely organic dyes were also conducted.
based on a tolerance factor. An additional consideration for the
formability of perovskite is the octahedral factor (m), m = rB/rX, 3.1 Strategies to design perovskite materials for the water
which was then proposed.59 For the alkali metal halide perovs- splitting reaction and degradation of organic dyes
kite, formability was determined from the tm mapping, where 3.1.1 Band gap engineering. The strategies to engineer the
the perovskite was stabilized for a tolerance factor ranging Ebg include donoracceptor coincorporation, using 4d and 5d
between 0.813 and 1.107, and an octahedral factor ranging from cations as donors with higher atomic d orbital energies to
0.442 and 0.895.59 For example, the ionic radii of rA in the APbX3 guarantee that the conduction-band maximum (CBM) energy
perovskite are estimated based on the effective ionic radii,52 level is not lowered and high electron mobility is maintained,
where the A cation radii range from B160 picometers (pm) to
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There are two main groups of elements that can act as active
cation components (B site) in a perovskite photocatalyst. The
first group includes Ti4+, Nb5+, Ta5+, W6+, Zr4+, and Ce4+ elements
with empty d orbitals. Elements, such as Ga3+, In3+, Ge4+, Sn4+
and Sb5+ in the second group with filled d orbitals have also been
Fig. 6 Diuse reflectance spectra of SrTiO3:M (0.5%). M = (a) Mn, (b) Ru,
considered to be good catalysts for the water splitting reaction.31,32 (c) Rh, (d) Pd, (e) Ir, and (f) Pt. A broken line represents a spectrum of
In this section, we will focus on the design of perovskite catalysts nondoped SrTiO3. Reproduced with permission from ref. 76. Copyright
using proposed strategies for the water splitting reaction to achieve 2004, American Chemical Society.
UV and visible light. Fig. 5 presents schematics of a high-level
summary of Section 3.
3.2.1 Band gap engineering In addition to SrTiO3, some other titanates have also attracted
3.2.1.1 Selection and doping process of B-site elements. Recently, considerable attention by doping suitable elements such as Cu,
there have been many reports about pristine and doped perovskite Sc, Cr and Fe in the B-site.75,77,78 CaTiO3 is one of the best-known
photocatalysts, such as Ti, Ta, and Nb-based perovskite oxides wide gap insulating oxides with a BG of approximately 3.5 eV.
for water splitting reaction under UV and visible lights.67,7375 However, careful doping with Cu in the B site could make
However, the undoped titanates always had a larger Ebg, which it conducting. CaTi1xCuxO3 (x = 0.01, 0.02, 0.03 and 0.04)
limited their applications in visible-light-driven water splitting compounds were prepared by the solgel method coupled with
reactions. For example, several metals, such as Rh, Mn, Ru and the ultrasonic technique and used as catalysts for H2 evolution
Ir were used to dope SrTiO3 to give visible light responses for H2 reactions under UV light.75 It was observed that 2 mol% Cu2+-
or O2 evolution reactions.76 Although SrTiO3 with a BG of 3.2 eV doped CaTiO3 exhibited the highest activity for the water splitting
could not absorb visible light, SrTiO3 doped with Rh, Ir, Ru and reaction. The excessive Cu2+ doping became the recombination
Mn exhibits absorption in the visible light region, as observed centers for photogenerated charges; therefore, the photocatalytic
in Fig. 6. The visible light responses were due to the electronic activity of hydrogen production decreased. The photocatalytic
transition from donor levels formed with dopants to the CBs of activity of doped CaTiO3 for H2 evolution under UV light was
the host photocatalysts. Among the various doped photocatalysts, increased dramatically by approximately 8-fold compared to
Rh-doped SrTiO3 exhibited the highest activity among the doped that of pure CaTiO3. However, the addition of Cu also led to the
photocatalysts for H2 evolution under visible light irradiation.76 absorption of visible light on the CaTiO3, which could be
In this case, the dopant exists as a trivalent ion (Rh3+) on the B-site attributed to the transition from the donor levels formed by
(Ti4+ site), which forms a donor level at a lower potential than the Cu2+ to the CB of copper-doped CaTiO3, as evidenced by density
top of the VB composed of O 2p orbitals, and the apparent BG functional theory (DFT) calculations.75 Yun et al. studied the
consequently became narrowed. stability, electronic structure and photocatalytic properties of
the Sc-doped Sr2TiO4 using first-principles calculations based
on DFT.77 The BG of Sr2Sc0.125Ti0.875O4 narrowed by approxi-
mately 0.25 eV compared to that of undoped Sr2TiO4, resulting
in a red-shift in the absorption spectra edge. In particular,
the dispersion of the CBs and VBs of Sr2Sc0.125Ti0.875O4 was
enhanced after the doping, which was preferable for the
photocatalytic performance. In addition, a new weak absorp-
tion appeared in the visible light region, which somehow
contributed to the photocatalytic activity of Sr2Sc0.125Ti0.875O4.
Hwang et al. also studied the effects of B-site metal dopants on
the band structure of the layered perovskite La2Ti2O7 and
observed that only Cr and Fe exhibited intense absorption
in the visible light region due to the decreased BG by the
Fig. 5 The schematics of the high-level summaries of Section 3. B-site doping.78 In addition, these two catalysts produced H2
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photocatalytically by the water splitting reaction under visible photocatalysts exhibited the best photocatalytic activities for
light irradiation. water splitting under visible light irradiation due to the small
BG. Although the photocatalytic activities of these photocatalysts
3.2.1.2 Selection and doping process of A-site elements. In under visible light irradiation are relatively low, it is an effective
addition to B-site doping of titanates, Zn2+ was also used route to designing new photocatalysts.
as an A-site dopant to modify SrTiO3 and BaTiO3 perovskites
(Sr2/3Zn1/3TiO3 and Ba5/6Zn1/6TiO3) to enhance the photoactivity 3.2.1.3 Selection and doping process of X-site elements. In
for water splitting reactions by reducing Ebg.67 It was observed addition to the A/B site doping of perovskite oxides, doping at
that the top of the VBs dominantly consisted of the O 2p orbital, the O site with N3 to form oxynitrides was also considered
whereas the bottom of the CBs was composed of the Ti-3d orbital as an eective approach to enhance the activity for the water
and Zn-3d orbital. Furthermore, with increasing Zn content, the splitting reaction under visible light.68,82,83 In these materials,
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contribution of the Zn-3d orbital to the CBs increased; thus, the the N 2p orbitals form a new VB, thus reducing the Ebg. LaMO2N
BG narrowed for Zn-doped SrTiO3 and Zn-doped BaTiO3, and (M = Ti, Zr), LaMON2 (M = Nb, Ta), and AEMO2N (AE = Ca, Sr, Ba;
the BG values decreased with increasing concentration of Zn M = Nb, Ta) are well-known perovskite oxynitrides. Most of these
atoms.67 This study demonstrated that the partial doping of the materials can absorb light with wavelengths up to 600 nm or
A-site with Zn ions could change the crystal and band structures longer. Furthermore, BG is flexible in a wide range from the UV
and significantly promote the carrier mobility of the catalysts to to the near-IR region by forming solid solutions with other
result in good photocatalytic activities.67 Specifically, the BGs for perovskite oxides and oxynitrides. The superior chemical and
Zn ions doped at the Sr or Ba sites with dierent concentrations thermal stabilities of the oxynitrides made them attractive for
were all narrowed with respect to pure SrTiO3 or BaTiO3. The applications as visible-light-responsive photocatalysts for the
reduced BG values were 0.675, 0.555 and 0.526 eV by Zn doping at water splitting reaction. For example, tantalum oxynitride series
the Sr site with molar ratios of 1/3, 1/6 and 1/10, respectively, ATaO2N (A = Ca, Sr, and Ba) and PrTaON2 are promising
whereas the BG values were reduced to 0.169, 0.118 and 0.087 eV candidates for the photocatalytic splitting of water under visible
by doping with Zn at the Ba site with molar ratios of 1/3, 1/6 light. It was observed that BaTaO2N, SrTaO2N and CaTaO2N have
and 1/10, respectively. cubic, tetragonal and orthorhombic symmetries, respectively,
Some researchers have also investigated the A-site cation in whereas PrTaON2 is orthorhombic and isostructural with CaTaO2N.
tantalate and niobate systems for the optimization of Ebg for The corresponding structures are shown in Fig. 7.82 Smaller A-site
realizing water splitting reactions under visible light irradiation. cations lead to more octahedral tilting and less dispersed CBs and
For example, the band structures of perovskite-type materials thus a higher energy for the CB edge. Increasing the nitrogen
ATaO3 (A = Li, Na, K, Ag) were studied by Kato et al.74 It was content leads to an upward shift in the position of the VB edge. All
observed that the Ebg of AgTaO3 was 3.4 eV, lower than those of the proposed catalysts have CB edges that lie above the reduction
LiTaO3 (4.7 eV), NaTaO3 (4.0 eV) and KTaO3 (3.6 eV). The authors potential for water and are therefore suitable for the photocatalytic
considered that the dierences in BG were not determined by production of hydrogen, whereas the VB edges lie near the oxida-
the TaOTa bond angle in the perovskite because the TaOTa tion potential of water.
bond angle in KTaO3 was closer to 1801, which was beneficial for Some perovskite-type niobium oxynitrides (CaNbO2N, SrNbO2N,
the reduction of Ebg. A hybrid orbital of Ag 4d and O 2p forming BaNbO2N, and LaNbON2) prepared by heating the precursors
a VB at a more negative level than O 2p orbitals should be attributed under flowing NH3 at an appropriate temperature are also
to the smaller BG of AgTaO3. In addition, AgTaO3 exhibited reason- examined for hydrogen and oxygen evolution from water under
able photocatalytic activity for the water splitting reaction. Machida visible light. These materials possess visible-light absorption
et al. studied the effects of dual doping at the A-site on the band
structure and photocatalytic activity for the water splitting
reaction for the layered perovskite MLnTa2O7 (M = Cs, Rb,
Na, and H; Ln = La, Pr, Nd, and Sm).79 The optical Ebg was
dependent on lanthanum, Ln, but negligibly affected by the
monovalent interlayer cations, M. The effect of Ln can be explained
by the shift of the Ln 4f levels from the CB edge to the VB edge
with an increasing number of Ln 4f electrons. In contrast, the
photocatalytic activity was strongly affected by not only Ln, but
also M; the highest activity was attained by a series of M = Rb
with a sequence of Ln:Nd 4 Sm 4 La 4 Pr. Similar results were
obtained by Machida et al. in the RbLnTa2O7 system.80 Yin et al.
developed a series of photocatalysts by changing the ionic radius
in the A-site cations in MIn0.5Nb0.5O3 (M = Ca, Sr, and Ba) with
the ABO3-type perovskite structure.81 It was observed that the Fig. 7 Structures of cubic BaTaO2N, tetragonal SrTaO2N, and orthorhombic
larger ionic radius in the A-site cations led to a smaller BG and CaTaO2N or PrTaON2. Reproduced with permission from ref. 82. Copyright
that BaIn0.5Nb0.5O3 had the smallest BG. The BaIn0.5Nb0.5O3 2013, American Chemical Society.
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phase was observed to have a larger number of effective states under visible light irradiation, which should be improved
available for the photo-induced electrons and holes. The longer further in the future.
lifetime of the free electrons and holes is expected to increase
the probability of their participation in water splitting. For 3.3 Degradation of organic dyes
the crystalline structure, the bond angle of TaOTa for the As discussed previously, a semiconductor catalyst in the con-
monoclinic phase was approximately 1801, a value ideal for taminated water can absorb solar energy to result in the formation
delocalization of the excited energy in tantalate crystals. The larger of electron donor (reductive) sites and electron acceptor (oxidizing)
surface area and the advantageous features in the electronic and sites, which facilitate the oxidation of carbon-containing pollutants
crystalline structures for the monoclinic phase resulted in a remark- to carbon dioxide, water and other anions, such as nitrate, sulfate
ably higher photocatalytic activity for the solgel-synthesized or chloride. In this section, we will focus on the material develop-
NaTaO3 than for the solid-state-synthesized material. ment of perovskite catalysts for the photocatalytic degradation of
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The photocatalytic activities of the selected perovskite-based dierent dyes, such as methyl orange (MO), methylene blue (MB)
photocatalysts for the water splitting reaction are listed in and rhodamine B (RB) based on the strategies for the designation
Table 1. As shown in this table, in addition to the choice of of perovskite catalysts. The strategies for the development of
photocatalyst, the photocatalytic activity for the water splitting catalysts for the degradation of organic dyes are similar to those
reaction is also strongly dependent on the sacrificial reagent for the water splitting reaction, including band gap engineering
and the cocatalyst. Overall, the addition of sacrificial reagent and reducing the recombination rate of the electronhole pairs.
and the cocatalyst is helpful for improving the photocatalytic 3.3.1 Band gap engineering
activity. Sometimes, the addition of an excess Pt cocatalyst 3.3.1.1 Selection and doping process of B-site elements. The
of 1.5 wt% could reduce the activity. A loading of 1.0 wt% undoped Ti-based perovskite always had large BGs due to the large
provided a proper cover ratio and size of the cocatalyst and dierence in electronegativity between Ti and O. The replacement
hence induced the highest H2 evolution rate for the cubic of Ti by another element with higher electronegativity, such as Ni,
NaNbO3 photocatalyst. In addition, not all catalysts had high is an eective approach to reduce Ebg. For example, LaNiO3 was
activity for both O2 evolution and H2 evolution reaction, and synthesized using a solgel combustion technique for the degra-
some of them showed high selectivity to the individual reaction. dation of the MO reaction under visible light.93 The BG of LaNiO3
As shown in Table 1, NaTaO3 is the most widely investigated was 2.26 eV, suggesting potential visible-light-induced photo-
photocatalyst and generally showed superior activity than catalytic activity, which was evaluated by the degradation of MO
NaNbO3, KNbO3 and KTaO3. The eect of the preparation in water under visible light irradiation. It was observed that the
methods and the selection of A-site elements for doping on photo-degradation of MO over LaNiO3 was a zero-order reaction,
the photocatalytic activity of NaTaO3 have been studied inten- that the rate constant k of LaNiO3 was 0.152 (102 g L1 h1)
sively. Although a nanostructure is formed in the A-site doped and that the degradation percentage after 5 h on the sample
NaTaO3 with improved activity, its BG is unchanged, which may was approximately 74.9%, suggesting the effective degradation
restrict its wider applications in the visible light-induced water activity of MO on the LaNiO3 catalysts.
splitting reaction. In the future, co-doping of the A-site with La, In addition to tailoring the B-site element, Fei et al. also
Sr, etc. and the O site with N, S, etc. on NaTaO3 should be an examined the eect of partial substitution of the titanium cation
eective way to obtain both a nanostructure and a reduced BG. on the photocatalytic oxidation activity for the degradation of the
However, a reduced BG does not always bring about improved Nile blue reaction in the CeCoxTi1xO3+d perovskite system
activity. For example, SrNbO2N, BaNbO2N, LaNbON2 with BGs prepared using the solgel method.94 Based on UV-vis diffuse
lower than 2 eV showed almost no photocatalytic activity for the reflectance measurements, it was observed that the perovskite
water splitting reaction because the absolute energy position of catalysts exhibited significantly lower BG (1.452.15 eV) than
the BG is also important for the water splitting reaction. For the P25 (3.2 eV); however, the Ebg remained almost unchanged at a
SrSnO3 catalyst prepared by a wet chemistry method, doping in doping level of x 4 0.1, as shown in Fig. 14. The incorporation
the O site should be a useful way to further enhance the activity of 5 mol% Co in the B-site led to a decrease in BG from 2.15 eV
by reducing the BG. Nevertheless, doped perovskites always to 1.57 eV. Using the oxidative photodegradation of a aqueous
show a lower BG than the commercial TiO2 and higher activity Nile blue solution for activity evaluation, the CeCo0.05Ti0.95O3.97
under visible light irradiation should be expected with perovs- perovskite was the best in the series with a conversion of 91% in
kite catalysts. Advanced methods, such as nanosheet processing, a 3 hour run and was also suitable for the solar photocatalysis
template-based methods, hydrothermal process and solgel because it could be activated by visible light (l o 785 nm).
process, are beneficial for achieving high photocatalytic activity. Su et al. applied a hydrothermal route for the dual substitu-
However, solid state reaction is still the most investigated tions of a single Cr dopant in a perovskite lattice of NaTaO3 for
methods because of its convenience and more importantly, the degradation of the MB reaction under visible light.95 It was
universality. In the future, it will be of great importance to observed that the pure orthorhombic perovskite phase was
improve the universality of these advanced technologies. In retained regardless of Cr3+ doping. The undoped NaTaO3 had
addition, in most of the studies mentioned in this review paper, a BG of 4.13 eV (corresponding to a 300 nm absorption edge) with
the solar-energy conversion efficiency for this system was not an excitation from O 2p to Ta 5d. Upon increasing the doping
presented and the presented values are very low, particularly level of Cr3+, a systematic redshift of the absorption edge and
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Table 1 Photocatalytic activity of the selected perovskite-based photocatalysts for the water splitting reaction
O2 evolutiona H2 evolutiona
Rate Rate
BG (mmol Sacrificial (mmol h1 Sacrificial Quantum Preparation
No. Photocatalyst (eV) h1 g1) reagent g1) reagent Cocatalyst yields method Light type Ref.
1 Sr2/3Zn1/3TiO3 3.15 732 Ethanol Solgel UV 67
2 Sr2/3Zn1/3TiO3 3.15 121
3 Ba5/6Zn1/6TiO3 3.2 575 Ethanol
4 Ba5/6Zn1/6TiO3 3.2 29
5 CaNbO2N 2.0 10 AgNO3 312 Methanol 1 wt% Pt 1.1% at Polymerized l 4 420 nm 68
420.5 nm complex
6 SrNbO2N 1.8 0 15
7 BaNbO2N 1.7 0 0
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8 LaNbON2 1.6 0 0
9 Cubic NaNbO3 3.29 423 Methanol Furfural alcohol l 4 300 nm 69
10 Orthorhombic 3.45 241 derived
NaNbO3 polymerization
11 Cubic NaNbO3 3.29 425 0.5 wt% Pt oxidation
12 Cubic NaNbO3 3.29 520 1 wt% Pt
13 Cubic NaNbO3 3.29 324 1.5 wt% Pt
14 NaTaO3 4.0 0.78 AgNO3 10.3 Methanol Solid state l 4 270 nm 70
15 2 mol% La doped 4.09 1.7 13.2 56% at reaction (SSR)
NaTaO3 270 nm
16 NaNbO3 3.08 950 Methanol Hydrothermal UV 73
17 KNbO3 3.14 100
18 NaTaO3 3.96 36 750
19 KTaO3 3.42 1040
20 CaTiO3 670.1 Methanol NiOx Solgel coupled UV 75
21 CaTi0.98Cu0.02O3 5410.8 with ultrasonic
22 CaTiO3 0 dispersing technique l 4 400 nm
23 CaTi0.98Cu0.02O3 22.7
24 Mn-doped SrTiO3 2.7 9 AgNO3 0.67 Methanol 0.5 wt% Pt SSR l 4 440 nm 76
25 Ru-doped SrTiO3 1.9 13 5.7
26 Rh-doped SrTiO3 1.7 0 57.3 5.2% at
420 nm and
6% at 365 nm
27 Ir-doped SrTiO3 2.3 1.3 27.7
28 RbLaTa2O7 B3.9 3 6 SSR UV 79 and
29 RbPrTa2O7 B3.6 o0.5 4.5 80
30 RbNdTa2O7 B4.2 126.5 235
31 RbSmTa2O7 B4.1 28.5 53
32 2 mol% Ca doped 4.11 113 AgNO3 756 Methanol SSR 400 W Hg 85
NaTaO3 lamp
33 2 mol% Sr doped 4.11 186 830
NaTaO3
34 2 mol% Ba doped 4.09 160 696
NaTaO3
35 NaTaO3 4.03 40 563
36 NaTaO3 4.0 B1000 MHT 87
37 NaTaO3 4.0 B400 CHT
38 Sr0.5TaO3 3.7 177 733 Direct dehydration 400 W Hg 88
39 RE-Sr0.5TaO3 3.7 366 1400 Nanosheet lamp
processing
40 SrTiO3 300 Methanol 0.5 wt% Pt M13 virus template UV 89
method
41 SrSnO3 4.04 57.3 Wet chemistry UV 91
42 SrSnO3 4.01 7 SSR
43 NaTaO3 4.1 B900 2050 SSR 400 W Hg 92
44 NaTaO3 4 6 13 Solgel lamp
a
For a clear comparison, the units of the rates are also correlated to mmol h1 g1 by a simple calculation.
the appearance of two broad absorptions in the range 400 transition for Cr3+.96,97 The single or dual substitutions of
750 nm were observed with increased intensities. Furthermore, Cr on the B site or both A site and B site depended on the
Ebg decreased from 4.13 eV for the undoped sample to 3.14 eV doping level of Cr. Specifically, at a lower doping level of Cr3+
for the 6.39 mol% Cr3+ doped sample. The absorption observed (2.47 mol%), Cr3+ primarily occupied the Ta5+ (B site) sites,
in the range of 400500 nm was ascribed to the charge transfer creating certain oxygen vacancies, resulting in no obvious
from the 3d orbital of Cr3+ to the 5d orbital of Ta5+, whereas impact on the lattice dimension but enhanced photocatalytic
that ranging from 550750 nm corresponded to the dd activities. With a further increase in the Cr3+ content, Cr3+
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Fig. 14 Band-gap energy of various CeCoxTi1xO3+d perovskites and TiO2. Nitrogen doping is known to shift the absorption edge
Reproduced with permission from ref. 94. Copyright 2005, Elsevier Inc. toward higher wavelengths because of the contribution of N 2p
orbitals to the VB comprised of O 2p orbitals, thereby moving the
VB upwards. The nitrogen-doped K2La2Ti3O10xNx photocatalyst
started to simultaneously substitute for both Na+ in the 12-fold
was successfully prepared using conventional solid-state reac-
coordination sites and Ta5+ in 6-fold coordination states of the
tions and a wet chemical process.99 After nitrogen doping, Ebg of
perovskite NaTaO3. This dual substitution was further observed
K2La2Ti3O10 was decreased from 3.69 to 3.44 eV. The degradation
to yield a certain concentration of oxygen vacancies, a systematic
of dyes under UV and visible light radiation was better with a
decrease in lattice dimensions, an increased surface area and
K2La2Ti3O10xNx photocatalyst than with a pure K2La2Ti3O10
a decreased Ebg. However, the higher dopant concentration
photocatalyst. In addition, the K2La2Ti3O10xNx photocatalyst
resulted in a significant decrease in photocatalytic activity.
exhibited significantly higher visible-light photocatalytic activity
A schematic diagram of the electronic intraband transitions
than pure TiO2 (P25) in organic dye solution under visible
of the Cr-doped NaTaO3 could be speculated and is presented
light irradiation.
in Fig. 15.95 Under visible light irradiation, electrons will be
A noticeable lowering of Ebg has been achieved for the
excited directly from the O 2p VB to the Ta 5d CB, corres-
layered perovskite K2La2Ti3O10 as a result of the attempts made
ponding to an excitation of 44 eV in the UV spectrum for pure
to incorporate N3 ions. Nitrogen incorporation was attempted
NaTaO3 (Fig. 15a). Accordingly, the excitation of O 2p to Ta 5d is
by the solid-state reaction of the parent oxide with urea at
expected to red shift due to the hybridization of Cr 3d and Ta 5d
approximately 400 1C in air. Nitridation using urea resulted in
in the CB for the model of Cr@Na (Fig. 15c). In contrast, in the
not only nitrogen doping but also sensitization due to the presence
model of the dual substitution Cr@(Na, Ta), there may be two
of carbon nitride (CN) polymers, which resulted in visible light
types of photoexcitation electrons under visible light irradiation
absorption. Simple doping of nitrogen under an ammonia atmo-
(Fig. 15d), which may explain the two different absorptions in
sphere at 400 1C for 6 h in N-K2La2Ti3O10 resulted in a BG reduction
the long-wavelength visible region estimated from the UV-vis
from 3.63 eV (K2La2Ti3O10) to 3.59 eV (N-K2La2Ti3O10),98 which is
reflectance spectra. The dual substitution yielded mid-gap levels
comparable to the earlier observed BG reduction of 3.69 eV
between the CB and VB, which resulted in a decrease in the BG
(K2La2Ti3O10) to 3.44 eV (K2La2Ti3O10xNx).99 However, CN polymers
energies, which is beneficial for visible-light absorption.
become incorporated as in the present case of CN-K2La2Ti3O10,
whose UV-visible absorption spectra exhibited a larger red shift of
3.3.1.2 Selection and doping process of A-site and X-site elements.
approximately 100 nm. The BG was reduced to 2.92 eV for the CN
Some researchers have focused on reducing Ebg of the perovskites
polymer-incorporated nitrogen-doped K2La2Ti3O10. The noticeable
via selective A-site or X-site doping.98,99 Lowering the BGs was
reduction in the BG (0.71 eV) of CN-K2La2Ti3O10 can only be
achieved by Kumar et al. for the layered perovskite K2La2Ti3O10
explained by the presence of CN polymers, rather than by
simple doping of nitrogen for oxygen, suggesting a new route
for the N doping for perovskites.
3.3.2 Reduction of the recombination rate of the
electronhole pair
3.3.2.1 A/B-site doping process. Many researchers have focused
on developing highly active photocatalysts for the degradation
of organic dyes using doping foreign elements at the A site or
B site to reduce the recombination rate of electronhole pairs
by reducing the particle size.64,65,100 Among the various doping
processes, Sr and Mn were used to dope BiFeO3 and LaFeO3
Fig. 15 A schematic diagram of the electronic intraband transition of (a)
perovskite catalysts at the A site and B site, respectively, which
NaTaO3, (b) Cr doped NaTaO3 for Cr replacing Ta atom, (c) Cr doped
NaTaO3 for Cr replacing Na atom, (d) Cr doped NaTaO3 for Cr replacing Ta
resulted in reduced particle sizes of the perovskite.64,65 Using
and Na atoms. Reproduced with permission from ref. 95. Copyright 2012, the A-site doping of Ca for LaFeO3 catalysts (La1xCaxFeO3,
Royal Society of Chemistry. x = 0.050.20) for the photocatalytic degradation of MB reaction
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as an example revealed that partial substitution of La3+ in for the degradation of organic dyes by reducing the possibility
LaFeO3 with Ca2+ decreased the crystalline size and enhanced of the recombination of electronhole pairs.72,102106 LaFeO3
the visible light absorption and photocatalytic activity.100 The exhibits significant physical and chemical properties, making
10 mol% doping of Ca resulted in the best photoactivity among them important for use in photocatalysis.72,102,103 For the
the various catalysts, and the degradation rate of MB improved preparation of LaFeO3, several wet chemical methods have
from 48.9 to 77.5% after 1 hour operation with visible light after been proposed to improve the homogeneity and reproducibility
the 10 mol% doping of calcium. Based on the results, we can of the powders and reduce the preparation temperature, such
see that La0.9Ca0.1FeO3 exhibited strong photocatalytic activity as solgel and hydrothermal methods. For example, LaFeO3
for the decomposition of MB under visible light irradiation. nanoparticles were directly synthesized using a one-step microwave-
There are three factors that are related to the photocatalytic assisted route without an additional high-temperature calcination
activity. First, the photocatalytic activity increases with increas- process.102 It was observed that the prepared LaFeO3 was a
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ing Ca concentration because the particle size decreases and the single-phase perovskite with a sphere-like shape that exhibited
surface area increases, leading to an increase in the adsorption strong visible-light absorption and an optical absorption onset
of pollutants on the photocatalyst. Second, when the La3+ ion of 525 nm, corresponding to a BG of 2.36 eV. These results
was displaced by the Ca2+ ion, CaLa 0 donor centers and oxygen showed that LaFeO3 was highly visible-light photocatalytic
vacancies were formed. When the doping concentration was active for the degradation of MB. The degradation rate of MB
relatively low, the number of CaLa 0 donor centers increased was approximately 100% after 1 h operation with visible light,
with increasing dopant concentration, resulting in an increase which was even much higher than the Ca-doped LaFeO3
in the number of photoinduced electrons and an increase in catalysts prepared by the reverse microemulsion method under
the photocatalytic activity. However, when the doping concen- the same conditions, suggesting the effective improvement in
tration was too high, the dopant likely acted as an electron activity by adopting the microwave-assisted route. In addition,
hole recombination center and decreased the photocatalytic nanosized LaFeO3 photocatalysts for the photo-degradation of
activity. Finally, the photocatalytic activity was also related to the RB reaction under visible light irradiation were also synthe-
photo absorption. The Ca-doped photocatalyst exhibited a sized using a solgel method. The activity of the as-prepared
larger light absorption capacity at l 4 420 nm than that of LaFeO3 was much higher than that of commercial Degussa P25
the undoped photocatalyst. TiO2 under visible irradiation, and the degradation rate of RB
It was observed that the dierence in the filled f shell of the on the LaFeO3 after sintering at 500 1C was approximately
A-site dopant also aected the recombination rate of the 8 times higher than that of P25 TiO2.
electronhole pair of the perovskite catalysts. Li et al. studied In addition to the aforementioned methods, the hydrothermal
the effect of the Ln element doping on the performance of method has been widely used for the preparation of nanosized
La2Ti2O7 perovskite for the photocatalytic degradation of MO LaFeO3 perovskite with the advantages of a well-controlled size,
reaction.101 Nanocrystalline La1.5Ln0.5Ti2O7 (Ln = Pr, Gd, Er) low temperature growth, cost eectiveness, and less complicated
was prepared using a polymeric complex method. Among the product. Thirumalairajan et al. successfully synthesized micro-
three doped perovskites, La1.5Gd0.5Ti2O7 exhibited the best spheres composed of LaFeO3 nanoparticles with an orthorhombic
photocatalytic activity, and it was assumed that the half-filled structure via a citric-acid-assisted hydrothermal method.103
electronic configuration of Gd3+ promoted charge transfer and Morphological analysis revealed microspheres with diameters
then enhanced the photocatalytic activity. The difference in the of 24 mm composed of nanoparticles with an average size of
photocatalytic activity for La1.5Ln0.5Ti2O7 (Ln = La, Pr, Gd, Er) 85 nm. The absorption edge at 600 nm emphasized that LaFeO3
can be related to the different Ln 4f shell. Among the various could serve as a potential visible-light-driven photocatalytic
dopants, Gd3+ is different from other rare-earth ions because catalyst for the degradation of RB aqueous solutions with good
this ion has a half-filled f shell. The half-filled configuration of photocatalytic activity. The formation mechanism of the LaFeO3
the metal ion is more stable, and this ion has a strong tendency microspheres is illustrated schematically in Fig. 16.103 In the
to return to the original stable state when such a configuration initial stages of the hydrothermal reaction, metal ions in the
is destroyed. This particular characteristic of the dopant ion solution react with citric acid to form relatively stable distorted
with the half-filled electronic configuration can promote charge primary particles of LaFeO3 under supersaturated condition,
transfer and efficiently separate the electronhole pairs by which decreased the free metal ion concentration in solution and
shallowly trapping electrons.101 Although other metal ions can resulted in the slow generation of primary particles. Generally,
also trap the photo-excited electrons, detrapping is more difficult the Ostwald ripening process involves the formation of aggre-
on these metal ions. Therefore, La1.5Gd0.5Ti2O7 exhibits higher gates with primary crystallites through the crystallization process
efficiency in the separation and transfer of charge carriers and due to the energy difference. The formed LaFeO3 nanoparticles
exhibits higher reactivity than other rare-earth La1.5Ln0.5Ti2O7 aggregated together, driven by minimization of the interfacial
compounds (Ln = La, Er and Pr). energy. The aggregated nanoparticles would act as primary
cores that favor homogenous assembly to produce larger self-
3.3.2.2 Preparation methods. Some researchers have observed assembled aggregates via the self-assembly process. The aggre-
that the preparation methods also have a strong eect on the gated particles tend to form a spherical shape, as the aggregation
photocatalytic activity of LaFeO3 and LaCoO3 perovskite catalysts speed of the nanoparticles from each direction to the core
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microspheres. Reproduced with permission from ref. 103. Copyright 2012, and solid-state reaction method, on the photocatalytic perfor-
Elsevier Inc. mance of the LaCoO3 catalysts.104 The LaCoO3 catalyst prepared
using the microwave-assisted process exhibited the highest
activity at the same sintering temperature. Specifically, the rate
could be the same. The effect of the reaction time and calcina-
constant k of LaCoO3 prepared with the microwave-assisted
tion temperature on the LaFeO3 microsphere morphology also
process was 1.7 and 40 times higher than that of the catalysts
supports the finding that the Ostwald ripening effect is an
prepared by the malic acid method and solid-state reaction
essential mechanism.
method, respectively. Fu et al. reported a simple method to
LaFeO3 nanostructures, such as nanocubes, nanorods and
synthesize perovskite-type LaCoO3 hollow nanospheres at a
nanospheres, tailored using dierent surfactants, were synthe-
relatively low calcination temperature at 550 1C by utilizing
sized using the hydrothermal process by Thirumalairajan et al.;72
the carbonaceous colloids as a template and internal heat
the authors considered that the possible growth mechanism
sources.105 The formation process of perovskite-type LaCoO3
of the formation of LaFeO3 nanostructures was based mainly
hollow spheres, which can be divided into two steps, is illu-
on the self-assembly growth mechanism occurring due to the
strated in Fig. 18.105 The carbonaceous colloid template is
localized Ostwald ripening process. The morphologies of the
hydrophilic and negatively charged and is prepared from a
LaFeO3 nanostructures synthesized by hydrothermal reactions
saccharide solution and functionalized with OH and C@O
with and without structure-directing agents are shown in Fig. 17.72
groups with large surface area and nano-scale pores distributed
The cube-like LaFeO3 morphology was obtained by direct hydro-
uniformly on its surface. First, carbon@LaCo are formed
thermal synthesis without the use of any structure-directing
through the surface-layer-adsorption process: the functional
agents. These cube-like structures have sharp edges and a smooth
groups and nano-scale pores in the surface layer can bind or
surface, as illustrated in Fig. 17a. When urea was used as a
capture La3+ and Co2+ cations through coordination or electro-
structure-directing agent, nanorods of LaFeO3 were obtained,
static interactions upon the dispersal of the carbonaceous
as shown in Fig. 17b. The use of another structure-directing
spheres in the solution with [La3+] : [Co2+] = 1 : 1. The sequential
agent, citric acid, resulted in sphere-shaped nanostructures
removal of the carbon cores, densification, cross-linking, and
phase transformation of La and Co in the layer via a calcination
process resulted in the formation of LaCoO3 hollow spheres.
It was also clearly demonstrated that the carbonaceous poly-
saccharide microspheres played a dual-functional role as tem-
plates and internal heat sources in the formation process,
which could be attributed to the low-temperature formation
of a perovskite-type structure at temperatures as low as 550 1C.
The LaCoO3 hollow spheres exhibited broad and strong absorp-
tion at 220550 nm regions with a narrow BG of 2.07 eV. The
LaCoO3 hollow nanospheres also exhibited excellent photo-
catalytic activity for the degradation of MB, MO and neutral
red, which is comparable to P25 after a 100 min reaction,
making it a promising candidate for environmentally friendly
applications, such as the treatment of wastewater.
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Table 2 Photocatalytic activity of the selected perovskite-based and P25 photocatalysts for the degradation of organic dyes
4. Perovskite materials in energy-related extra current with a decrease in voltage. Through a trade-o of
photovoltaic reactions (solar cells) these two eects, the optimal BG is approximately 1.4 eV for a
solar cell prepared from a single material. Researchers have
Within the past 2 years, the eciencies of the hybrid organic observed that the BG of perovskite materials will decrease with
inorganic perovskite solar cells have increased to more than (1) a decrease in the dierence in the eective electronegativity
15%. These solar cells are solution-processable, inexpensive and between the metal (B site) cation and the anion, (2) a decrease
composed of earth-abundant materials, making them promising in the electronegativity of X site anions, (3) an increase in the
candidates for highly efficient and low-cost solar power genera- dimensionality of the BX6 network, and (4) an increase in the
tion systems. In this section, first of all, some strategies used to angle of the BXB bonds.107
design perovskite light absorbers in solar cells are given and
related perovskite designation is also presented in detail. 4.1.1.1 Decrease of the dierence in electronegativity between
B-site cation and anion. Some perovskite oxides, such as alkaline-
4.1 Strategies to design perovskite light absorbers in earth metal titanates (ATiO3, A = Ca, Sr, Ba), have wide BGs
solar cells (35 eV) due to the large difference in electronegativity between
4.1.1 Band gap engineering. Materials for solar light harvest- the oxygen and titanium atoms (3.5 vs. 1.5).108 By modifying the
ing are diversified but the good candidates all have a common composition by reducing the difference in electronegativity
feature: broad and strong absorption over the visible to near between oxygen and the B site element in the perovskite,
infrared region of the solar spectrum. It is believed that semi- a low BG of 2.7 eV was obtained for BiFeO3 perovskite due
conductors with a BG below 1.1 eV are suitable for solar light to the higher electronegativity of Fe than Ti.109 In addition,
absorption. However, if the BG is too narrow, the cell will collect for the CH3NH3PbI3 system, due to the smaller difference in
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viable replacements for Pb in the perovskite material are Sn and Fig. 23 Representative SEM images of the (a) CH3NH3PbI3 and (b)
CH3NH3Sn0.5Pb0.5I3 films on top of the mesoporous TiO2 electrodes.
Ge because these metals have larger XBX angles, as mentioned
The scale bars represent 1 mm. (c) EDS elemental mapping of Pb, Sn and
above, which are beneficial for reducing Ebg. However, the major I in film (b). Reproduced with permission from ref. 136. Copyright 2014,
problem with the use of these metals is their chemical instability American Chemical Society.
in the required oxidation state. A recent study by Ogomi et al.
reported a mixed metal, SnPb, perovskite that enabled the
tunability of the BG of the perovskite absorber by varying the
These results were confirmed by optical measurements of the
Sn : Pb ratio, indicating that Sn could be a good choice for metal
materials, and for example, an optimal short-circuit photo-
ions, especially for lower BG solar cells.116 The best performance
current density over 20 mA cm2 was obtained for the mixed
was obtained using CH3NH3Sn0.5Pb0.5I3 perovskite and a PCE of
alloy CH3NH3Sn0.5Pb0.5I3 under AM 1.5G simulated sunlight
4.18% with a Voc of 0.42 V, FF of 0.50 and Jsc of 20.04 mA cm2
of 100 mW cm2. The anomalous trend in the BG of
was reported. The edge of the incident photon to the current
CH3NH3SnxPb1xI3 was the same as the trend observed in
efficiency curve reached 1060 nm, which was red-shifted by
Pb1xSnxTe.136 In this system, band inversion occurred with
260 nm compared to that of CH3NH3PbI3 perovskite. However,
varying x, which was associated with a systematic change in the
the same study reported that the CH3NH3SnI3 perovskite did not
atomic orbital composition of the CBs and VBs. This occurred
exhibit significant photovoltaic properties, as shown in Fig. 22
because the CBM in SnTe had a similar orbital composition as
and that a minimum content of Pb was needed to stabilize the
the VBM in PbTe and vice versa, which could be attributed to
Sn2+ oxidation state.
the anomalous trend rather than the expected Vegards law
Hao et al. examined the performance of perovskite solar cells
trend in Ebg. An in-depth understanding of this unique effect,
based on alloyed perovskite solid solutions of methylammonium
which is responsible for being able to significantly extend the
tin iodide and its lead analogue (CH3NH3Sn1xPbxI3).136 Ebg of
solar absorption spectrum of perovskite-based systems, will require
the mixed PbSn compounds did not follow a linear trend
careful electronic band structure calculations. In addition, the
(Vegards law) in between these two extremes of 1.55 and
Sn doping in CH3NH3PbI3 could also affect the morphology of
1.35 eV but had a narrower BG (o1.3 eV), thus extending
the thin film. Fig. 23 shows two representative SEM images of
the light absorption into the near-infrared region (1050 nm).
CH3NH3PbI3 and CH3NH3Sn0.5Pb0.5I3 films on mesoporous
TiO2 electrodes. The CH3NH3PbI3 film was composed of inter-
connected nanoscale domains with sizes ranging from 200 to
500 nm with good film coverage. However, the CH3NH3Sn0.5Pb0.5I3
film displayed superior film quality and coverage. Compared to the
CH3NH3PbI3 film, the contrast features apparent in the hybrid
CH3NH3Sn0.5Pb0.5I3 film suggest the formation of smaller crystallite
domains, implying more efficient film formation via favorable
crystal growth of the mixed-metal perovskite. Fig. 23c presents
elemental maps of Pb, Sn, and I in the CH3NH3Sn0.5Pb0.5I3 film
obtained via SEM-energy dispersive spectroscopy (EDS). It is
apparent that Sn and Pb are distributed homogeneously
throughout the film with no evident phase separation.
Very recently, Noel et al. employed a completely lead-free
perovskite, CH3NH3SnI3, for perovskite-based solar cells.137
A PCE greater than 6% was achieved under simulated full
Fig. 22 IV curves for CH3NH3SnxPb(1x)I3 perovskite solar cells. Com-
sunlight with a Voc of 0.88 V and a BG of 1.23 eV. However,
position: CH3NH3SnxPb(1x)I3/P3HT. Solar cells were measured under
100 mW cm2 (AM 1.5G) light illumination with masked area 0.4 mm
the stability of CH3NH3SnI3 remains a challenge, and the main
0.4 mm. Reproduced with permission from ref. 116. Copyright 2014, issue is now the stabilization of the material then the oxidation
American Chemical Society. of the Sn is suppressed. By solving this issue, it can be expected
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devices if the formation of the yellow d-FAPbI3 component could absorber had smaller electronhole diffusion lengths of B100 nm.
be fully avoided. Similarly, FAPbI3 was introduced successfully Similarly, Xing et al.117 also reported that the electronhole diffu-
into hole-conductor-free fully printable mesoscopic perovskite sion lengths of CH3NH3PbI3 absorber were approximately 100 nm
solar cells with a carbon counter electrode. Using the sequential by applying femtosecond transient optical spectroscopy to bilayers
deposition method, the FAPbI3-based solar cell yielded an effi- that interface this perovskite with either selective-electron or
ciency of 11.9%, which is superior to that of the MAPbI3 solar cell selective-hole extraction materials.
of 11.4% due to broadening the light to 840 nm. By optimizing Recently, Wehrenfennig et al. examined the charge carrier
the FA and MA cation mixing ratio to 3 : 2, a PCE of 12.9% was dynamics in vapor-deposited CH3NH3PbI3xClx using ultrafast
achieved with this low-cost fully printable mesoscopic solar cell, THz spectroscopy, revealing the carrier mobility and recombi-
which indicated a promising prospect for low-cost photovoltaic nation rates.145 Under typical solar-cell operation conditions, the
technology. Choi et al. demonstrated cesium-doping in methyl- charge carrier lifetimes were limited by only mono-molecular decay
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ammonium lead iodide perovskite (CsxMA1xPbI3) light absorbers processes, such as trap-mediated recombination, which have
to improve the performance of perovskite-based solar cells. The previously been observed to be exceptionally slow. The resulting
CsxMA1xPbI3 perovskite devices with an optimized 10 mol% Cs charge diusion length was observed to be 3 mm, highlighting
doping concentration exhibited remarkable improvement in the ability of dual-source evaporation as a fabrication route for
the device efficiency from 5.51 to 7.68% due to increases in organolead halide absorber layers in highly ecient planar-
Jsc and Voc.144 This improvement should be attributed to the heterojunction solar cells.
increased light absorption capability, improved film morphology Because of their longer diusion lengths of electronhole
and almost unchanged Ebg. The optical BG of CsxMA1xPbI3 pairs, CH3NH3PbI3xClx series have attracted increasing atten-
perovskite gradually increased from 1.52 eV for pure MAPbI3 to tion.146150 Ma et al. synthesized CH3NH3PbI3xClx via a two-
2.05 eV for pure CsPbI3 with increasing Cs content, which step sequential solution deposition process using a mixture of
suggests that the optical BG can be tuned easily by controlling PbCl2 and PbI2 as the precursor to overcome the low solubility
the amount of Cs in CsxMA1xPbI3 perovskites. of pure PbCl2 with easy morphology control, and an achieved a
4.2.3 Increase in the diusion length of the electronhole PCE of 11.7%.146 Although excellent photovoltaic performance
pair. It is well known that the recombination lifetime of the was achieved using CH3NH3PbI3xClx, the formation of this
electronhole pair is a crucial factor that contributes to the mixed halide perovskite and the role of the chloride is unclear.
charge diffusion length of light-absorbing materials and hence Colella et al. studied the role of the chloride dopant on the
affects their photovoltaic performance. In other words, longer transport and structural properties of CH3NH3PbI3xClx light
charge diffusion lengths are associated with longer recombination absorbers.147 These authors observed that independent of the
lifetimes of electronhole pairs, which is beneficial for improving ratio of components in the precursor solution, Cl incorporation
the performance of perovskite light-absorber-based solar cells. For in an iodide-based structure is possible only at relatively low
example, for CH3NH3PbI3 and CH3NH3PbI3xClx, both perovskites concentrations (below 34%). The PCE increased from 3.85 to
have a similar light absorption range, whereas CH3NH3PbI3xClx 6.15% with Cl doping. The strong difference in the halogen
has a longer recombination lifetime than CH3NH3PbI3, followed ionic radii interferes with the formation of a continuous solid
by a longer diffusion length. The relatively large charge carrier solution. However, even if the BG of the material remains
diffusion lengths arise from the higher mobility and larger substantially unchanged, the Cl doping dramatically improves
charge carrier lifetimes in these materials. Therefore, light- the charge transport within the perovskite layer, explaining the
generated electrons and holes can move ultra-long distances in outstanding performance improvement of this material.
the perovskite, resulting in the generation of a photocurrent, It was observed that the doping amount of Cl in CH3NH3PbBr3
instead of losing their energy as heat within the solar cells. was much larger than that in CH3NH3PbI3, which led to increased
In addition, unlike CH3NH3PbI3, CH3NH3PbI3xClx does not recombination lifetimes of electronhole pairs. Zhang et al.
require a mesoporous electron transport layer (e.g., TiO2). The reported that the mixed halide perovskites CH3NH3PbBr3xClx
long electron diffusion length enables CH3NH3PbI3xClx to (x = 0.61.2) exhibited different optical properties.151 In parti-
work perfectly on insulating scaffolds and even in bulk films. cular, the thin films prepared with these perovskites exhibited
A longer electron diffusion length facilitates a larger optimized extraordinary photoluminescence emission intensities and pro-
thickness of the light-absorbing layer, where charge carriers longed recombination lifetimes, which are desirable for light-
can be extracted in a timely manner before recombination. emitting and photovoltaic applications. The recombination lifetime
A thicker light-absorbing layer will eventually contribute to of CH3NH3PbBr3xClx was determined by measuring the photo-
more effective light utilization by employing more absorbers. luminescence decay at the emission peak wavelengths. The time-
Specifically, Stranks et al. used transient absorption and resolved photoluminescence decay curves of CH3NH3PbBr3xClx
photoluminescence-quenching measurements to determine the with different Cl substitution ratios are presented in Fig. 25.
electronhole diffusion lengths, diffusion constants and lifetimes CH3NH3PbBr3xClx exhibits a longer average recombination life-
in CH3NH3PbI3xClx and CH3NH3PbI3 perovskite absorbers.118 It time than CH3NH3PbBr3. In particular, for CH3NH3PbBr2.4Cl0.6,
was observed that the diffusion length was larger than 1 mm in the the average recombination lifetime can be extended up to
CH3NH3PbI3xClx perovskite, which is an order of magnitude 446 ns compared to 100 ns and 44 ns for CH3NH3PbBr3 and
greater than the absorption depth. In contrast, the CH3NH3PbI3 CH3NH3PbI3xClx, respectively. However, the corresponding
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due to the reduced recombination in the GBs and the TiO2/ The PCEs were 8.5, 4.5 and 1.6% under AM 1.5G illumination
perovskite surface. Additionally, the GB property of the perovs- for the spiro-MeOTAD, P3HT and DEH, respectively. Electron
kite film behaved dierently after passivation. This controllable lifetime measurements showed that the recombination of the
self-induced passivation technique represents an important step separated charges in the device using spiro-MeOTAD as the
to understanding the polycrystalline nature of hybrid perovskite HTM was more than 10 times slower than that in the device
thin films and judiciously contributes to the development with P3HT and more than 100 times slower than that in the
of perovskite solar cells. Future work focused on the nature of device with DEH. These results suggest that the nature of the
the GBs of perovskite materials to design a rational approach to HTM is essential for charge recombination and suggests that
passivate the film will be needed. Recently, Noel et al. reported finding an optimal HTM for the perovskite solar cell includes
that treatment of organicinorganic metal halide perovskite controlling the perovskiteHTM interaction. However, spiro-
films with the Lewis bases thiophene and pyridine resulted in MeOTAD alone in HTM is insufficient for obtaining high PCEs
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a significant decrease in the rate of non-radiative recombination because of the low conductivity and other problems. Adding
in perovskite films.161 These results were attributed to the electronic different types of functional additives to spiro-MeOTAD can
passivation of under-coordinated Pb atoms within the crystal. The further improve the properties of HTM and ensure high-
Lewis base molecules bind to the under-coordinated Pb ions in efficiency perovskite solar cells.163165 Zhang et al. used a stable
the perovskite crystal, thus passivating these defect sites. Using ionic liquid N-butyl-N0 -(4-pyridylheptyl) imidazolium bis(trifluoro-
this method of Lewis base passivation, the PCEs for solution- methane)sulfonimide (BuPyIm-TFSI) as a dual-functional additive
processed planar heterojunction solar cells were enhanced from to simultaneously improve the electrical property of spiro-
13% to 15.3% and 16.5% for the untreated, thiophene-treated and MeOTAD and suppress charge combination in perovskite solar
pyridine-treated solar cells, respectively. cells.163 The PCE increased greatly from 3.83% to 7.91% with this
4.2.5 Other issues concerning CH3NH3PbI3-based perovskite additive, which is comparable to that of the conventional spiro-
solar cells MeOTAD containing lithium salt and 4-tert-butylpyridine (TBP).
4.2.5.1 Development of active hole-transporting materials to Moreover, using such a dual-functional additive can effectively
suppress electronhole pair recombination. Perovskite solar cells simplify the components of the HTM and help reduce the
generally consist of a conductive substrate, a compact TiO2 layer, production costs.
an organohalide lead perovskite light-absorption layer (single or The highest cost of materials in perovskite-based solar cells
combined with a porous scaffold), a hole-transporting material come from spiro-MeOTAD, which is very expensive because of
(HTM), and a metal cathode (Ag or Au). Studies have focused its multistep synthesis process. The current commercial price
mainly on designing scaffold layers, optimizing the perovskite of high purity spiro-MeOTAD is more than ten times that of
layer and exploring alternative structures. As one of the key gold and platinum precious metals. Therefore, it is imperative,
components in perovskite solar cells, the HTM separates the from a commercialization viewpoint, to develop ecient and cost-
photo-excited electronhole pairs and transports the holes to eective HTMs. Some new organic HTMs based on triptycene core,
the external circuit. Recently, researchers have focused on the 3,4-ethylenedioxythiophene, quinolizino acridine, polythiophene
development of a HTM suitable for organohalide lead perovskites and tetrathiafulvalene derivatives have recently been developed
to achieve high performance. Appropriate HTMs for perovskite with high PCEs.166171 For example, Li et al. reported an electron-
solar cells should primarily meet the following requirements: rich molecule based on 3,4-ethylenedioxythiophene (H101).167
good hole mobility, a compatible HOMO (Highest Occupied When H101 was used as the HTM in a perovskite-based solar
Molecular Orbital) energy level relative to the perovskites and cell, the PCE reached 13.8% under AM 1.5G solar simulation.
low cost for commercialization. Fluorine-doped CsSnI3 was This result is comparable to that obtained using the well-known
adopted by Kanatzidis and co-workers in 2012 as a p-type HTM spiro-MeOTAD, highlighting its potential to replace the
solid HTM in DSSCs with N719 (bis(tetrabutylammonium)[cis- expensive spiro-MeOTAD given its much simpler and less
di(thiocyanato)-bis(2,20 -bipyridyl-4-carboxylate-4 0 -carboxylic acid)- expensive synthesis. Despite its high cost, the most investigated
ruthenium(II)]) as the absorber.133 This study was the first to wide-gap spiro-MeOTAD almost exhibited no absorption in
use a perovskite material as the HTM in a solid-state DSSC the visible and near-IR region of the solar spectrum. In this
with efficiencies reaching 10.2%, which revived the concept of respect, low BG donoracceptor (DA) polymers with strong
all-solid-state inorganic solar cells and demonstrated that absorptions in this spectral region should be designed for the
perovskite materials could be good HTM candidates.133 The HTM in perovskite-based solar cells. Low BG oligothiophenes
next breakthrough occurred in late 2012, when M. Gra tzel and incorporating S,N-heteropentacene central units were developed
co-workers teamed with N. G. Park, who used CH3NH3PbI3 as a by Qin et al.172 and used as an HTM in solid-state perovskite-
light harvester in combination with solid HTM spiro-MeOTAD based solar cells. In addition to appropriate electronic energy
on mesoporous TiO2, leading to a PCE of 9.7%.50 Spiro-MeOTAD levels, these materials exhibit high photo absorptivity in the low
was demonstrated to be an effective HTM for perovskite-based energy region and could contribute to the light harvesting of
solar cells. For example, Bi et al. studied the effects of HTMs on the the solar spectrum, which opens up a new avenue for the
performance of CH3NH3PbI3-based solar cells, and various HTMs fabrication and material selection of perovskite-based devices.
include spiro-MeOTAD, poly(3-hexylthiophene-2,5-diyl) (P3HT) Solution-processed CH3NH3PbI3-based devices using this HTM
and 4-(diethylamino)-benzaldehyde diphenylhydrazone (DEH).162 achieved PCEs of 9.510.5%.
Chem. Soc. Rev. This journal is The Royal Society of Chemistry 2015
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The developed HTMs are all organic compounds, which are BG of 1.39 eV at room temperature and exhibits a photocurrent
likely to remain expensive due to the synthetic methods and density that is approximately 50 times larger than that of the
high purity required for photovoltaic applications. Therefore, classic ferroelectric (Pb,La)(Zr,Ti)O3 material. The ideal match
the design of new inorganic HTMs is suggested. Compared to of the BG of KBNNO to the solar spectrum, its compositional
organic HTMs, inorganic p-type semiconductors appear to be an tuning throughout the visible range and its photo-response
ideal choice given their high mobility, stability, ease of synthesis, properties open up the possibility of ferroelectric photovoltaic
and low cost. Copper iodide (CuI) was recently reported as a hole efficiency of above 3% in a thin-film device and the use of
conductor in lead halide perovskite-based devices, exhibiting a ferroelectric materials as solar absorber layers and carrier
PCE of 6.0%.173 CuI has a higher FF than spiro-MeOTAD because separators in practical photovoltaics. The capability of KBNNO
of its higher electrical conductivity. However, the eciency to absorb 3 to 6 times more solar energy than the current
obtained with CuI remains lower than that for spiro-MeOTAD ferroelectric materials suggests a route to viable ferroelectric
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because of the exceptionally high voltages obtained in spiro- semiconductor-based cells for solar energy conversion and
MeOTAD solar cells. Recently, Qin et al. demonstrated an eective other applications. This is also important for ferroelectric
and inexpensive inorganic p-type HTM, copper thiocyanate perovskites as visible-light-absorber for solar cells. Similar
(CuSCN) on CH3NH3PbI3 perovskite-based devices.174 Using a results have also been reported by Zhou et al.,182 and it was
low-temperature solution-process deposition method, a PCE of observed that KBNNO with compositions of x = 0.10.3 have
12.4% was achieved under AM 1.5G solar simulation. This opens a narrow Ebg of below 1.5 eV, which is much smaller than the
the door for integrating a class of abundant and inexpensive 3.2 eV BG of the parent KNbO3 (KNO) due to the increasing
materials for photovoltaic applications.174 Ni 3d electronic states within the gap of KNO. Furthermore, the
KBNNO materials exhibit room-temperature ferromagnetism
4.2.5.2 Stability. The degradation of CH3NH3PbI3 is often (RTFM) near a tetragonal-to-cubic phase boundary. With increasing
ignored, which is a large concern for practical applications. x from 0 to 0.3, the magnetism of the samples developed from
Perovskite CH3NH3PbI3 films were observed to be extremely diamagnetism to ferromagnetism and paramagnetism, originating
sensitive to moisture in air.119 Gra tzel and co-workers demon- from the ferromagneticantiferromagnetic competition. These
strated that the device fabrication should be performed under results are helpful in achieving a deeper understanding of the
controlled atmospheric conditions with a humidity of o1%.119 phase transitions, Ebg tunability, and magnetism variations
Niu et al. systematically studied the stability of CH3NH3PbI3 in perovskite oxides and demonstrate that such materials
films and also observed that CH3NH3PbI3 was sensitive to could play a potential role in perovskite solar cells and multi-
moisture.175 To improve the stability of CH3NH3PbI3, alumina ferroic applications.
oxide was used as a post-modification material in all-solid-state Table 3 listed the photovoltaic performance of the selected
perovskite solar cells. Al2O3 could protect this perovskite from perovskite light absorbers-based solar cells. CH3NH3PbI3 is the
degradation. Moreover, the solar cells post-modified with Al2O3 most investigated material up to now but it suers from a large
exhibited more brilliant stability than those prepared without BG and small diusion length of the electronhole pair. The
modification when exposed to moisture. The Al2O3 layer could BG can be tailored by A-site, B-site and X-site doping and
act as an insulator barrier to protect CH3NH3PbI3 from degradation replacement and some excellent results are obtained. The
by moisture and suppress the electron recombination between B-site doping of a less toxic element Sn4+ for Pb2+ was used to
TiO2 and spiro-MeOTAD. The restrained electron recombination is modify the CH3NH3PbI3 materials to reduce the BG; however,
caused by the coverage of Al2O3 on TiO2 and CH3NH3PbI3, which the performance has not been satisfactory to date. In addition,
was verified by the decreased dark current and increased interface some divergences have been observed in the efficiency of
resistance in the dark. This study would open a new pathway to Sn-doped CH3NH3PbI3 light absorber and more research is
improve the long-term performance of all-solid-state solar cells. needed to study the photovoltaic performance of the Sn-doped
CH3NH3PbI3 in the future. The doping of the A site with
4.3 Other perovskite-based light absorbers formamidinium and the X site with Cl or Br could be used to
Ferroelectric perovskites have recently attracted attention as increase the diffusion length of CH3NH3PbI3. However, the
candidates for use in photovoltaic devices due to their special incorporation of Br led to an increase in BG and then a sharp
properties, such as the promotion of the desirable separation of decrease in PCE was obtained. Thus, the content of Br should
photo-excited carriers and allowing voltages higher than the be well controlled in future research. CH3NH3PbI3xClx was
BG.176180 Ferroelectric oxides are also stable in a wide range demonstrated to be a highly efficient light absorber with both
of mechanical, chemical and thermal conditions and can be high Voc and PCE. However, it was reported that only 34% Cl
fabricated using low-cost methods, such as solgel thin-film could be incorporated in the X site of CH3NH3PbI3, resulting a
deposition and sputtering. Grinberg et al. described a family relative high BG, which is comparable to CH3NH3PbI3. The
of single-phase solid oxide solutions made from low-cost and doping of the A site of formamidinium can result a higher PCE
non-toxic elements using conventional solid-state methods: than CH3NH3PbI3 and it is expected that some other organic
[KNbO3]1x[BaNi1/2Nb1/2O3d]x (KBNNO).181 These oxides exhibit cations with suitable radius will be widely developed in the
both ferroelectricity and a wide variation of BGs in the range of future. It was found that HTM also played an important role in
1.13.8 eV.181 In particular, the x = 0.1 composition has a direct achieving high PCEs. Spiro-OMeTAD is more active than some
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Table 3 Photovoltaic performance of the selected perovskite light absorbers-based solar cells
No. Light absorbera HTM Preparation method and/or treatment BGa (eV) PCE (%) Voc (V) FF Ref.
1 CH3NH3PbI3 Spiro-MeOTAD Spin coating 1.5 9 0.888 0.62 50
2 CH3NH3PbI2Cl Spiro-MeOTAD Spin coating 1.55 10.9 1.1 0.63 51
3 CH3NH3PbI3xClx Spiro-MeOTAD Spin coating 12.3 1.02 0.67 54
4 CH3NH3PbI3xClx Spiro-MeOTAD Solution-processed 8.6 0.84 0.58 55
5 CH3NH3PbI3xClx Vapour-deposited 15.4 1.07 0.67
6 CH3NH3PbI3xClx Spiro-MeOTAD Spin coating 11.4 0.89 0.64 56
7 MAPbI3 Spin coating 1.56 10.64 0.977 0.6113 110
8 MAPb(I0.88Br0.12)3 1.62 8.13 0.890 0.6531
9 MAPb(I0.05Br0.95)3 2.23 1.03 0.832 0.4981
10 CH3NH3PbBr3 Spin coating 2.17 3.13 0.96 0.59 111
11 CH3NH3PbI3 1.55 3.81 0.61 0.57
B2.2
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other organic HTMs, such as P3HT, etc. Some inorganic HTMs, unsatisfactory. As shown in Table 3, spin coating is the most
such as CuI and CuSCN, have been developed to reduce the investigated method for the preparation of the perovskite layer
high cost of spiro-OMeTAD but the photovoltaic performance is in solar cells. However, poor crystallinity and non-uniform
Chem. Soc. Rev. This journal is The Royal Society of Chemistry 2015
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morphology are always obtained with the spin coating method. activities of electrode materials.199 The light-to-electricity con-
Some modifications for the spin coating method, such as introdu- version of 1.1% is preliminarily reached on the DSSC made of
cing functional additives of NH4Cl, CH3NH3Cl, 1,8-diiodooctane, the co-precipitation-derived BaSnO3 particles. However, Li et al.
thiophene and pyridine and replacement of DMF solvent by DMSO also reported the synthesis of one-dimensional BaSnO3 hollow
were investigated and some convincing results are reported. A architectures with a length of 1.55 mm as a photoelectrode of
PCE as high as 16.5% was delivered based on the spin coating DSSCs using BaCO3@SnO2 coreshell nanorods as precursors.200
method with pyridine additive. Some advanced methods, such The absorption band of BaSnO3 is in the UV region and N719-
as vapor-assisted solution process, fast deposition crystallization, sensitized BaSnO3 films exhibited a clear photovoltaic response.
controllable passivation technique, two-step deposition, spray However, the performance of the above BaSnO3-based DSSCs
deposition etc. have been developed, and among them, vapor- was very poor with conversion efficiencies less than 1.1%.
assisted solution process was considered to be the most efficient. Recently, highly crystalline BaSnO3 nanoparticles were synthe-
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However, the PCEs with new methods are generally lower than sized by Kim et al. using a simple liquid-phase reaction followed by
those of spin coating, which need to be improved along with the a calcination process.201 A PCE of 5.2% was achieved for a DSSC
morphology and crystallinity. with the synthesized BaSnO3 nanoparticles acting as the photo-
anode, which was fabricated without any functional layers or
4.4 Perovskite-based photoanodes treatments. The formation process of these BaSnO3 nanoparticles
4.4.1 A brief overview of the photoanodes. DSSCs have is summarized in Fig. 29. Initially, amorphous BaSnO3 particles
attracted considerable attention due to their low fabrication precipitated before the particles gradually crystallized to form low-
cost and the capability of varying many components. A DSSC is crystalline peroxo-precursor particles during the liquid-phase
typically composed of a sensitizer, an electron-transporting reaction; these precursor particles then formed highly crystalline
phase, a hole-transporting phase and current-collecting sub- BaSnO3 perovskite nanoparticles through calcination.
strates. To overcome the problem of low energy conversion The thickness of the BaSnO3 film was observed to strongly
eciency, tremendous eorts have been devoted to several aect the photovoltaic performance. An obvious increase in
areas, including the use of nanostructures of oxides and addi- eciency was observed with increasing thickness of the BaSnO3
tional compact blocking layers to allow eective injection and film. The highest eciency was obtained at a thickness of 43 mm.
collection of photo-generated charge carriers and the use of Further increases in thickness did not have a positive eect. The
panchromatic dyes or multi-dye systems to improve the light- highest photovoltaic performance, which was obtained from the
harvesting capabilities. Among the various methods to enhance DSSC based on the 43 mm-thick BaSnO3 film, was attributed to
the eciency of DSSCs, the photoanode is highly critical in its superior electron collection property, which indicates that
determining the performance because this component allows BaSnO3 has great potential for use as a photoanode material in
the practical use of the charge carriers that are generated by light DSSCs. Shin et al. examined the eect of a TiCl4 treatment on the
harvesting. The most commonly used material is TiO2 with a physical, chemical and photovoltaic properties of BaSnO3-based
wide BG of 3.2 eV, whereas most relevant studies have focused DSSCs.202 The TiCl4 treatment was observed to form an ultrathin
on modification of the TiO2 electrodes.183190 However, the sole TiO2 layer on the BaSnO3 surface. The formation of the TiO2
use of TiO2 could limit the selection of other components. shell layer improved the charge-collection eciency by enhan-
For example, small semiconductor quantum dots occasionally cing the charge transport and suppressing charge recombina-
cannot be used as sensitizers for a TiO2 electrode because their tion. The optimized treatment time to achieve a high eciency
CB level is lower than that of TiO2; therefore, the excited photo- of 5.5% compared to 4.5% for the bare BaSnO3 was found to be
electrons cannot be injected from the sensitizer to TiO2. 3 min. The conversion eciency could be further increased to
Although several other oxides or mixed oxides, such as ZnO, 6.2% by increasing the thickness of the BaSnO3 film, which is
SnO2, Nb2O5, and Zn2SnO4 have also been reported as photo-
anodes for DSSCs,191198 these materials always exhibit lower
photovoltaic performance compared with DSSCs with TiO2.
Therefore, it is of great importance to develop highly active
photoanodes to replace TiO2. As mentioned above, some per-
ovskites with an ABO3 structure exhibited superior photoactivity
compared to TiO2, and their activity as well as band structure
could be well controlled by suitable doping or replacement of the
A site and/or B site and the preparation methods.108,199203
4.4.2 Material development. Recently, there have been
many reports on the photovoltaic properties of BaSnO3-based
DSSCs because BaSnO3 perovskite is an n-type semiconducting
Fig. 29 The formation process of BaSnO3 nanoparticles shown with TEM
material with a BG of approximately 3.1 eV.199202 For example,
images of (a) as-precipitated powders, (b) precursor powders obtained at a
various preparation methods including co-precipitation, hydro- liquid phase reaction time of 12 h, and (c) calcined powders in air.
thermal reaction and solid-state reaction were employed by Guo Reproduced with permission from ref. 201. Copyright 2013, Wiley-VCH
et al. to synthesize BaSnO3 particles to optimize the photoelectric Verlag GmbH & Co. KGaA, Weinheim.
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1. For example, the incorporation of 5 mol% Co to the B site the stability of the perovskite under wet conditions should be
of CeCoxTi1xO3+d perovskite catalysts led to a reduction in the well addressed, even though there are a few pre-treated methods
BG from 2.15 eV to 1.57 eV. The Ebg decreased from 4.13 eV for to improve the stability. Well-designed doping processes and/or
the undoped NaTaO3 sample to 3.14 eV for the 6.39 mol% Cr3+ pre-treatment processes would also be effective ways to enhance
doped sample. The amount of the doped element should be the stability against moisture.
well controlled as excessive doping amount may have a negative 3. The HTM in the perovskite-based solar cells is currently a
eect on the photocatalytic activity. bottleneck for the realization of cost-eective and stable
2. Many methods are suitable for the preparation of devices. The most investigated HTM is spiro-MeOTAD, which
perovskite-based photocatalysts, such as microwave, solgel, exhibits low conductivity and other problems, leading to a low
hydrothermal, ultrasonic irradiation-assisted self-combustion PCE. Adding dierent types of functional additives, such as
and surface-ion adsorption methods. Among these approaches, BuPyIm-TFSI to spiro-MeOTAD can improve the PCE of the
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the hydrothermal and microwave techniques have attracted solar cells. In addition, due to the high cost of spiro-MeOTAD
increasing attention for nanostructured catalysts and some and some new organic HTMs, some inorganic HTMs, such as
excellent results have been reported. However, in addition to CuI and CuSCN, have been investigated, but the PCEs were
the hydrothermal method, some other methods are limited to relatively low. These studies may bring a new aspect to the
prepare a specific perovskite, which have not demonstrated as development of HTMs for perovskite-based solar cells.
general methods for the perovskite synthesis. 4. The deposition methods of perovskite films have a strong
3. In addition to the development of perovskite-based photo- eect on the crystallinity and morphology of the film and thus
catalysts, several key technical constraints for some other aspects the performance of the solar cells. The simplicity of making
exist, such as the need for a catalyst immobilization strategy to solar-cell components via liquid-phase chemical reactions and
provide a cost-eective solidliquid separation, improvement of depositing the materials by methods such as spraying, spin
the photocatalytic operation for wider pH, and effective design of coating, screen-printing and ink-jet printing may make their
a photocatalytic reactor system for higher utilization of solar use widespread in practical applications in the future.
energy to reduce the costs. In addition, the low efficiency design
of current solar collecting technology has encouraged the devel- 5.4 Photoanodes for DSSCs
opmental progress of photocatalytic technology in the water Perovskite materials have also been investigated as photoanodes in
treatment industry. solar cells. For the development of perovskite photoanodes, BaSnO3
and some titanates have been used. For BaSnO3, a PCE of 5.2% was
5.3 Light absorbers for perovskite-based solar cells
achieved for a DSSC with the synthesized BaSnO3 nanoparticles
Rapid progress in the development of perovskite solar cells has as the photoanode, which was fabricated without any functional
been attained in recent years. The strategies for the designation layers or treatments; this value is higher than that of the previously
of perovskite light absorbers include band gap engineering, investigated conventional BaSnO3 anode. Further study is needed
increasing the diusion length to reduce electronhole pair to understand the physical origin of such remarkable electron
recombination and improving the crystallinity and morphology transport properties as well as the operation principles or mecha-
of the perovskite film. The main achievement, problems and nism of the BaSnO3-based solar cells with improved performance.
perspectives are shown below. For the titanates, the selection of A-site elements is very important
1. To date, there are few reports of other candidates from for the improvement of the photoactivity. Novel architectures should
CH3NH3PbI3-based materials that are suitable for solar cells. be widely used in this field because there are numerous opportu-
The B-site doping of a less toxic element Sn4+ for Pb2+ was used to nities for further improvements through systematically engineering
modify the CH3NH3PbI3 materials to reduce the BG; however, the high-electron-mobility electrodes, such as nanofibers, nanospheres,
performance has not been satisfactory to date. Many elements, nanowires and nanocubes.
such as Co2+, Fe2+, Mn2+, Pd2+ and Ge2+, can be incorporated
through various structural adaptations with the guidance of the
Goldschmidt tolerance factor to form a stable perovskite struc- Acknowledgements
ture. The A-site doping of CH3NH3PbI3 was limited to several
The authors would like to thank the Australia Research Council
organic cations, such as alkylammonium, formamidinium as well
for supporting the project under contract FT100100134. Dr Wei
as methylviologen and the related reports are limited. In the
Wang also acknowledges Curtin University for a postdoctoral
future, the combination of A sites, B sites, and/or I sites could be a
fellowship.
useful method for developing highly active CH3NH3PbI3-based
light absorbers and FAPb1xSnxI3xClx may be a possible candi-
date for light absorbers in perovskite-based solar cells. In addi- Notes and references
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