Jin 2020 - A Critical Review On Bismuth and Antimony Halides

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Journal of Materials Chemistry A Accepted Manuscript

A critical review on Bismuth and Antimony halides based
perovskites and derivatives for photovoltaic applications: recent
Received 00th January 20xx,
advances and challenges
Accepted 00th January 20xx
Zhixin Jin,ab Zheng Zhang,b Jingwei Xiu,b Haisheng Song, a* Teresa Gatti,c* and
Published on 17 July 2020. Downloaded by University of Exeter on 7/17/2020 2:46:49 AM.
DOI: 10.1039/x0xx00000x
Zhubing Heb*
For the past decade, lead halide perovskites have experienced impressive progress in
photovoltaics with the certified device conversion efficiency over 25%, owing to their outstanding
optoelectronic properties. However, the toxicity and environmental instability of the core lead
halides materials would strongly limit their commercialization. Within this scenario, research
investigations directed at assessing properties and opportunities offered by emerging lead-free
halide perovskites are becoming everyday more relevant to pinpoint new low-cost/low-toxicity
solutions for solar-to-electricity conversion. In this review, Group VA metalS, namely Bismuth (Bi)
and Antimony (Sb) halide based perovskites and derivatives with different valence states are
classified based on formulas of A3B2X9, A2AgBX6, also known as double perovskites, and
AgaBibXa+3b, called Rudorffites (A = MA, Cs, Rb, etc.; B = Bi, Sb; X = I, Br, Cl). Here, we summarize
the recent progresses in exploitation of these materials, with a special attention devoted to the
description of the crystal structures, the thin film preparation methods and the performances in
real device, including both theoretical insights and experimental observations. With this survey,
we are able to provide reasonable perspectives for the future development of high-performance
photovoltaic devices based on lead-free bismuth/antimony halide based perovskite and
derivatives.
Br-, Cl-. The APbX3 perovskite is an excellent photo-

1. Introduction active material for photovoltaics due to the unique
Organic-inorganic hybrid lead halide perovskite optoelectronic properties, including the direct and
solar cells (PvSCs) have attracted huge attention in the suitably narrow band gap,2 the extremely high
last decade as one of the most promising low-cost absorption coefficient,3 the long charge carrier diffusion
technologies with power conversion efficiency (PCE) length,4 the high defect tolerance,5 the excellent
overcoming the 25% threshold.1 The mostly ambipolar charge carrier transport properties6 and the
investigated metal halide perovskites have formula possibility to undergo solution-processing at low
APbX3, where A is a monovalent cation, e.g., temperature.7
methylammonium (CH3NH3+, MA+), formamidinium Lead-based PvSCs have been largely developed
(HC(NH2)2, FA+), Cs+ and X is a halide anion such as I-, due to the above summarized advantages. However, two
main bottlenecks, that hinder future industrialization
and commercialization of these solar technologies, are
a. Wuhan National Laboratory for Optoelectronics, Huazhong University of
Science and Technology, Luoyu Road 1037, Wuhan 430074, P.R. China. found in the poor stability towards environmental
b. Department of Materials Science and Engineering, Shenzhen Key Laboratory
factors (humidity, heat, UV-radiation etc.) and the high
of Full Spectral Solar Electricity Generation (FSSEG), Southern University of
Science and Technology, No. 1088, Xueyuan Rd., Shenzhen 518055, toxicity of lead. These disadvantages of Pb-based
Guangdong, China.
c. Center for Materials Research, Justus Liebig University, Heinrich Buff Ring
perovskites prompted many researchers to seek
17, 35392, Giessen, Germany. alternatives based on more stable and environmentally
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ARTICLE Journal Name
friendly elements. Lead-free halide perovskite-based Accordingly, we also provide critical hintsViewon future
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light absorbers mainly include post-transition metal or challenges for these materials to become protagonists in
metalloid elements like Sn,8 Ge,9 Sb,10 Bi,11,12 and research on next-generation, ultra-cheap photovoltaics.
others.13 The Sn and Ge elements belong to the same

group of Pb in periodical table, but Sn2+ and Ge2+ can be
easily oxidized into Sn4+ and Ge4+, resulting in the rapid
2. Structures and properties of group
degradation of the corresponding perovskite’s VA metal halides based perovskites
photovoltaic properties. In addition, tin compounds are and derivatives
also toxic and their effects on the environment and on As the adjacent element of Pb, the VA group
humans are well known and documented. On the other metals (Bi and Sb) have been employed to replace lead
hand, main group VA metals like Bi and Sb, also largely in well-known lead halide perovskite light absorbers in
available from natural sources, are characterized by a photovoltaic devices. Since Bi and Sb have three
high chemical stability in their trivalent form and by a valence electrons in the outmost shell and thus stand as
lower toxicity compared to Pb2+ and Sn2+. These ions trivalent cations in their halides perovskites and
have similar electronic configuration, electronegativity, derivatives. When replacing Pb2+, Bi3+ (Sb3+) would
and ionic radius to Pb2+. Capitalizing on the excellent form BiX63- (SbX63-) octahedron by bonding halide
stability and low-toxicity, research on Bi- and Sb- anions, coordinating with amines or cesium cations to
halides based perovskites and derivatives solar cells construct different phase structures with different
have emerged as a new, largely explored sector for solar dimensionality. In this section, typical A3B2X9 (A =
cells. Nowadays, the excellent level of maturity for MA+, FA+, Cs+ etc.; B = Bi3+, Sb3+; X = I-, Br-, Cl-)
them allows us to make insightful considerations from polymorphs and other derivatives will be discussed. The
data analysis. multiple connection mode of BX63- leads to a large
Indeed, in recent years of photovoltaic research, dimensional variability in crystal structures of VA metal
group VA metal halides based perovskites and halides based materials. Generally, the A3B2X9 is
derivatives have been tentatively developed. And many commonly adopted in Bismuth halides halides or
material combinations have been identified as emerging Antimony halides based compounds, along with zero
light absorbers, such as MA3Bi2I9, Cs3Bi2I9, MA3Sb2I9, dimensional (0D) or two dimensional (2D) structures. In
Cs3Sb2I9 and more. However, relatively wide bandgaps, addition, the double perovskite structures, with a
high exciton binding energies and heavy carrier general formula of A2BIBIIIX6, maintain a three
effective masses ultimately limit their photovoltaic dimensional (3D) corner-sharing perovskite structures
performance. Currently, the PCE of VA metal halides with monovalent metals (BI) and trivalent metals (BIII =
based PvSCs lay far behind that of lead halides based. Bi, Sb). Another family of photovoltaic perovskite
In this review, we provide a summary of the recent derivatives of formula AgaBibXa+3b (A = Ag+, Cu+, etc.;
developments on VA metal halides based perovskites B = Bi3+, Sb3+; X = I-, Br-, Cl-) can shape as Rudorffite
and their derivatives, mainly focusing on low structures which have 3D structures based on edge-
dimensional A3B2X9, double perovskite and Rudorffite shared [AX6] and [BX6] octahedral. Here we denote
structures. We further discuss the potential applications them as 0D, 2D, double perovskite (3D) and Rudorffite
of these emerging species in photovoltaics with (3D) structures (Fig. 1).
emphasis on theoretical and physico-chemical studies,
thin films fabrication strategies, carrier extraction layers .
screening and device structure optimization.
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Fig. 1 Crystal structures of Group VA metal halide based perovskites and derivatives. Reproduced with permission.28
Copyright 2017, Wiley-VCH. Reproduced with permission.101 Copyright 2019, Elsevier. Reproduced with permission.106
Copyright 2019, Wiley-VCH.
Pb in the perovskite lattice. Hence, Bi3+ is a good

2.1 Bismuth halide based perovskites and potential candidate for lead substitution.
derivatives Bismuth halides based perovskite derivatives
A3Bi2I9 (A = K, Rb, and Cs) have been successfully
From the point of electronic structure, the
synthesized and utilized in photovoltaics.16 The
outstanding properties of lead halide based perovskites
compounds can have two kinds of structures, namely
can be ascribed to the 6s26p0 electronic configuration of
0D and 2D. Cs3Bi2I9 crystallizes in the space group
Pb2+, which allows the hybridization of the iodide 5p
P63/mmc with a 0D hexagonal close packing structure
orbitals in the valence band with the 6p orbitals of lead
containing isolated Bi2I93- cluster dimeric units
in the conduction bands. The large absorption
comprising pairs of face-sharing Bi-I octahedra (Fig.
coefficient is mainly derived from the high density of
2a). The reduced dimensionality of 0D A3Bi2X9 systems
states which are produced by the p-orbital-based
with respect to 3D ABiX3 materials can deliver better
interatomic transition and s-p-orbital-based intra-atomic
stability against phase degradation. On the other hand,
transition. The existence of shallow defect states relies
compounds like K3Bi2I9 and Rb3Bi2I9 have 2D structures
on the strong antibonding coupling between the 6s
with corrugated layers based on corners connected Bi-I
orbital of lead and 5p orbital of iodide in the valence
octahedron (Fig. 2b). More importantly, lattice
band.14,15 Fortunately, Bi3+ and Pb2+ have very similar
parameters in A3B2X9 can be tuned by A, B, X site
ionic radii, and also have the same 6s26p0 electronic
substitutions. The band gaps can vary from 1.9 to 3.1
configuration, which may make it easy for Bi to replace
eV.17 By computing dielectric properties, anomalously
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large Born effective charge tensors on Bi3+ are found with optical absorption coefficients approaching 105Online
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due to the proximal structure instabilities of the Bi3+ 6s2 1. A long photoluminescence (PL) decay of at least 760
lone pair. The defect screening and the effective charge ps, with a bulk lifetime possibly closer to 5.6 ns, was
carrier transport are improved by these Born effective measured by Hoye et al.18 Sulfur-doped MA3Bi2I9 have

charges. The band positions of A3Bi2I9 are shown in Fig. been obtained by in situ sulfur doping via the thermal
2c, as obtained by combining density functional theory decomposition of a Bi(xt)3 (xt = ethyl xanthate)
(DFT) calculations and experimental values. precursor. Compared to MA3Bi2I9, the sulfur doping can
MA3Bi2I9 is the most studied polymorph among all shrink its bandgap to 1.45 eV. Colors of the obtained
the Bismuth halides based absorbers. The structure of films clearly changed from orange to black when
MA3Bi2I9 comprising two face-sharing bismuth iodide annealed from 80 to 150 ºC (Figure 2d).
octahedra, is a 0D dimer at room temperature. In Simultaneously, sulfur-doped MA3Bi2I9 exhibited a
contrast to MAPbX3, pure phase MA3Bi2I9 has been much higher carrier mobility and carrier concentration
synthesized by solution and vapor methods and is air than pristine MA3Bi2I9.19
stable. MA3Bi2I9 has an indirect bandgap of 2.04 eV,
Fig. 2 Crystal structures of (a) Cs3Bi2I9 and (b) Rb3Bi2I9 with details of a single octahedron. (c) Trends in band gaps of
compounds A3Bi2I9 (A is an alkali metal). Reproduced with permission.16 Copyright 2015, American Chemical Society. (d) XRD
patterns and color variations for sulfur-doped MA3Bi2I9 at different temperatures. Reproduced with permission.19 Copyright
2016, American Chemical Society.
Other organic groups replacing MA+ have also also been prepared by spin coating.22 C5H6NBiI4
been employed. MA3Bi2Cl9 is a one dimensional (1D) ([py][BiI4])(py: pyridinium) and C6H8NBiI4
organic-inorganic hybrid bismuth compound with ([mepy][BiI4])(mepy: 1-methylpyridnium) have been
double chains of distorted BiCl63- octahedra structure.20 prepared containing 1D BiI4- anionic chains built by
1D thermally stable (H3NC6H12NH3)BiI5 was edge-sharing BiI6.23 Dark-red (NH4)3Bi2I9 was
synthesized as photoactive layer including organic 1,6- synthesized through a solution method and featured a
hexanediammonium groups. Compared to MAPbI3, 2D layered derivative structure, with a measured band
(H3NC6H12NH3)BiI5 exhibited better thermal stability.21 gap of 2.04 eV.24
A new organic-inorganic compound of formula Bismuth based 3D double perovskites were also
C6H14NBi2I9 exhibiting a 0D structure has been developed, as the 3D lead-based ones show the best
synthesized by solvent evaporation. Thin films have optoelectronic performances. A 3D double perovskite

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with the chemical formula of A2BIBIIIX6 has been To achieve correct charge balance, the hypothetical
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produced by incorporating a monovalent metal into Bi3+ perovskite compound CsSbI3 may produce the crystal
site. The total charge neutrality is maintained thanks to structure of the 2D layered Cs3Sb2I9 after removal of one
the presence of monovalent and trivalent cations layer in every third Sb layer along the <111> direction

occupying the BI and BIII sites (Fig. 3a). Giorgi and (Fig. 3b).10 2D Cs3Sb2I9 has an optical band gap of 2.05
Yamashita theoretically investigated double perovskite eV and an enhanced stability under ambient air
of the type MA2TlBiI6, where Pb2+ cations in MAPbI3 compared to MAPbI3. Cs can be replaced by other alkali
are substituted by the Tl+/Bi3+ ionic pairs.25 Although it metals such as Rb and K, providing compounds with
is predicted to have good photoelectric potential, general formula A3Sb2X9. Experiments have proven that
monovalent Tl is highly toxic and therefore it is not the A-site cation plays an important role in determining
suitable for practical applications. The double the structural and optoelectronic properties of these
perovskite structure that currently attracts the largest compounds. Rb3Sb2I9 and K3Sb2I9 have a direct bandgap
attention is Cs2AgBiX6. Cs2AgBiBr6 is characterized by and 2D structures due to the smaller ionic radius of Rb+
a long room-temperature PL lifetime of more than 600 and K+ compared to Cs+, which stabilizes this type of
ns and has an indirect bandgap of around 1.95 eV. This structure.29 In addition, colloidal Cs3Sb2I9 and Rb3Sb2I9
compound is characterized by a better stability to heat nanocrystals have been synthesized.30 They also exhibit
and moisture compared to MAPbI3.26 McClure et al. 2D crystal structures and a high absorption cross-section
reported on the double perovskite Cs2AgBiBr6 and of 1015 cm2, standing out as good candidates for
Cs2AgBiCl6 synthesized from both solid state and optoelectronic applications.
solution routes.27 They found indirect band gaps of 2.19 The hexagonal structure of methylammonium
eV and 2.77 eV, respectively, by diffuse reflectance antimony iodide (MA3Sb2I9) is isomorphous with
measurements and band structure calculations. When Cs3Sb2I9 at room temperature.31 Hebig et al. reported a
exposed to air these compounds are stable, but when MA3Sb2I9 compound produced by a solution process.
exposed to both air and light for more than a week, Depending on photothermal deflection spectroscopy
Cs2AgBiBr6 starts to degrade. Finally, another family of (PDS), amorphous MA3Sb2I9 shows an absorption
photovoltaic halide based on two aliovalent metals is the coefficient α ≈ 105 cm-1 and an optical band gap of 2.14
one with general formula AgaBibIx (x=a+3b), based on eV, with a pretty large energetic disorder, as evidenced
edge-shared AX6 and BX6 octahedra. This structure is by an Urbach tail (Eu) of 62 meV and a weak PL
called Rudorffite and has a 3D R3m trigonal lattice (Fig. emission shifted at 1.58 eV, likely originated from
1). Several Ag-Bi-I Rudorffites structures have direct radiative recombination involving subgap states.32 So
band gaps in the range of 1.79-1.83 eV and feature far, most synthesized antimony halides based double
highly stability in air.28 perovskites appear to have large bandgaps (> 2 eV). As
reported recently, Cu2+-doped Cs2SbAgCl6 has a
reduced indirect bandgap of 1.02 eV compared to 2.65
2.2 Antimony halide based perovskites and
eV for Cs2SbAgCl6.33 On the other hand, the layered
derivatives
double perovskites Cs3+nM(II)nSb2X9+3n, where [SnI6]
Being also member of group VA, antimony, a and [GeI6] octahedral layers are introduced between
metalloid, is also expected to exhibit optoelectronic [Sb2I9] clusters. Providing an increased electronic
behavior similar to Bi when integrated into perovskite dimensionality (Figure 3c), it owns smaller bandgap,
derivatives structures. Sb3+ ions have similar structure to smaller carrier effective masses, larger dielectric
Bi3+ and ternary halide semiconductors such as Cs3Sb2I9 constants, lower exciton binding energies and higher
have been examined by computational and experimental optical absorption compared to Cs3Sb2I9.34 Vargas et al.
approaches. The 0D dimeric form (space group have reported that the bandgap of Cs4Mn1−xCuxSb2Cl12
_ (x = 0−1) can be modulated from 3.0 eV to 1.0 eV by
P63/mmc) and the 2D layered form (P3m1) are two
adjusting the ratio of manganese to copper in the mixed
structural modifications in Cs3Sb2I9.
chlorides,35 as shown in Figure 3d. Meanwhile, the
magnetic properties of those antimony halide based

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DOI: 10.1039/D0TA05433J
modulated by compositional engineering.

Fig. 3 (a) The structure of double perovskite model. Reproduced with permission.39 Copyright 2016, American Chemical
Society. (b) The modification of the structure of 2D layered Cs3Sb2I9 following removal of one Sb-layer every 3 along the
<111> direction. Reproduced with permission.10 Copyright 2015, American Chemical Society. (c) Schematic representation of
the crystal structure of M2+-doped Cs3Sb2I9. Reproduced with permission.34 Copyright 2018, American Chemical Society. (d)
The change in band gap after compositional engineering of Cs3+nM(II)nSb2X9+3n. Reproduced with permission.35 Copyright 2018,
American Chemical Society.
3. Theoretical studies on Group VA first principles calculations, providing meaningful

metal halide based perovskites and information on their band gaps, defects
distributions, charge carriers mobilities, absorption
derivatives 37,38 spectra and more.
Bismuth halides based PvSCs have been By theoretical simulation, all the elements of the
simulated using the General-Purpose Photovoltaic periodic table which can be integrated into double
perovskites with general formula A2BB3+X6 are showed
Device Model (GPVDM). The results show the
in Fig. 4a. The A+, B+, B3+, X- sites can be occupied by
bismuth halides based photovoltaic device can own
7, 8, 34, 5 elements, respectively. These elements can
a PCE of 20% at an active layer thickness of 450 yield nearly 10000 compounds. However, following
nm.36 At the same time, a series of theoretical Goldschmidt’s rules on perovskite structure stability,
simulations on VA metal halide based perovskites the majority of these compounds are unstable. By the
and derivatives were carried out. First principles most rigorous screening criteria, there are more than
DFT calculation can simulate the electronic 600 compounds whose synthesis could be attempted.39
structures of many body systems from atomic level The double perovskites based on Bi or Sb have been
quantum mechanics. For example, the electronic analyzed through the first-principle calculations and
structures of various perovskites were simulated by experimentally.40 Their electronic band structure and

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effective masses have been calculated using the PBE0 by first-principles calculations exploiting theViewstrategy of
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hybrid functional and DFT/LDA (local density cation-transmutation and are characterized by an
approximation), respectively (Fig. 4b). Most double intrinsic thermodynamic stability, relatively small band
perovskites were predicted to display an indirect gap gaps and light carrier effective masses. Among them,

from calculations, unless some new experimental Cs2InSbCl6 and Cs2InBiCl6, two materials with a 1.0 eV
strategies were developed for changing them into direct- direct band-gap, show the greatest potential as
gap. For example, the synthesized Cs2AgBiCl6 photovoltaic materials (Fig. 4c).41 However,
compound is a face-centered cubic double perovskite perspectives for perovskites based on low-toxicity
with an indirect gap of 2.2 eV. In general, the eleven bismuth ions might expand well-beyond the Cs2AgBiX6
optimal double perovskite materials have been screened motif, as predicted by first principle calculations. 42
Fig. 4 (a) Elements that can constitute halide double perovskites with general composition A2BB3+X6. Reproduced with
permission.39 Copyright 2016, American Chemical Society. (b) Calculated band gaps and effective hole/electron masses for
Cs2BiMX6 and Cs2SbMX6 (M = Cu, Ag or Au, X = Cl, Br or I). Reproduced with permission.40 Copyright 2016, American Chemical
Society. (c) Variation of band gaps, electronic band structures and orbital projected density of states of typical materials in
the categories: Cs2NaBiCl6, Cs2AgBiCl6, Cs2InBiCl6. Reproduced with permission.41 Copyright 2017, American Chemical Society.
(d) Electronic and optical properties of hypothetical halide double perovskites of formulas MA2InBiBr6, (Cs/MA)2InBiBr6, and
(MA/FA)2InBiBr6. Reproduced with permission.48 Copyright 2017, American Chemical Society.
Compounds like MABiSeI2 and MABiSI2 doped compounds have been identified to be a
could be prepared by introducing two anions for direct band gap of 1.3 eV to 1.4 eV, ideal for
preserving the charge neutrality from the split- single-junction solar cells (Figure 5).45 Other
anion approach.43, 44 These chalcogen elements theoretical calculations on possible double

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perovskite structures were also carried out.46, 47 systematically by tuning lattice parameters. The
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Volonakis et al. theoretically investigated bandgap of ordered Cs2AgBiBr6 is an indirect one
Cs2InBiX6 and the mixed-cation of 1.93 eV and could be modified into a pseudo-
(Cs/MA/FA)2InBiBr6 halide double perovskites. direct disordered one of 0.44 eV through a tight

A2InBiBr6 could be stabilized by employing of MA control on doping and growth temperature.49 The
and FA as the cations. The calculated bandgaps difference between the pseudo-closed s2 orbitals of
with DFT/PBE0 of MAPbI3 and MA2InBiBr6 are Tl and In could lead to different semiconducting
1.9 eV and 2.0 eV, respectively. Bandgaps of 1.7 behavior Tl-Bi and In-Bi bromide double
eV and 1.9 eV are calculated for mixed cation perovskites, as evidenced by DFT calculations. Tl-
species such as [(Cs0.5MA0.5)2InBiBr6] and Bi double perovskite shows p-type semiconducting
[(FA0.5MA0.5)2InBiBr6], respectively (Figure 4d). properties, while In-Bi ones are p-type metallic
That suggests that a certain tuning of bandgap is ones. Therefore, this analysis emerges that In-Bi
possible within a limited range for mixed cation bromide double perovskite should be disregarded
double perovskites.48 Yang et al. found that the as light absorbers, but could be perhaps suitable as
bandgap of Cs2AgBiBr6 can be changed hole-transport materials (HTM) in PvSCs.50
Fig. 5 (a) Details on crystal structures of MABiSeI2 and MAPbI3. (b) HSE (Heyd-Scuseria-Ernaerhof)-SOC (spin-orbit coupling)
calculated band gaps of MABiXY2 where X is Te, Se or S and Y is I, Br or Cl. The dashed line marks the optimal band gap of a
single-junction solar cell according to the Shockley-Queisser theory. Reproduced with permission.45 Copyright 2016, the Royal
Society of Chemistry.
cations in the pristine Sb2S3 to yield Cs2Sb8S13 and

Deng et al. synthesized double perovskite
MA2Sb8S13 leads to a significant decrease in bandgap
Cs2AgSbCl6 via a solution method. This compound has
depending on that specific A cation. Thus, it allows to
a computed indirect bandgap of 2.41 eV by projected
obtain good performances for solar harvesting
augmented wave (PAW) + HSE06 hybrid functional
applications.52
calculations. The result is comparable with the
experimental value of 2.60 eV. In addition, 4. Group VA metal halides based
Cs2AgSbCl6/TiO2 heterostructures show an improved
perovskites and derivatives for
light absorption compared to the pure perovskite and a
decreased interfacial bandgap due to the formation of photovoltaics
interfacial states.51 The structures and electronic Due to their unique optoelectronic properties and
properties of Sb2S3, Cs2Sb8S13, MA2Sb8S13 have been structural stabilities, the low-toxicity Bi- and Sb halides
investigated by first-principles techniques. Their based halide perovskites and derivatives are considered
electronic band structures are predicted through as promising absorbers to substitute the lead halide
DFT/HSE06 to have bandgaps of 1.72, 1.85 and 2.08 based counterparts in PvSCs and have done enormous
eV, respectively. Remarkably, the introduction of the A progresses in recent years in terms of improved PCE. In

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the following part of this review, we will provide a nanostructured. Comparison of the device View Article data
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detailed summary of the main examples presented in the indicates that the best is Cs3Bi2I9, with a short
recent literatures on the use of these compounds in circuit current density (Jsc) of 2.15 mA cm-2, an
photovoltaic devices. open circuit voltage (Voc) of 0.85 V, a fill factor

4.1 Bismuth halide based solar cells (FF) of 0.60 and an overall PCE of 1.09% in a
4.1.1 Photovoltaic devices based on perovskite- mesoscopic solar cell architecture. In contrast,
derivatives structures MA3Bi2I9 shows Jsc of 0.52 mA cm-2, Voc of 0.68 V,
The recorded device performances of bismuth FF of 0.33, and PCE of 0.12%, while MA3Bi2I9-
halides based PvSCs are summarized in Table 1. xClx provides very poor figures of merit (PCE
Park et al. first reported A3Bi2I9 utilized as light =0.003%). Photocurrent density-voltage (J-V)
absorber in solar cells.11 The synthesis of Cs3Bi2I9, curves of these devices are shown in Figure 6b. The
MA3Bi2I9, and MA3Bi2I9Clx was realized through authors point out that the sub-optimal morphology,
simple one-step spin-coating method. The light constituted of MA3Bi2I9-xClx particles surrounded
absorption spectra and bandgaps for the three by amorphous BiCl3 is the major cause of the
different materials were shown in Figure 6a for extremely low efficiency found for MA3Bi2I9-xClx.
comparison. Among them, Cs3Bi2I9 shows the At the same time, the first inverted planar
highest absorption coefficient and the lowest heterojunction device based on MA3Bi2I9 was
structural disorder, which results from the reported. The bandgap of MA3Bi2I9 is as high as
morphology difference of their based films. Doping 2.9 eV, and therefore its PCE is very low as about
with chlorides further changes the morphology of 0.1% (Fig. 6c).53
the film from interconnected and smooth to

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Fig. 6 (a) Tauc plots for MA3Bi2I9Clx, MA3Bi2I9, Cs3Bi2I9 thin films. (b) J-V curves for PvSC based on the three different materials
as light absorbers. Reproduced with permission.11 Copyright 2015, Wiley VCH. (c) Energy level diagram and (d) J-V curves
under illumination for planar heterojunction devices based on the MA3Bi2I9 absorber. Reproduced with permission.53
Copyright 2016, Elsevier.
Taking poly(3-hexylthiophene-2.5-diyl) (P3HT) to efficiency of the PvSC was further improved to 0.42%
replace spiro-OMeTAD as the HTM in PvSC, Lyu et on a mesoporous TiO2 electron transporting layer (ETL)
al. demonstrated a device PCE of 0.19% by substituting scaffold.55 The MA3Bi2I9 devices were found to be very
MAPbI3 with MA3Bi2I9. 54 The morphology and stable in ambient air, maintaining a stable 0.2% PCE for
crystallinity of the solution-processed MA3Bi2I9 film more than 10 weeks.56 Further studies indicate that the
and photovoltaic properties of the resulting solar PCE of MA3Bi2I9 devices can be further increased by
devices would be affected by the precursor solution improving thin film quality and optimizing the device
concentration and substrate used for deposition. The structure.57
Table 1 Summary of device performances for bismuth halides based PvSCs
Device structure Eg (eV) Jsc (mA/cm2) Voc (V) FF PCE (%) Ref.
FTO/TiO2/meso-TiO2/MA3Bi2I9/Spiro-OMeTAD/Ag 2.10 0.52 0.68 0.33 0.12 [11]
FTO/TiO2/meso-TiO2/Cs3Bi2I9/Spiro-OMeTAD/Ag 2.20 2.15 0.85 0.60 1.09 [11]
FTO/TiO2/meso-TiO2/(H3NC6H12NH3)Bi5/Spiro- 2.10 0.115 0.40 0.43 0.027 [21]
OMeTAD/Au

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ITO/PEDOT:PSS/MA3Bi2I9/PCBM/Ca/Al 2.90 0.22 0.66 0.49 0.1 [53]
FTO/TiO2/meso-TiO2/MA3Bi2I9/P3HT/Au 2.10 1.157 0.35 0.464 0.19 [54]
FTO/TiO2/meso-TiO2/MA3Bi2I9/Spiro- 2.10 1.00 0.67 0.625 0.42 [55]

OMeTAD/MoO3/Ag
FTO/TiO2/meso-TiO2/MA3Bi2I9/Spiro-OMeTAD/Au - 0.83 0.56 0.49 0.26 [56]
FTO/TiO2/MA3Bi2I9/Spiro-OMeTAD/Au 2.10 0.49 0.72 0.32 0.11 [57]
FTO/TiO2/meso-TiO2/MA3Bi2I9/Spiro-OMeTAD/Au 2.26 2.95 0.81 0.69 1.64 [59]
FTO/TiO2/meso-TiO2/MA3Bi2I9/P3HT/Au 2.20 4.02 1.01 0.78 3.17 [60]
ITO/PEDOT:PSS/MA3Bi2I9/C60/BCP/Ag 2.22 1.39 0.83 0.34 0.39 [61]
FTO/TiO2/meso-TiO2/MA3Bi2I9/Spiro-OMeTAD/Au - 0.94 0.51 0.61 0.31 [62]

FTO/TiO2/meso-TiO2/MA3Bi2I9/PIF8-TAA/Au 2.10 1.15 0.85 0.73 0.71 [65]
FTO/TiO2/MA3Bi2I9/Spiro-OMeTAD/Ag 2.10 0.37 0.69 0.32 0.08 [67]
FTO/FPDI/MA3Bi2I9/Spiro-OMeTAD/Ag 2.10 0.37 0.61 0.28 0.06 [68]
FTO/TiO2/meso-TiO2/MA3Bi2I9/PTAA/Ag 2.10 0.27 0.57 0.50 0.08 [69]
FTO/TiO2/MA3Bi2I9/Spiro-OMeTAD/Au 2.20 1.12 0.61 0.43 0.29 [70]
FTO/TiO2/TiO2 NR/MA3Bi2I9/Spiro-OMeTAD/Au 2.10 0.69 0.59 0.37 0.15 [71]
FTO/TiO2/meso-TiO2/MA3Bi2I9/PTAA/Ag 2.08 1.07 0.59 0.42 0.26 [81]
FTO/TiO2/meso-TiO2/Cs3Bi2I9/P3HT/Ag 2.30 5.78 0.86 0.64 3.20 [73]
FTO/TiO2/meso-TiO2/CsBi3I10/P3HT/Ag 1.77 3.40 0.31 0.30 0.40 [74]
FTO/TiO2/meso-TiO2/Cs3Bi2I9/P3HT/Ag 2.03 0.18 0.02 0.37 0.02 [74]
FTO/TiO2/meso-TiO2/CsBi3I10/TQ1/Ag 1.77 2.38 0.62 0.52 0.77 [75]
ITO/PEDOT:PSS/Cs3Bi2I9/PCBM/AZO/Ag 2.08 3.42 0.74 0.51 1.26 [76]
FTO/TiO2/meso-TiO2/MA3Bi2I5.22Cl3.78/PTAA/Ag 2.25 0.68 0.46 0.60 0.18 [81]
FTO/TiO2/meso-TiO2/MA3BiI3Cl6/Spiro-OMeTAD/ Au - 0.67 0.22 0.33 0.47 [82]
FTO/TiO2/meso-TiO2/MA3Bi2I9-2xSx/Spiro-OMeTAD/Au 1.67 0.58 0.54 0.48 0.15 [83]
ITO/NiOx/Cs3Bi2I6Br3/PCBM/C60/BCP/Ag 2.03 3.15 0.64 0.57 1.15 [84]
Note: Mesoporous TiO2 is abbreviated as meso-TiO2. TiO2 nanorod is abbreviated as TiO2 NR. 2,2',7,7'-Tetrakis[N,N-di(4-
methoxyphenyl)amino]-9,9'-spirobifluorene is abbreviated as Spiro-OMeTAD. [6,6]-Phenyl C61 butyric acid methyl ester is abbreviated as
PCBM. 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline is abbreviated as BCP. Poly[bis(4-phenyl)(2,4,6-triMethylphenyl)aMine] is
abbreviated as PTAA. C60 Fullerene is abbreviated as C60. Poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] is
abbreviated as TQ1. Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) is abbreviated as PEDOT:PSS. Aluminium-doped zinc oxide is
abbreviated as AZO.
The bismuth halide based compounds crystallize characterization methods.58 The maintenance of a
directly and rapidly into a textured polycrystalline continuous polycrystallinity within MA3Bi2I9 films is
microstructure from a precursor solution without crucial to the good performance of the resulting solar
evolving through intermediate crystalline solvated cells. Recently, some new methods have been applied to
phases, as determined by multi-probes in situ synthesize MA3Bi2I9 thin films. A highly compact, large

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grained MA3Bi2I9 film can be prepared employing a hysteresis-free J-V curves were recorded with anArticle
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two-step approach based on the subsequent thermal PCE of 3.17% on mesoporous DOI: TiO10.1039/D0TA05433J
2 ETLs, with
evaporation of BiI3 and MAI. By employing this excellent reproducibility (Figure 7c-d).60 This is one of
method, an excellent PCE of 1.64% was achieved.59 the highest performances found among MA3Bi2I9-based

(Figure 7a-b) The vapor assisted solution processing lead-free PvSCs. The uniform and compact MA3Bi2I9
(VASP) method also allows the preparation of thin film was prepared by a two-step (evaporation and
homogeneous MA3Bi2I9 films by exposing solution spin-coating) and the inverted planar PvSCs exhibited a
processed BiI3 films to MAI vapors. Given the very PCE of 0.39%. More excitingly, the value of Voc among
good film quality obtained by applying this method, the inverted MA3Bi2I9 devices is up to 0.83 V.61
Fig. 7 (a) Top-view SEM image of a thermally evaporated MA3Bi2I9 thin film. (b) J-V curves for the best PvSC based on a
MA3Bi2I9 light absorber obtained employing different deposition conditions. Reproduced with permission.59 Copyright 2017,
American Chemical Society. (c) Top-view SEM image of VASP deposited MA3Bi2I9.on mesoporous TiO2. (d) J-V characteristics
for BiI3 and VASP-deposited MA3Bi2I9. Reproduced with permission.60 Copyright 2018, Elsevier.
For thin-film solar cells, the film morphology the optimal device with a top PCE of 0.31% and
plays an important role in device performance. high reproducibility. Devices also maintained
Hence, a lot of work has been done to optimize the stable figures of merits for up to 30 days in a
morphology of MA3Bi2I9 thin films. A uniform relative humidity of 50-60%.62 MA3Bi2I9 cuboids
film of MA3Bi2I9 was successfully produced by can also be synthesized by an antisolvent assisted
adding 1-methyl-2-pyrrolidinone (NMP) into the crystallization method, which based mesoscopic
MA3Bi2I9-DMF precursor solution. That leads to

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DOI: 10.1039/D0TA05433J
stability in air for more than 60 days.63

Fig. 8 Multiple top view SEM images of MA3Bi2I9 films prepared through different methodologies. MA3Bi2I9 film morphology
depends on the amount of DMSO solvent added to DMF and on whether chlorobenzene (CB) is added. (a) DMF without CB,
(b) DMF with CB, (c) DMSO:DMF = 0.05:0.95 (v:v) with CB, (d) DMSO:DMF = 0.2:0.8 (v:v) with CB, and (e) DMSO with CB. (f)
MA3Bi2I9 particles size and packing density curve with variation of the DMSO/DMF ratio. Reproduced with permission.65
Copyright 2018, American Chemical Society. (g) MA3Bi2I9 perovskite derivative films fabricated with DMF (left) and ethanol
(right). Reproduced with permission.66 Copyright 2017, Wiley VCH. (h) MA3Bi2I9 films prepared via gas-assisted and
conventional methods. Reproduced with permission.67 Copyright 2017, Elsevier. (i) Cs3Bi2I9 (right) and CsBi3I10 (left) film
morphologies, color and absorption coefficients. Reproduced with permission.74 Copyright 2016, American Chemical Society.
By tuning the ratio of DMSO/DMF solvent 0.85 V.65 Dense and uniform MA3Bi2I9 films can
couple, Shin et al. obtained compact thin films of be obtained by employing ethanol as the solvent,
MA3Bi2I9, Cs3Bi2I9, FA3Bi2I9 (Figure 8a-e). differently from the porous and rough ones
Depending on the control of nucleation and growth obtained with DMF (Figure 8g). The PvSC based
rates, a film formation mechanism was proposed by on ethanol treated MA3Bi2I9 films showed a high
authors that the existence of three different regions Voc of 0.84 V, a Jsc of 0.17 mA cm-2, a FF of 0.35,
for the film growth shown in Figure 8f. PIF8-TAA, and a PCE of 0.053%.66 A dense and smooth
a co-polymer of triarylamine and benzo-fused MA3Bi2I9 active layer can also be obtained by a
difluorene units, was used to replace the classical gas-assisted deposition method.67 By further
spiro-OMeTAD HTM, obtaining a device PCE of applying a fluorinated perylene diimide (FPDI) as
0.71% for the MA3Bi2I9 based PvSC.64 More ETL in a MA3Bi2I9 PvSCs, a limited PCE
excitingly, the highest value of Voc was reported to degradation (- 0.06%) was recorded when
date for the MA3Bi2I9 photovoltaic devices, namely

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17 days.68 obtained for the modified device.75 However, Khadka et
Lan et al. designed a (BiI3)1-x(MA3Bi2I9)x mixed al. fabricated solution processed Cs3Bi2I9 and CsBi3I10
species to improve its photovoltaic output. The thin films via a solvent vapor annealing step. They

(BiI3)0.8(MA3Bi2I9)0.2-based PvSCs showed indeed an found that the Cs3Bi2I9 film has a wider bandgap (2.08
increase in Voc from 0.44 to 0.57 V compared to the one eV) than the CsBi3I10 one (1.8 eV), but it is more stable
based on pristine MA3Bi2I9, with a PCE of 0.08%.69 under annealing conditions. The Cs3Bi2I9 film achieved
Song and coworkers compared the conventional one- a PCE as high as 1.26% for the resulting device. For
step solution processing for MA3Bi2I9 with a two-step comparison, the CsBi3I10 based PvSC exhibits only poor
method based on the interdiffusion of solution- efficiency.76 Hence, we believe there are still many
processed BiI3 and CH3NH3I stacking layers, achieving problems to be solved when CsBi3I10 is employed as
a higher PCE with the latter approach in a mesoscopic light absorber in PvSCs.
PvSC compared to the use of the former (0.29% vs The layered polymorph of Cs3Bi2Br9 was studied
0.15%).70 MA3Bi2I9 PvSCs have been also fabricated by by Melot and coworkers experimentally and via DFT.
Chen et al. employing a two-step solution process The structure of this compound is a corrugated layer of
method on rutile TiO2 nanorod array ETL. Although corners sharing BiBr63- octahedra. An exciton binding
tested PCE was still very low, devices didn’t suffer any energy of 940 meV is found, substantially higher than
degradation of performance after 67 days of storage in values found in other halide perovskite derivatives and
ambient condition.71 A cation displacement approach closer to values seen in alkali halide crystals. This
was also employed to improve the morphology of indicates a strongly localized exciton character and it is
MA3Bi2I9 film. This consists in first depositing from a also the cause of a highly structured emission. Such a
solution of ethylammonium iodide and BiI3 and then large exciton binding energy, coupled to a large band
transforming the resulting hybrid material into MA3Bi2I9 gap of 2.64 eV, is of course detrimental for a
by keeping the film in a methylamine atmosphere. The photovoltaic material and the compound requires further
MA3Bi2I9 film has a smooth, uniform, and compact compositional engineering to be applied for this scope.
77 Single crystal of MA Bi Br has been studied by Leng
surface morphology. By employing it as light absorber 3 2 9
in a mesoporous PvSC architecture, a PCE of 0.33% et al. and the compound resulted to display a trigonal
_
was achieved, about two times higher than the value symmetry (P3m1 space group), characterized by metal
(0.15%) obtained with a one-step spin-coating method.72 halide octahedral layers (Fig. 9a). MA3Bi2Br9 has a
High-quality ultrathin Cs3Bi2I9 nanosheets have direct bandgap of 2.5 eV and a photoluminescence
been developed by Zhang and coworkers employing a quantum yield (PLQY) up to 12% when the material is
dissolution-recrystallization process and applied as light in the form of quantum dots (em max = 430 nm).78
absorbers in PvSC, obtaining an impressive PCE value FA3Bi2Br9 quantum dots also exhibit a bright blue
of 3.20% when CuI was used as the HTL.73 In order to emission at 437 nm with a high PLQY of 52%.79
optimize the photoelectric performance of Cs3Bi2I9, Another four organic-inorganic bismuth halides
Johansson et al. investigated a new type of cesium perovskite derivatives were also synthesized through a
bismuth iodine compound of CsBi3I10. Compared to the solvothermal method (Fig. 9b for details of the crystal
band gap of 2.03 eV found for Cs3Bi2I9, the CsBi3I10 structures). Halogens appear to change configurations in
film reached a value of 1.77 eV, with absorption these bismuth halides derivatives. For example,
maximum shifting from 610 nm to 700 nm (Fig. 8i). (TMP)[Bi2I5] (with TMP indicating the di-cationic
The absorption coefficients for CsBi3I10 increased as molecule tetramethylpiperazine) with one single halide
well by an order of magnitude compared to Cs3Bi2I9. At species shows a 1D chain structure, while
last, the PCE of a PvSC based on CsBi3I10 was 0.4% (TMP)1.5[Bi2I7Cl2], with mixed halogens (I and Cl) is a
higher than that of the reference.74 Subsequently, the rare case of 2D structure. This compound is a potential
group conducted further research on this material. By light harvesting material because of the band gap of
using dopant-free hole-transporting polymers, the 2.10 eV, promising photoconductivity and high stability
energy mismatch between the CsBi3I10 film and the HTL under prolonged exposure to humid air or light.80

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Fig. 9 (a) Crystal structure of single-crystalline MA3Bi2Br9. Reproduced with permission.78 Copyright 2016, Wiley VCH. (b) Four
structures of (TMP)1.5[Bi2I7Cl2]. Reproduced with permission.80 Copyright 2017, American Chemical Society. (c) Energy level
diagram for [py][BiI4] and [mepy][BiI4]. (d) J-V curves of the [py][BiI4]-based champion cell. Reproduced with permission.23
Copyright 2017, the American Institute of Physics.
The properties of bismuth halides based perovskite species reaches 0.152%.83 We have also carried out
derivatives can be partially regulated through halogen some innovative works on the Cs3Bi2I9 system.84
doping. MA3Bi2I9 has been doped with Cl- and a series Cs3Bi2I9-xBrx was prepared by Cs3Bi2I9 doping with
of MA3Bi2I9-xClx films were prepared. The mixed anion bromide. By systematically comparing the crystal
MA3BiI5.22Cl3.78 employed as an absorption layer also structure, the band structure and absorbance of the
provided a maximum PCE of 0.18%, with a high FF of Cs3Bi2I9-xBrx materials (Figure 10), we found that
almost 60% and an excellent long term stability of more Cs3Bi2I6Br3 is the compound with the lowest bandgap
than 700 days for devices stored under inert (2.03 eV, with that of Cs3Bi2I9 being 2.20 eV). More
atmosphere.81 In addition, the PCE of MA3Bi2I9-xClx importantly, a novel phase transition from space group
_
was found to rise with the increase of Cl- doping P63/mmc to P3m due to the alloying of three bromide
content.82 The low-pressure VASP method was applied atoms was first discovered. Simultaneously, a champion
to obtain a MA3Bi2I9-2xSx perovskite films. The sulfur device with PCE of 1.15% was obtained with
incorporated in the perovskite derivative films leads to a Cs3Bi2I6Br3 as light absorbing layer.
reduced bandgap of 1.67 eV and a compact
morphology. The optimal PCE for PvSC based on this

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Fig. 10 The crystal structure of (a) Cs3Bi2I9 and (b) Cs3Bi2Br9, respectively. The calculated band structure of (c) Cs3Bi2I9 and (d)
Cs3Bi2Br9, respectively. (e) The calculated absorbance of Cs3Bi2I9, Cs3Bi2I6Br3 and Cs3Bi2Br9 materials. (f) The variation of the
_
band gaps in Cs3Bi2I9-XBrX in the P63/mmc and the P3m phases with the composition x. Reproduced with permission.84
Copyright 2019, the Royal Society of Chemistry.
It is widely accepted that defects in A3B2X9 PCE can be further improved by passivating these
are responsible for that low device PCE. In a defects.
relevant solid-state physics study, Pal and Another 1D chain-like structure,
coworkers introduced the scanning tunneling (H3NC6H12NH3)BiI5 (HDABiI5), was synthesized from a
spectroscopy (STS) method to understand the non-toxic trivalent bismuth iodide and thermally stable
nature of defects in bismuth trihalides perovskite 1,6-hexane diammonium groups. HDABiI5 shows better
thermal stability than lead-based perovskites (up to 200
derivatives material system. The bandgap of
ºC), although still providing very low PCE in PvSC, due
Cs3Bi2I9 prepared with BiI3-rich precursor
to the relatively large band gap.21
decreases from 2.01 eV employing the exact Similar 1D chain-like organic-inorganic
stoichiometric ratio to 1.81 eV, due to formation of iodobismuthates, namely C5H6NBiI4 ([py][BiI4])(py:
mid-gap deep defects, as evidenced by such STS pyridinium) and C6H8NBiI4 ([mepy][BiI4]) (mepy:
studies.85 Hence, it is promising that the device methylpyridinium), have been prepared by Sun et al.
The organic moieties, constituted of protonated

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transport in [py][BiI4] and [mepy][BiI4]. These significant degradation.87
compounds have band gaps of 1.78 eV and 2.38 eV,
respectively. The efficiency of an HTL-free PvSCs
4.1.2 Photovoltaics devices based on double

approached 0.9%, which is a good result for bismuth
perovskite structures
halides based perovskite derivative phottovoltaic
The A2BIBIIIX6 perovskites are characterized as a
material (Fig. 9c, d).23 Additionally, a series of 1D
3D structure with two kinds of B cations (BI and BIII)
chain-like Sb/Bi halide based organic-inorganic hybrid
dominated octahedral cells, which are adjacent to each
alloys of formula [4ApyH]SbxBi1-xIyBr4-y, where
other in the cubic phase. These A2BIBIIIX6 double
4ApyH stands for the 4-aminopyridine cation, were
perovskites usually show a high tolerance to defects,
synthesized. Among these systems, [4ApyH]Sb0.8Bi0.2I4
due to the strong ionic nature of the basic constituents.
and [4ApyH]SbI4 provided detectable light to electricity
On the other hand, they unfortunately have large

conversion efficiencies of 0.29% and 0.30%,
bandgaps compared to the lead-based reference, which
respectively.86 Finally, a dense and pinhole-free
limits the amount of light they can absorb from the solar
(C6H5NH3)BiI4 film was fabricated using an eco-
spectra, coupled to high exciton binding energies. The
friendly gas pump treatment technique by Yang and
performances in bismuth halide based double perovskite
coworkers. The material can tolerate continuous
PvSCs reported up to now are summarized in Table 2.
Table 2 Summary of performance for bismuth halide based double perovskite solar cells
FTO/SnO2/Cs2AgBiBr6/P3HT/Au 2.05 1.78 1.04 0.78 1.44 [88]
FTO/TiO2/meso-TiO2/Cs2AgBiBr6/spiro-OMeTAD/Au 2.21 3.93 0.98 0.63 2.43 [89]
FTO/TiO2/Cs2AgBiBr6/Spiro-MeOTAD/Au 1.95 1.55 1.06 0.74 1.22 [90]
FTO/TiO2/meso-TiO2/Cs2AgBiBr6/PTAA/Au 2.10 1.84 1.02 0.67 1.26 [91]
FTO/TiO2/Cs2AgBiBr6/P3HT/Au 2.05 1.79 1.12 0.68 1.37 [92]
FTO/Cu-NiO2/Cs2AgBiBr6r/C60/BCP/Ag 2.05 3.19 1.01 0.69 2.23 [93]
FTO/TiO2/meso-TiO2/Cs2AgBiBr6/N719/spiro-OMeTAD/Au 2.02 5.13 1.06 0.52 2.84 [94]
FTO/TiO2/meso-TiO2/Cs2NaBiI6/spiro-OMeTAD/Au 1.66 1.99 0.47 0.44 0.42 [95]
Note: (di-tetrabutylammonium cis-bis(isothiocyanato) bis(2,2′-bipyridyl-4,4′ dicarboxylato) ruthenium (II)) is abbreviated as N719.
Due to the large bandgap, reports on those double main monovalent cations that have been used so far,
perovskite solar cells are rather limited, but their making them suitable for octahedral coordination.
promising optoelectronic properties make us optimistic The main breakthroughs obtained with double
on their future and fruitful implementation in perovskite absorbers in PvSCs are summarized in the
photovoltaics. Reports disclosing the optoelectronic following lines. A low-pressure assisted solution
properties of halide double perovskites of formula method was used to prepare high-quality Cs2AgBiBr6
A2BIBIIIX6 demonstrate the excellent features of these double perovskite for the first time. Excitingly, a device
materials, similar to those of their 3D APbX3 based on such a lead-free absorber showed excellent
counterparts. Bi3+ is the most commonly used trivalent thermal and environment stability without any
cation in double perovskites, because it has the same encapsulation. Annealing temperature of 250 ºC is
isoelectronic configuration as Pb2+ (6s26p0) as required to obtain a full conversion from the precursors
mentioned above, and its toxicity is significantly to Cs2AgBiBr6. The corresponding planar
reduced. For the B site, Ag+, K+, Na+, In+ or Tl+ are the heterojunction device based on Cs2AgBiBr6 reached an

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optimal PCE value of 1.44%.88 Another reported obtained films exhibited large grain sizes and View uniform,
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photovoltaic device exhibited a PCE close to 2.5%, with smooth surface properties. The solar cells with planar
Jsc of 3.93 mA cm-2, Voc of 0.98 V, and FF of 0.63 structure showed a PCE of 1.37% and an excellent
(Figure 11a and b). Furthermore, compared to MAPbI3, stability to standard environmental conditions (Fig.

the light soaking test result shows high stability in 11d).92 A high quality Cs2AgBiBr6 film was further
ambient environment, and no detectable PCE realized via an anti-solvent quenching process, followed
degradation was found after 25 days.89 A uniform by an annealing step. An inverted planar heterojunction
Cs2AgBiBr6 thin film fabricated by simple one-step spin PvSC based on this film exhibits a PCE of 2.23%.93
coating method enabled high performance planar PvSCs Recently, a multifunctional N719 dye interlayer was
featuring long electron-hole diffusion lengths (more introduced in Cs2AgBiBr6 PvSCs for improving the
than 100 nm). An average PCE over 1% was achieved PCEs and stability.94 The device showed a PCE of
by employing a planar TiO2 ETL.90 Pantaler et al. 2.84%, which was the highest value reported for
reported also hysteresis-free mesoporous double PvSCs Cs2AgBiBr6 PvSCs so far. Moreover, a new lead-free
base on the Cs2AgBiBr6 absorber. A maximal PCE of double perovskite material of formula Cs2NaBiI6 was
1.26% was recorded using PTAA as the HTM.91 synthesized and applied in PvSC. A narrow band gap of
New ideas have been developed to improve the 1.66 eV and the excellent stability have been found in
performance of double perovskites-based devices. such a shuttle-like 3D Cs2NaBiI6 material. The
Cs2AgBiBr6 thin films were prepared through a Cs2NaBiI6 based PvSCs obtained an optimal PCE of
sequential vapor deposition procedure (Fig. 11c). The 0.42%.95

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Fig. 11 (a) Scheme depicting a tested preparation route for Cs2AgBiBr6 thin films. (b) J-V curve of the best performing device
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prepared as in (a). Reproduced with permission.89 Copyright 2017, the Royal Society of Chemistry.DOI: (c)10.1039/D0TA05433J
Scheme for the
sequential vapor deposition processing of Cs2AgBiBr6 thin films. (d) J-V curve of the optimized solar cell prepared as in (c).
Inset: cross-sectional SEM image of the resulting device. Reproduced with permission.92 Copyright 2018, Wiley VCH. (e)

Crystal structures and band structures of MAPbI3, (MA)2TlBiBr6, and Cs2AgBiBr6. Arrows showing the direct (left and center)
and indirect (right) bandgap transitions. Reproduced with permission.96 Copyright 2017, American Chemical Society.
Composition engineering has also been taken to significant drawbacks of these materials, namely the
decrease the band gap of double perovskite materials. low absorption coefficient and high exciton binding
Recently, Tl was added to Cs2AgBiBr6 as an impurity to energy. The orbital interaction between monovalent BI
form opaque black crystals with formula Cs2(Ag1-aBi1- and trivalent BIII species in the marginal zone generally
b)TlxBr6. The content of Tl varied from 0.03% to 0.75%. involves the movement of the conduction band
Tl cations can replace both Ag+ (as Tl+) and Bi3+ (as minimum (CBM) and valence band maximum (VBM),
Tl3+) sites, as evidenced by theoretical and experimental leading to an indirect gap. By band gap engineering,
studies. At higher concentrations of Tl, its substitution indirect semiconductors can be converted into direct
of Ag+ is preferable. The reflectivity measurements semiconductors by adjusting the relative proportions of
clearly show that the experimental bandgap decreases the trivalent BIII cations.100
with an increase of Tl content, with a minimum value of Other main disadvantages of the double
1.57 eV at x = 0.075. When Tl3+ replaces Bi3+, a new perovskites seem to be related to the difficulties in
lower energy conduction band with Tl 6s and Ag 4d employing solution-processing to fabricate highly
character is formed, which reduces the band gap energy crystalline films. More systematic studies are required
and leads to an indirect transition, as predicted by DFT. to fabricate dense films. It is well-known that thermal
When Tl+ substitutes Ag+, the Tl 6p states together with evaporation under vacuum conditions is a good choice
Br 4p and Bi 6p states form a new conduction band with compared to spin coating. Powder or single crystal of
lower energy that generates a direct transition, as shown the double perovskite compound synthesized by
in Figure 11e.96 A similar bandgap engineering of hydrothermal method can be used as the starting
Cs2AgBiBr6 was also carried out by introducing Sb3+ via material.
a versatile solution method. The Sb-substitution enables Recently, our group successfully produced large-
an obvious reduction of bandgap by 0.25 eV.97 In area, single-crystalline Cs2AgBiBr6 films by use of so
addition, two other hybrid double perovskites, called capillary-assisted dip-coating method.101 The
(MA)2TlBiBr6 and (MA)2AgBiBr6 have been fabrication process of highly oriented Cs2AgBiBr6 films
synthesized, with interesting optoelectronic properties. is shown in Figure 12a, and this method can be applied
Both perovskites were prepared through the to various substrates. The thus obtained optimized films
hydrothermal method and crystallized in the same cubic approach single crystalline, as verified by φ-scan XRD
space group Fm3m. In agreement with what prospected (Figure 12c-d). The substrate lift speed is responsible
by DFT, the direct band gap of (MA)2TlBiBr6 was for the final crystal growth habit of the films (Figure
experimentally found to be 2.16 eV.98 Tl does not 12e-g). By changing the substrate growth temperature,
change the crystal momentum of the valence and the bandgap of the thin films can be tuned from 2.65 to
conduction bands, hence maintaining the same strong 2.25 eV. By DFT calculations, it was further to
absorption ability of APbX3 materials. However, highlight that the band structure of these films displayed
(MA)2TlBiBr6 contains Tl, a highly toxic element that a typical n-type characteristic. Our results show that the
may limit its use as a substitute for lead based Cs interstitials and Br vacancies derived deep defects fix
perovskite materials. On the other hand, similar to the Fermi level there. This method offers new directions
Cs2AgBiBr6, (MA)2AgBiBr6 has an indirect band gap of for the preparation of double perovskite thin films,
2.02 eV.99 which may bring a step-change in overall device
The indirect character of the electronic transitions performances.
of the double perovskites leads to the initially discussed

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Fig. 12 (a) Schematic illustration of the Capillary-assisted Dip Coating process used for the production of Cs2AgBiBr6 films. (b)
Schematic structure of the cubic double perovskite Cs2AgBiBr6. (c) XRD patterns of an as synthesized Cs2AgBiBr6 film and
powder. (d) φ-scan XRD pattern of the as synthesized Cs2AgBiBr6 film. Top-view SEM images of Cs2AgBiBr6 films prepared by
applying a lifting speed of 10 μm/s (e), 50 μm/s (f) and 25 μm/s (g). Reproduced with permission.101 Copyright 2019, Elsevier.
4.2 Antimony halides based solar cells According to the synthetic conditions used,
Cs3Sb2I9 can form different solid-state structures. When
Similar to Bi, Sb can also form different prepared from solution, Cs3Sb2I9 prefers to form a 0D
combinations with organic/inorganic cations and halide, structure with isolated dimers of face sharing octahedra
as discussed in Section 2.2.102 Among them, the (P63/mmc). The formation of 2D layered structures
Cs3Sb2I9 and MA3Sb2I9 compounds are the mostly takes place during solid or gas reactions (space group P
investigated in the context of photovoltaics research. _
3m1). Cs3Sb2I9 thin films preparations and

Table 3 summarizes the the device photovoltaic characterizations were first reported in 2015, together
performance of antimony halides based perovskite and with the first solar cell employing this compound as the
derivative materials. light absorber. Cs3Sb2I9 thin film prepared via a two-
step deposition method have a red colored layered

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structure, differently from the orange color of 0D As mentioned above, Cs3Sb2I9 films View prepared
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Cs3Sb2I9. The bandgap of the 2D Cs3Sb2I9 thin film was through solution processing are DOI: 10.1039/D0TA05433J
more inclined to
determined to be 2.05 eV, with an absorption coefficient organize in the dimeric form. To solve this problem, we
of 105 cm-1 and an ionization potential of 5.6 eV, as have also carried out pioneering investigations in the

reported by Saparov et al.10 The stability of the thin area.106 Hydrochloric acid (HCl) as an additive was
films in ambient air is better than that of MAPbI3 films. introduced into the precursors solution. In this way,
Due to nonradiative recombination caused by deep chloride acted as in inhibitor in the reaction, slowing
defects, the device PCE of Cs3Sb2I9-based PvSCs is very down the formation of Sb-I-Sb bond. Hence, a layered
low (below 1%) and the Voc is between 0.25 and 0.3 V. Cs3Sb2I9 film was developed from an intermediate
The 0 D Cs3Sb2I9 structure with a band gap of 2.0 eV coordinated phase using this HCl-assisted strategy
was also applied in planar PvSCs. When HI was (Figure 13a). From a series of characterizations, the
employed as additive, the devices showed a champion bandgap of the layered compound results to be 2.05 eV,
PCE of 0.84%, with a Voc of 0.60 V.103 Correa-Baena et thus smaller than that of the dimeric one of 2.47 eV
al. reported that the 0 D Cs3Sb2I9 is an indirect bandgap (Figure 13b). The all inorganic layered Cs3Sb2I9 device
semiconductor with a large exciton binding energy, showed a top PCE value of 1.21%, while the dimer-
which explained the low photocurrent and PCE.29 A based device only acquired a PCE of 0.43% (Figure
layered polymorph and a dimeric form of Cs3Sb2I9 were 13c). The PCE improvement in the layered Cs3Sb2I9 thin
prepared via vapor-assisted solution processing. The films is due to lower trap density, doubled carrier
measured exciton lifetime and binding energy for the mobility and improved junction quality, as determined
layered Cs3Sb2I9 resulted to be 6 ns and 100 meV, by space-charge-limited-current measurement (Figure
respectively. The layered and the dimeric Cs3Sb2I9 13d, e). Through the addition of HCl, the problem that
forms used in PvSC obtained the device PCE of 1.5 and with solution method is easier to form the dimeric form
0.89%, respectively.104 Meanwhile, Zhou et al. also can be effectively solved. We believe that this novel
prepared high-quality films composed of the layered method will greatly promote the fast progress of
phase MA3Sb2ClxI9-x by adding methylammonium Cs3Sb2I9-based lead-free PvSCs.
chloride into the precursor solutions.105

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Fig. 13 (a) Schematic representation of the anti-solvent solution method used by us for the preparation of layered and
dimeric Cs3Sb2I9 thin films. (b) Calculated bandgaps from Tauc Plot of dimeric and layered phases. (c) J-V curves of PvSC
containing the two forms of the Cs3Sb2I9 absorber. J-V scans of dimeric Cs3Sb2I9 thin films (d) and of layered one (e).
Reproduced with permission.106 Copyright 2019, Wiley VCH.
In addition to our HCl-assisted method, the were found to provide poor figure of merit, namely, a Jsc
introduction of alkalis can also regulate the electronic of 2.11 mA cm-2, a Voc of 0.55 V and PCE of only 0.66
structure of Cs3Sb2I9 film. A lot of work in this respect %.107 A3Sb2I9 thin film in which the A site cation was
has been done. Harikesh et al. found that this compound Cs, Rb, and K were prepared by solution-processing to
can easily form layered structures via solution methods be used for photovoltaics. The A-site cation has an
when Cs is replaced by Rb (Fig. 14a). With the help of important effect on the structural and optoelectronic
DFT, they compared the formation energies of the properties of these thin films. The large exciton binding
dimeric and layered forms of A3Sb2I9 with A = Cs and and carrier effective masses of A3Sb2I9 give rise to low
Rb. Compared to the ionic radius of Cs (1.88 Å), that of photocurrents. A maximum PCE of 0.76% was recorded
Rb (1.72 Å) is smaller and therefore Rb3Sb2I9 is more when Rb3Sb2I9 was employed as the absorber.29 Weber
prone to feature the layered phase. In addition, Rb3Sb2I9 et al. found that the crystalline lattice does not change
has better heat resistance compared to the analogous Cs when the smaller bromide is used to substitute iodide.
compound, a favorable property for an efficient solar On the other hand, the absorption onset appears blue
cell operation. Unfortunately, the Rb3Sb2I9 shifted, with a band gap rising from 2.02 to 2.46 eV. In
semiconductor has an indirect bandgap of 2.1 eV, and this work, solar cells based on the Rb3Sb2I9 absorber
PvSCs based on it employing poly-TPD as the HTL

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displayed a PCE of 1.37%, the top efficiency recorded film. The molar ratios of precursorsViewand the
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of a Rb3Sb2I9 based PvSC.108 concentration of HI were optimized,DOI:

to 10.1039/D0TA05433J
reach a PCE of
2.04% on a planar architecture device.103 The fabricated
Unlike the inorganic A3Sb2I9, that often forms two
MA3Sb2I9 PvSC prepared with two-step procedure also
different structures (the layered and dimeric ones), when

shows good performance with a remarkable Voc of 740
using an organic cation such as MA+, the antimony
mV.109 MA3Sb2I9 surface morphology significantly
halide based perovskite derivatives of formula
influences the recorded PCE. Recently, large grain
MA3Sb2I9 only forms a 0D dimeric structure, with MA+
MA3Sb2I9 crystals were prepared by inserting a
cations surrounded by octahedric anionic metal halide
hydrophobic scaffold, such as perylene and pyrene, into
units (Sb2I9)3-. Hebig et al. first reported MA3Sb2I9 as an
the precursor solution (Fig. 14b). Films with improved
absorber material in PvSC. MA3Sb2I9 have an optical
quality and decreased number of voids were obtained.
band gap of 2.14 eV and an absorption coefficient α ≈
Using these films as absorbers, a record efficiencies of
105 cm-1. Experiments indicate the presence of a large

2.77% was obtained (Fig. 14c).110 Dai et al. produced
energetic disorder in MA3Sb2I9 film. Furthermore, due
high-quality two-dimensional MA3Sb2I9-xClx film by
to the low photocurrent, the device achieved a PCE of
introducing bis(trifluoromethane)sulfonamide lithium
only 0.5%.32 The single step method was used to
(LiTFSI) to control the dimensional transformation. By
prepare MA3Sb2I9 films through solution processing. It
this method, antimony halide based PvSCs further
is worth noting that HI as an additive may improve the
achieved a PCE of 3.34%, which is the highest recorded
quality of antimony halide based perovskite derivative
PCE for pure antimony halide based PvSCs.111
Table 3 Summary of the device photovoltaic performance of antimony halide perovskite and derivatives as light
absorbers
Note:(poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b’]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) is abbreviated as PEPDTBT.
Device structure Eg (eV) Jsc (mA/cm2) Voc (V) FF PCE(%) Ref.
FTO/TiO2/meso-TiO2/Cs3Sb2I9/spiro-OMeTAD/Au 2.43 0.13 0.40 0.58 0.03 [29]

ITO/PEDOT:PSS/Cs3Sb2I9/PCBM/C60/BCP/Al 2.00 2.91 0.60 0.48 0.84 [103]
ITO/PEDOT:PSS/Cs3Sb2I9/PCBM/Al 2.05 2.82 0.77 0.41 0.89 [104]
ITO/PEDOT:PSS/Cs3Sb2I9/PCBM/Al 2.05 5.31 0.72 0.39 1.50 [104]
FTO/TiO2/Cs3Sb2I9/Au 2.05 3.55 0.61 0.56 1.21 [106]
FTO/TiO2/meso-TiO2/K3Sb2I9/spiro-OMeTAD/Au 2.02 0.41 0.34 0.50 0.07 [29]
FTO/TiO2/meso-TiO2/Rb3Sb2I9/spiro-OMeTAD/Au 2.03 1.84 0.66 0.63 0.76 [29]
ITO/PEDOT:PSS/MA3Sb2I9/PCBM/C60/BCP/Al 1.95 5.41 0.62 0.61 2.04 [103]
FTO/PEDOT:PSS/Pyrene/MA3Sb2I9/PCBM/C60/Al 1.90 6.64 0.7 0.60 2.77 [110]
FTO/TiO2/m-TiO2/MA3Sb2I9-xClx/Spiro-OMeTAD/Au 2.17 5.04 0.69 0.63 2.19 [105]
FTO/TiO2/MA3Sb2I9-xClx /Spiro-OMeTAD/ Au 1.89 7.38 0.70 0.65 3.34 [111]
ITO/Cu:NiO/ MA3(Sb1-xSnx)2I9/ZnO /Al 1.55 8.32 0.56 0.58 2.70 [112]
FTO/TiO2/meso-TiO2/MASbSI2/PEPDTBT/Au 2.01 8.12 0.65 0.59 3.08 [114]
ITO/PEDOT:PSS/(NH4)3Sb2IxBr9-x /PCBM/Al 2.27 1.15 1.03 0.42 0.51 [115]
FTO/TiO2/ FA4GeSbCl12/spiro-OMeTAD/Au 1.30 23.1 0.65 0.31 4.70 [117]

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Currently, some efforts have been made to reduce doping sulfur in that system, MASbSI2 was fabricated
the band gap of MA3Sb2I9 through element doping or for the first time as light harvester for photovoltaic
replacing cation or anion. Pal et al. reported the lowered application.113 The MASbSI2 compound was prepared
optical bandgap of MA3Sb2I9 from 2 eV to 1.55 eV by by such a sequential reaction as chemical bath
introducing Sn4+ in the MA3Sb2I9 structure. In addition, deposition of Sb2S3, then multiple cycles of spin coating
the conduction band edge of the perovskite gradually of SbI3 and MAI and finally thermal annealing in argon
shifts towards n-type, due to the hetero-valence atmosphere (Figure 14d). That MASbSI2 based device
substitution in MA3Sb2I9. With an increase in the tin shows an optimal PCE of 3.08% (Figure 14e).114 New
content, STS and density of state spectra indicate that perovskite derivative materials of formula
the type of electronic conductivity can be tuned from p- (NH4)3Sb2IxBr9-x (0< x <9) were also developed. The
type to n-type. However, the decrease of bandgap is at light absorption edge of these materials can vary from
the expenses of an increased surface roughness for the 558 to 453 nm. Single crystal of (NH4)3Sb2IxBr9-x owns
films. The tin content was optimized to find a trade-off hole mobility of 4.8 cm2V-1s-1 and electron mobility of
between low bandgap and surface roughness of the thin 12.3 cm2V-1s-1. A high Voc of 1.03 V and a PCE of 0.51
films. In this way, a planar heterojunction PvSC got an % were obtained for (NH4)3Sb2IxBr9-x PvSC.115
excellent Jsc of 8.32 mA cm-2 and a PCE of 2.69%.112 By
Fig. 14 (a) Schematic representation showing the influence of the A cation size on the structure of A3Sb2I9. Reproduced with
permission.107 Copyright 2016, American Chemical Society. (b) Schematics of the deposition of HI-MA3Sb2I9 thin films with
hydrophobic organic additives, and cross-sectional SEM image of devices containing them. (c) J-V curve of Sb-based PvSCs
prepared as depicted in (b). Reproduced with permission.110 Copyright 2018, Elsevier. (d) Process for preparing the MASbSI2

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perovskite derivative layer. (e) J-V curves in forward and reverse scan mode of the best performing MASbSI 2 PvSC.
View Article Online
Reproduced with permission.114 Copyright 2018, American Chemical Society. (f) Diagram showing the electronic structure at
DOI: 10.1039/D0TA05433J
different x of Ag3BiI6-2xSx. (g) J-V curve of Ag3BiI6-2xSx -based PvSCs with almost no hysteresis. Reproduced with permission.121
Copyright 2019, Wiley VCH.

Antimony halide based double perovskite materials semiconductors in PvSCs in recent years.118 Sargent and
are a viable platform for the development of lead-free coworkers reported a new solution-processed material
PvSCs and for this reason have attracted a significant of formula AgBi2I7. AgBi2I7 has a cubic structure, which
attention for the past five years. Sb partial substitution introduces monovalent silver cations into an
has also been explored, as in the case of a layered iodobismuthate structure. The thin films have a dense
perovskite of formula Cs4CuSb2Cl12, where one Sb3+ ion and pinhole-free surface morphology and a bandgap of
was substituted with Cu2+. The material has a direct 1.87 eV. In PvSC, this material allows to reach a PCE of
bandgap of 1.0 eV and a high photo- and thermal 1.22% and an excellent environmental stability.119 Ag-
stability.116 Karmakar et al. also reported Cu2+ doped Bi-I Rudorffites are indeed promising non-toxic
Cs2SbAgCl6, showing a decreased optical indirect photovoltaic materials and for this reason have been
bandgap from 2.6 eV to 1.0 eV. The Cu-doped material investigated.120 When Ag3BiI6 was used as the light
exhibited long term structural and photophysical absorber, the resulting solar cell provided a top PCE of
stability up to one year, when it was maintained in 4.3%.28 The optoelectronic properties of AgaBibIa+3b
thermal and moisture stress conditions.33 Based on the have been further tuned by partial substitution with
principles of increased electronic dimensionality, by disulfide anions. AgaBibIa+3b was modified with sulfur,
inserting [MIIX6] octahedra layers into Cs3Sb2X9, a reducing the bandgap by 0.1 eV and upshifting the
layered double perovskite family of Cs3+nM(II)nSb2X9+3n valence band edge by 0.1 - 0.3 eV (Fig. 14f). The
(M = Sn, Ge) can be designed. Compared to Cs3Sb2X9, resulting solar cells exhibited a PCE of 5.51% and good
the double perovskites have smaller bandgaps and stability under ambient conditions for over 1 month
smaller carrier effective masses. These parameters can (Fig. 14g).121 Ag2BiI5 PvSCs with PCE above 2.5%
be tuned by inserting different thickness of octahedral were also fabricated in air by a dynamic hot casting
layers.34 Recently, the FA4GeSbCl12 double perovskite technique.122
has also been demonstrated to be a stable and efficient A copper bismuth iodide (CuBiI4) was prepared via
semiconductor with a direct bandgap of 1.3 eV. a solution method. The material has a wide bandgap of
FA4GeSbCl12 based PvSCs were prepared to achieve the 2.67 eV and its PvSC provides a low PCE of 0.82%, but
PCE up to 4.7%, without the use of any additive.117 shows excellent long-term stability when maintained for
over 40 days in ambient conditions.123 Zhang reported a
4.3 Photovoltaic devices based on Rudorffite highly facile route for the in-situ production of CuBiI4
structures with a favorable band gap of 1.81 eV. Its PvSC
displayed good photovoltaic performance with a top
3D materials are more favorable for photovoltaic
PCE of 1.119%.124 Device performance parameters for
applications than 2D species, in view of the lower
the light absorbers discussed in this paragraph are
bandgaps, smaller exciton binding energies and longer
summarized in Table 4.
exciton diffusion lengths. Silver iodobismuthate
compounds have been investigated as lead-free
Table 4 Summary of photovoltaic performance for Rudorffite structure based PvSCs
FTO/TiO2/meso-TiO2/ Ag3Bi2I6/P3HT/Au 1.83 10.70 0.63 0.64 4.30 [28]

FTO/TiO2/meso-TiO2/AgBi2I7/P3HT/Au 1.87 3.30 0.56 0.67 1.22 [119]

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[120]
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FTO/TiO2/meso-TiO2/Ag3BiI6-2xSx /PTAA/Au 1.80 14.70 0.57 0.66 5.51 [121]
FTO/TiO2/meso-TiO2/Ag2BiI5/P3HT/Au 1.80 6.04 0.69 0.62 2.60 [122]
FTO/TiO2/CuBiI4/Spiro-OMeTAD/Au 2.67 2.19 0.63 0.57 0.82 [123]

ITO/CuBiI4/Spiro-OMeTAD/Au 1.81 7.18 0.38 0.29 1.12 [124]
5. Conclusions and Outlook compared to the traditional one-step solution

processing.
In this review, we have summarized the structure, Rudorffite structures are considered competitive
theoretical prediction, preparation methods and candidates to lead halide based perovskites for the
photovoltaic performances of several lead-free Group realization of well-performing photovoltaic devices.
VA metals (Bi and Sb) halides based perovskite and However, as an excess of defects introduced during thin
derivatives, especially A3B2X9, Rudorffite and double films processing makes the photoelectric performance
perovskite. weak, they still hold difficulties to compete with the
As for A3B2X9 halide, it is worthy to remind here classical perovskite structures.
that the photovoltaic performance is closely related to As for the case of the double perovskites, we
the chameleonic structural and electronic dimensions. 0- can state that the large, indirect bandgaps of the
D dimeric species or vacancy-ordered perovskite currently fabricated Ag-Bi halides based materials
derivatives (2D) are generally unfavorable for are the cause of their limited photovoltaic
optoelectronic applications. Their exciton binding performance. The alloying/doping can help in
energies are indeed relatively large and exciton reducing the optical band gap. The synthesized
diffusion lengths are short. Some new materials may Cs2TlBiBr6 compound has a similar energy bands
hold great potential to solve these problems. For structure to that of lead-based perovskites, but its
example, compounds like 2D Rb3Sb2I9 or Cs3BiI6Br3, application is limited by the high toxicity of Tl. A
can undergo an increase in lattice dimension via a new double perovskite of formula FA4GeSbCl12 has
strategic compositional engineering, generally a doping a smaller bandgap of 1.3 eV. Hence, it is necessary
of the anion or cation sites. Hence, we believe that the to further explore other double perovskite structures
development of new active species of this kind by or to apply complex compositional engineering
employing different ion doping strategies is a rational strategies in the search for species with energy
choice to attempt the improvement of A3B2X9-type bands structures similar to those of lead-based
materials based photovoltaic performances. materials. This field is undoubtedly very
Another strategy to promote progresses in this challenging and wide open to new exciting
direction is through the improvement of the quality discoveries.
of the thin films based on these species. Bismuth Generally, researches on group VA-based lead-
halides based compounds crystallize directly and free perovskites and derivatives have reached good
rapidly into a textured polycrystalline achievements in some aspects, but mechanisms of
microstructure. New preparation methods need to films formation, charge separation and
be developed or more widely implemented to exert recombination at interfaces and grain boundaries
a tight control on the crystallization process, for need to be studied more deeply, especially for
example those like the two-steps solution gaining more information on the defects nature, in
processing, thermal evaporation, dip-coating and comparison with the lead-based counterparts, for
vapor assisted solution processing methods, to cite a which scientists have reached nowadays a high
few. All of these deposition methods have been level of understanding of these aspects. Therefore,
shown to hold the potential to form denser films further research should focus on developing new

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group VA metals-based materials with suitable 8 F. Hao, C. C. Stoumpos, P. Guo, N. Zhou, T.ViewJ. Marks, R.
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high quality light absorbing films and to improve 10 B. Saparov, F. Hong, J.-P. Sun, H.-S. Duan, W. Meng, S.
the quality of the interfaces with the charge Cameron, I. G. Hill, Y. Yan and D. B. Mitzi, Chem.
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extracting ancillary layers ( ETL and HTM). We 11 B.-W. Park, B. Philippe, X. Zhang, H. Rensmo, G.
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12 W. Zhang, Y. Sui, B. Kou, Y. Peng, Z. Wu and J. Luo,
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ACS Appl. Mater. Interfaces, 2020, 12, 9141-9149.
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14 A. Zakutayev, C. M. Caskey, A. N. Fioretti, D. S. Ginley,
Conflicts of interest J. Vidal, V. Stevanovic, E. Tea and S. Lany, J. Phys.
Chem. Lett., 2014, 5, 1117-1125.
There are no conflicts to declare. 15 C. Wu, Q. Zhang, G. Liu, Z. Zhang, D. Wang, B. Qu, Z.
Chen and L. Xiao, Adv. Energy Mater., 2020, 10,
1902496.
16 A. J. Lehner, D. H. Fabini, H. A. Evans, C.-A. Hébert, S.
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This work was supported by the National Natural 17 S.-Y. Kim, Y. Yun, S. Shin, J. H. Lee, Y.-W. Heo and S.
Science Foundation of China (NSFC) (No. 61775091, Lee, Scripta Mater., 2019, 166, 107-111.
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Table of Content DOI: 10.1039/D0TA05433J

Recent progresses in the crystal structure determination, the thin film preparation
methods and the performance in solar cells of Group VA metals (Bi and Sb) –halide
based perovskite and derivatives are reviewed, addressing limitations and perspectives
for these low toxicity photovoltaic materials.

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Br-, Cl-. The APbX3 perovskite is an excellent photo-

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