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REVIEWS

Chemically diverse and multifunctional


hybrid organicinorganic perovskites
Wei Li1,2, Zheming Wang3, Felix Deschler4, Song Gao3, Richard H.Friend4
and Anthony K.Cheetham5
Abstract | Hybrid organicinorganic perovskites (HOIPs) can have a diverse range of compositions
including halides, azides, formates, dicyanamides, cyanides and dicyanometallates. These
materials have several common features, including their classical ABX3 perovskite architecture
and the presence of organic amine cations that occupy the Asites. Current research in
HOIPs tends to focus on metal halide HOIPs, which show promise for use in solar cells and
optoelectronic devices; however, the other subclasses also exhibit a diverse range of physical
properties. In this Review, we summarize the chemical variability and structural diversity of all
known HOIP subclasses. We also present a comprehensive account of their intriguing physical
properties, including photovoltaic and optoelectronic properties, dielectricity, magnetism,
ferroelectricity, ferroelasticity and multiferroicity. Moreover, we discuss the current challenges
and future opportunities in this exciting field.

The word perovskite was coined to name the mineral halide to bridging molecular linkers, such as azide (N3),
CaTiO3, which was discovered in the Ural Mountains cyanide (CN) and borohydride (BH4), other families of
by the German mineralogist Gustav Rose and named HOIPs have been formed810. The introduction of addi-
in honour of the Russian Count, Lev A. Perovski1. The tional organic components into the X-site gives another
1
School of Physics and term perovskite now refers to a broad class of materials variety of HOIP derivative, namely metalorganic frame-
Wuhan National Laboratory
that have the same type of structure as CaTiO3, known work perovskites (FIG.1c). Metal formate and metal dicy-
for Optoelectronics,
Huazhong University of as the perovskite structure2. The general chemical for- anamide perovskites are well-known examples, in which
Science and Technology, mula for perovskite materials is ABX3, in which A and the A-sites are amine cations and the X-sites are HCOO
Wuhan 430074, China. B are cations of different sizes, and X is an anion that or N(CN)2 linkers, respectively 5,13.
2
Laboratory for Optical coordinates to B. The A-site cations are usually larger Similarly to conventional perovskites, HOIPs can
Information Technology,
Wuhan Institute of Technology,
than the B-site cations, and the B-site cation is six- be categorized from a structural perspective as ABX3
Wuhan 430205, China. coordinated by the Xsite anion to form a BX6 octahedron. perovskites, A2BBX6 double perovskites and A3BX
3
College of Chemistry These octahedra are corner-shared to form a 3D frame- antiperovskite subclasses. Many examples of double
and Molecular Engineering, work, in which the Asite cations are located in the hybrid perovskites have been created by replacing the diva-
Peking University,
framework cavities (FIG.1a). lent metals with mixed monovalent and trivalent metals
Beijing 100871, China.
4
Cavendish Laboratory, Hybrid organicinorganic perovskites (HOIPs) are in the azide14, cyanide8,15,16 and formate11,17 HOIPs (FIG.2a).
University of Cambridge, a subclass of ABX3 materials in which the Asite and/or However, hybrid antiperovskites are rare, and examples
JJ Thomson Avenue, Xsite ions are replaced by organic amine cations are limited to the ternary tetrathiafulvalenium salts,
Cambridge CB3 0HE, UK. and/or organic linkers, respectively (hybrid layered and (TTF)3[(X)(Mo6X14)] (TTF+ = tetrathiafulvalenium;
5
Department of Materials
Science and Metallurgy,
hexagonal perovskites are not discussed herein). The X = C1, Br or I), reported in 1991 (REF.12) (FIG.2b).
University of Cambridge, organic components in the structure of these HOIPs The abundant variations of organic components and
Charles Babbage Road, introduce additional functionalities and structural flex- metal salts offer enormous chemical possibilities for cre-
Cambridge CB3 0FS, UK. ibility that cannot be achieved in purely inorganic perov ating HOIPs, and, hence, this class of materials now spans
Correspondence to skites. Most importantly, their diverse structural and a considerable part of the periodic table. The ratio of ionic
W.L., S.G., R.H.F.andA.K.C. chemical variability offers substantial opportunities for sizes that perovskite architectures can tolerate is indicated
wl276@hust.edu.cn;
gaosong@pku.edu.cn;
tuning and modulating their physical properties by facile by the Goldschmidt tolerance factor (t)18. Because the
rhf10@cam.ac.uk; chemical modification6. Hybrid perovskites were struc- A-site and/or X-site ions in the HOIPs are replaced by
akc30@cam.ac.uk turally characterized in 1978, with the report of the cubic molecular building blocks, the tolerance factor is adapted
doi:10.1038/natrevmats.2016.99 phases of MAPbX3 (MA=methylammonium and X=Cl, to the following equation: t = (rAeff + rXeff)/2(rB + hXeff /2).
Published online 7 Feb 2017 Br or I)7 (FIG.1b). By extending the Xsite from a single In this equation, rB defines the Shannon ionic radius of

NATURE REVIEWS | MATERIALS VOLUME 2 | ARTICLE NUMBER 16099 | 1


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the Bsite metal ion, rAeff denotes the effective radius of radii. In addition, another geometric factor the octa-
the Asite cation, and rXeff and hXeff denote the effective hedral factor () was proposed, this determines the
radius and length of the Xsite molecular ions, respec- fit of the Bsite cation into the X6 octahedron and can
tively 19. By tabulating possible Asite, Bsite and Xsite be used to assess the compatibility of the A and Bsite
combinations (FIG.3) in HOIPs, a significant number of cations for the perovskite architecture. By using a 2D t
tolerance factors are found to lie in the range of ~0.81.0 structure mapping approach, the stability of nearly all
(REF.20) (TABLE1). These results are similar to those for hybrid perovskite halides has been successfully predicted.
conventional perovskites and demonstrate the extended The ideal
_ perovskite structure adopts the cubic space
validity of the Goldschmidt tolerance factors. In addi- group Pm3m and has no variable parameters in the
tion, it is evident that the packing density has a pivotal structure. By lowering the symmetry from this aristotype
role in the formation of HOIPs. Moreover, this simple architecture, many perovskite structures with distortions
semi-empirical approach for assessing size compatibility can be obtained. This group-theoretical analysis has
can guide the rational design and synthesis of new HOIPs been used to study the complex symmetry breaking and
using compositions with desired functionalities. The phase transitions of conventional perovskites28. In this
recent discovery of several formate and halide HOIPs has approach, the displacements of the A and Bsites, and
validated this powerful tool for predicting experimental the tilting of the BX6 octahedral units are the primary
realization25,26. However, caution is necessary because factors that cause structural distortions29,30. As the octa-
the tolerance factor metric shows limited suitability for hedral tilting usually has a much greater effect on lattice
predicting the stability of certain halide HOIPs27. Hence, parameters, it has been used to classify the allowed sym-
a modified tolerance factor metric has been developed metry changes of perovskites3133. For HOIPs in which
that takes into account the covalency of the BX bonds the Xsites are monatomic anions, such as halides, it is
(X=Cl, Br or I) when calculating the Shannon cation apparent that their octahedral tiltings are similar to those
in pure inorganic perovskites. As the Xsite evolves from
a a single atom to a molecular linker, the octahedra in the
lattice are no longer corner-sharing and the situation
becomes more complicated. However, most Xsite lig-
ands are rigid enough to mediate the tilt from one octa-
+ + hedron to another, extending the validity of the tilting
analysis from inorganic perovskites to HOIPs. Inevitably,
the much larger Xsites in HOIPs offer additional space
for the octahedra to distort (BOX1). In some cases, adja-
Ca 2+ Ti 4+ O 2 CaTiO 3 cent octahedra can even distort along the same orienta-
tion, adding new tilting possibilities that are inaccessible
b in perovskite oxides34,35.
In addition to the octahedral tilting of the Bsites, the
displacements of the Asites and the dynamic motions of
+ + the Asites and/or Xsites need to be taken into account
for the symmetry description of HOIPs. The displace-
ments are, in principle, identical to those in inorganic
perovskites and usually involve off-centre movements,
although the situation is complicated by the presence of
CH 3 NH 3 + Pb 2+ I [CH 3 NH 3 ][PbI 3 ] organic cations rather than single atoms on the Asites.
The dynamic movement of the organic Asite (occa-
c
sionally also occurring on the Xsite) is defined as dis-
order, and switching from a disordered to an ordered
state can induce symmetry changes. Interestingly, the
+ + orderdisorder of the Asite organic cation inevitably
changes the hydrogen bonding and dispersion forces,
which in turn can influence the symmetry variations36
(BOX1). Such synergistic combinations of octahedral
tilting, displacements and orderdisorder often result
CH 3 NH 3 +
Mn 2+
HCOO
[CH 3 NH 3 ][Mn(HCOO) 3 ] in more complicated phase transitions in HOIPs com-
pared with their inorganic counterparts. Moreover, the
Figure 1 | The evolution of perovskites. The figure shows the evolution
Nature Reviews | Materials Asite organic amine cations can be polar (for example,
from perovskite
oxides to hybrid organicinorganic perovskites (HOIPs) with an organic Asite, then to MA and dimethylammonium (DMA)), and their spe-
HOIPs with both organic A and Xsites. a|Example of an inorganic perovskite oxide,
cific alignments, which are often induced by hydrogen
CaTiO3 (orthorhombic, Pbnm)3. b|Example of a HOIP with an organic cation at the A-site,
MAPbI3 (orthorhombic, Pnma; MA=methylammonium) . c|Example of a HOIP with an
4 bonding with the perovskite framework, may cause bulk
organic cation at the A-site and an organic anion at the X-site (a metalorganic electric ordering 37. Such ferroelectric or antiferroelectric
framework perovskite), [MA][Mn(HCOO)3] (orthorhombic, Pnma) . Colour scheme: Ca,
5 ordering is consequently dependent on the strength of
violet; Ti, turquoise; Pb, green; Mn, lime; I, pink; O, red; N, blue; C, black; H, light grey. the hydrogen bonds and the dipole moments of the Asite
Hydrogen bonds are denoted as dotted purple lines. cations, as we discussbelow.

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a Hybrid halide perovskites


Hybrid metal halide perovskites. Solar-cell technology
requires materials with high efficiencies, simple pro-
cessability, low cost and abundant availability on Earth43.
Hybrid metal halide perovskites offer vast opportuni-
ties to integrate all these requirements4650. Although
the first known halide HOIPs to be synthesized were
MAPbX3 (X=Cl, Br or I) in 1978 (REFS7,51), it has been
suggested that these may have been prepared in the
1880s52. In the 1990s, the synthesis, characterization and
properties of solar cells based on metal halide HOIPs
were systematically researched, and this initiated the
study of these materials as optoelectronic materials5456.
In 2009, the incorporation of MAPbBr3 as the sensi-
tizer in mesoporous TiO2 was reported to give solar cells
with a lighttoelectricity conversion efficiency of ~3.8%
b (REF.57) . A few years later, dye-sensitized solar-cell
architectures with ~9% efficiency were constructed58,59.
In 2013, a planar device architecture with an efficiency
of ~15%, using the MAPbI3 layer solely as the light-
absorber and active layer, was invented60. This study
confirmed the function of the HOIP as both an absorber
and a charge-generating layer, and as a consequence
simplified the device design by excluding the TiO2
scaffolding. The latest progress has pushed the poten-
tial conversion efficiency, in a tandem configuration
with a silicon cell, to over 25% for small cells using a
mixed-cation/lead/mixed-halide perovskite absorber 61,
which is approaching the efficiencies of the best single-
junction GaAs cells (~29%; but only after nearly
60years of development)62.
Figure 2 | Hybrid organicinorganic perovskites with Despite their huge impact on photovoltaics and
double perovskite and antiperovskiteNature Reviews | Materials
structures. other applications, only a handful of solar-cell HOIPs
a|Example of a double perovskite structure, with advantageous properties for use in optoelectronic
[DMA]2[NaFe(HCOO)6] (DMA=dimethylammonium)11. applications have been discovered thus far 46. The Bsite
The DMA cation is equally disordered at three positions in cation is limited to the group IVA metals Pb and Sn, with
the double perovskite. b|Example of an antiperovskite divalent charge, and the Xsite anion is chosen from the
structure, [(TTF)3][Cl(Mo6Cl14)] (TTF+=tetrathiafulvale halides (that is, Cl, Br or I). The resulting BX3 frame-
nium)12. The light magenta octahedra are constructed from works can thus only accommodate the smallest organic
the central Cl atom and six neighbouring TTF+ cations.
cations, such as MA and formamidinium (FA), accord-
Colour scheme: Na, light cyan; Fe, chartreuse green; Mo,
cyan; S, yellow; Cl, green; O, red; N, blue; C, black. Hydrogen ing to the Goldschmidt tolerance factors19. Larger moi-
atoms and hydrogen bonds are omitted for clarity. eties at the Asite result in layered structures, which tend
to show limited bulk charge transport 53.
HOIPs commonly used in photovoltaic devices
Many important properties of perovskites, such as (TABLE1) are known to undergo successive phase tran-
ferroelectricity, magnetism and multiferroicity, are a sitions with temperature perturbation, many of them
consequence of phase transitions38. The cooperative first order, evolving from cubic to tetragonal, then to
behaviour of the A-, B- and Xsites across phase transi- orthorhombic symmetry on cooling 56,63. Free MA and
tions in HOIPs results in many functionalities that pure FA cations do not have the symmetry required for the
inorganic perovskites are unable to show. In particular, cubic and tetragonal phases and, hence, often have to be
hydrogen bonding has a substantial role in creating fer- orientationally disordered to stabilize those particular
roic39 and multiferroic40 properties, and in modulating symmetries4,64. The rotation of the A-site organic amine
the conductivity 41 as well as the dielectric42 properties of cations is more restricted in the lowest temperature
HOIPs. In addition to the interesting properties associ- phases of each compound, rotating only around the CN
ated with phase transitions, HOIPs offer other new prop- axis, if at all65. In contrast to their oxide counterparts, the
erties beyond those observed in inorganic perovskites. MA and FA cations interact with the perovskite frame-
For example, hybrid halide perovskites exhibit impres- work through NHI hydrogen bonding, in addition to
sive photovoltaic performance and striking light-emitting the electrostatic force, which consequently affects their
properties43, formate perovskites show tunable mechan- phase transitions, octahedral tilting and disorder 66. In
ical properties44, and dicyanamide perovskites display addition, the different hydrogen-bonding modes of
extraordinary thermal expansion45. MA and FA cations lead to divergent interactions with

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a A-site b X-site

Cl , Br or I
FA = (NH 2 ) 2 CH +
HIM = C 3 N 2 H 5 + GUA = C(NH 2 ) 3 +

CN

MA = CH 3 NH 3 +

AZE = (CH 2 ) 3 NH 2 +
HCOO
PIP = C 4 H 12 N 2 2+
HAZ = NH 2 NH 3 +

N3

TrMA = (CH 3 ) 3 NH +

DMA = (CH 3 ) 2 NH 2 +
N(CN) 2

TPrA = N(C 3 H 7 ) 4 +

EA = CH 3 CH 2 NH 3 + TMA = (CH 3 ) 4 N + M(CN) 2

Figure 3 | Structural diversity of the Asite and Xsite ions of hybrid organicinorganic perovskites.
Nature Reviews | Materials
a|The structures of a selection of possible Asite cations used in hybrid organicinorganic perovskites (HOIPs). b|The
structures of a selection of possible Xsite anions used in HOIPs.

the anionic framework and consequently to distinctive Ge2+ gives rise to very distorted GeI6 octahedra, which
phase-transition mechanisms and dynamics67. are composed of three typical and three elongated GeI
Concerns have been raised about the toxicity of Pb bonds. As a result, their bandgaps (~1.62.2eV) are
and Sn HOIPs and, hence, the potential limitations higher than in their Pb counterparts, which make them
to their wide-scale use in solar energy technology 68. less attractive for photovoltaic applications. In addition,
More severe limitations could be their instability under Ge2+ is more easily oxidized than Pb2+ and Sn2+, further
atmospheric conditions, in particular humidity, and the indicating that this strategy is probably impractical.
unclear effect of phase transitions at elevated tempera- Another approach is to construct double perovskites
tures on photovoltaic performance. These issues can be through substitution of the divalent metals (Pb, Sn or
partially addressed by device encapsulation, which is an Ge) with a combination of monovalent and trivalent
established technique for commercial photovoltaics69. metals. This has been realized in two inorganic com-
Nevertheless, a search has begun for more stable pounds (Cs2AgBiCl6 and Cs2AgBiBr6)7375 and a hybrid
and eco-friendly HOIP materials for use in photo perovskite ([(MA)2][KBiCl6])26, with bandgaps between
voltaic devices. Mixed cation perovskite films61 and ~2.2 and 3.0eV. These halide HOIPs, with eco-friendly
2D layered perovskites70 have been proposed as candi- compositions, have good thermal, moisture and mechan-
dates as a result of their increased stability. Thorough ical stability, indicating a possible route to an opti-
investigation of the fundamental properties of these mized material. However, they are all indirect-bandgap
systems and testing of devices for extended times are semiconductors with flat bands around the Fermi level,
required to establish their use in commercial appli- and their bandgaps are too wide for use as good solar-
cations. In particular, instability under illumination cell materials. An experimental breakthrough, guided
has been observed in systems with mixed-halide by first-principles calculations, demonstrated the
compositions71. Solar-cell HOIPs incorporating Ge successful preparation of a hybrid double perovskite,
(rather than Pb or Sn) have also been successfully pre- (MA)2TlBiBr6, which is isoelectronic with MAPbBr3 and
pared, including MAGeI3, FAGeI3 and [ACA][GeI3] shows similar optical behaviour with a direct bandgap
(ACA=acetamidinium)72. In these materials, the strong of ~2.0eV (REF.76). Obviously, the toxicity of Tl is more
stereochemical influence of the lone-pair s orbitals of disadvantageous than that of Pb; therefore, the use of

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other benign monovalent metals, such as Cu+ and Ag+, of states near to the Fermi level. However, the Asite
must be considered. Although the predicted bandgaps amine cations could influence the bandgap by distort-
of (MA)2CuBiBr6 and (MA)2AgBiBr6 are comparable ing the anionic framework through hydrogen bonding
to Pb HOIPs, the indirect character of their bandgaps and van der Waals interactions upon thermal and pres-
may preclude them as ideal single-junction photovoltaic sure perturbations46,48. Iodide HOIPs are most suitable
absorbers. In this regard, the double perovskite strategy for photovoltaic applications because their bandgaps
demands further justification, and alternative solutions (~1.21.6eV) are around the optimal value of ~1.11.5eV
must also be explored. for single-junction photovoltaic devices under the stand-
ard solar spectrum, according to the ShockleyQueisser
Physical properties. The good performance of Pb and Sn model77. To understand the fundamental electronic
halide HOIPs (AMiiX3; A=MA or FA, M=Pb or Sn, and structure of these halide HOIPs, we take the cubic phase
X=Cl, Br or I) in solar cells originates from their supe- of MAPbI3, which is computationally less demanding
rior semiconducting properties. They are direct-bandgap than the ambient tetragonal phase, to exemplify the elec-
semiconductors, with experimentally observed bandgaps tronic structure through recent theoretical studies78. The
ranging from ~1.22.8eV (REFS46,48) (FIG.4a). Their valence band maximum is mainly constructed from the
bandgaps are predominantly determined by the halides 5p states of I, mixed with a certain percentage of the 6s
because of the strong contribution of the halide porbitals states of Pb, while the conduction band minimum origi-
to the optical transition, but they can also be tuned by nates primarily from the 6p states of Pb, hybridized with
varying the Bsite metal. In general, their bandgaps are a small amount of the 5p states ofI (REF.78) (FIG.4b). By
weakly dependent on the Asite organic cations because taking into account the spinorbit coupling (SOC) of Pb,
the 2p orbitals of carbon and nitrogen and the 1s orbitals the calculated bandgap of cubic MAPbI3 is close to the
of hydrogen do not contribute significantly to the density experimental value64.

Table 1 | A summary of the chemical variabilities, crystal symmetries and physical properties of hybrid organicinorganic perovskites
HOIPs ASite BSite XSite Symmetry Tolerance factor Physical properties
Halides MA and FA Pb , Sn and Ge
2+ 2+ 2+
Cl , Br or

Orthorhombic ~0.9121.142 Semiconductivity
I Trigonal Photovoltaics
Tetragonal Laser physics
MA K+/Bi3+ and Tl+/Bi3+ * ~0.906923
Cubic Light-emitting diodes
Mechanical properties
PIP, [DABCOH2]2+ K+, Cs+ and Rb+ Cl Monoclinic ~0.9221.037
Orthorhombic
Trigonal
Formates Cs+, K+, NH4+, MA, FA, Mg2+, Mn2+, Fe2+, Co2+, HCOO Monoclinic ~0.7841.001|| Magnetism
GUA, EA, DMA, AZE, Ni2+, Cu2+, Zn2+ and Orthorhombic Dielectricity
HIM and HAZ Cd2+ Trigonal Ferroelectricity
Tetragonal Ferroelasticity
Multiferroicity
TrMA, DMA and EA Na+/Cr3+, Na+/Al3+, HCOO Triclinic ~0.8971.040 Mechanical properties
Na+/Fe3+ and K+/Sc3+ * Trigonal
Azides MA, DMA, TrMA and Mn2+, Cd2+ and Ca2+ N3 Triclinic ~0.7861.023 Magnetism
TMA Monoclinic Dielectricity
Cubic Ferroelasticity
TMA Na+/Cr3+, Na+/Fe3+, ~0.9341.008
K+/Fe3+ and K+/Cr3+ *
Dicyanamides BTBA, BTEA, SPh3+ and Mn2+, Fe2+, Co2+ and [N(CN)2] Orthorhombic ~1.1421.166 Magnetism
TPrA Ni2+ Tetragonal Dielectricity
Dicyanometallates PPN Cd2+ [Ag(CN)2] Monoclinic ~0.9981.141 Magnetism
Trigonal
Mn , Co , Ni and
2+ 2+ 2+
[Au(CN)2] Cubic
Cd2+
Cyanides HIM, DMA, MA, TMA, K+/Fe3+ and K+/Co3+ * CN Triclinic ~0.8401.031 Dielectricity
TrMA and GUA Monoclinic
Cubic
Borohydrides MA Ca2+ BH4 # Cubic ~0.980 Hydrogen storage
AZE, azetidinium; BTBA, benzyltributylammonium; BTEA, benzyltriethylammonium; DABCO,1,4diazabicyclo[2.2.2.]octane; DMA, dimethylammonium; EA,
ethylammonium; FA, formamidinium; GUA, guanidinium; HAZ, hydrazinium; HIM, imidazolium; HOIPs, hybrid organicinorganic perovskites; MA, methylammonium;
PIP, piperazinediium; PPN, bis(triphenylphosphoranylidene)ammonium; SPh3+, triphenylsulfonium; t, tolerance factor; TMA, tetramethylammonium; TrMA,
trimethylammonium. *Mixed Bsites in hybrid double perovskites. The tolerance factors of the hybrid double perovskites, A2BBX6, were calculated using the adapted
formula t = (rAe + rXe)/2(rB/2 + rB/2 + hXe/2). rAeff=rmass+rion, where rmass is defined as the distance between the centre of mass of the Asite organic cation and the
atom with the largest distance to the centre of mass (excluding hydrogen atoms), and rion is the corresponding ionic radius of the aforementioned atom. rXeff can be
defined in a similar way to rAeff. [PIP][KCl3], [PIP][CsCl3], [PIP][RbCl3], [DABCOH2][RbCl3] and [DABCOH2][CsCl3] are not discussed in the halide HOIPs as they are not
solar-cell metal halide perovskites21. ||The unique tolerance factors of KCo(HCOO)3 (REF.22), CsCo(HCOO)3 (REF.23) and [NH4][Cd(HCOO)3] (REF.24), which lie in the
range ~0.6200.700, are not presented in the table owing to the special antisyn coordination mode of the formate linker. The BTBA, BTEA and SPh3+ cations are
larger than the pseudocubic cavity and, as a result, it is not possible to calculate the tolerance factors. #The molecular structure of BH4 is not listed in the table
because of the structural unavailability of [MA][Ca(BH4)3].

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The properties of the crystal structure also affect the into shallow trap states energetically close to the band.
electronic properties, in particular the transport prop- The low apparent defect densities are potentially related
erties, through carrierphonon scattering. Reports on to the low-temperature processing of the material and
hot carrier scattering 79,80 and emission broadening 81,82, have been attributed to the flexibility of the perovskite
as well as calculations8385, suggest that carrierphonon Asite, which allows spatial adjustment during fabri-
scattering rates in perovskites are reduced compared cation and consequently enables stress in the lattice to
with classical inorganic semiconductors. The response be released and pure crystals to form more easily, driv-
of the crystal lattice to the presence of non-equilibrium ing out structural defects. Defect tolerance can also be
charge carrier populations remains under investiga- achieved by using partially oxidized post-transition
tion, although a strong coupling between carriers and metals92 or through defect self-healing 46. A better under-
phonons has been hypothesized79,80. Calculations using standing of the nature of the defect states is required;
the BetheSalpeter method suggest that electrons and hitherto, this has been mainly addressed using theoretical
holes separate after light excitation to form polarons88. calculations93,94 and photoelectron spectroscopy in high
Nevertheless, more evidence is required to address the vacuum9599. Although high crystal-lattice order has been
proposition of localized charge carriers (polaron forma- reported from diffraction measurements on polycrystal-
tion86,87), particularly given the good transport values line films, more evidence is needed on both the actual
and long recombination lifetimes. size of the single-crystalline domains in these films,
Generally, to achieve high-performance photovoltaic which might be very different from the grain boundaries
devices, high-absorption cross sections for efficient light observed in microscopy, and their role in defect forma-
collection, efficient long-range charge separation, and tion. Importantly, future studies need to provide a clear
low-loss charge transport and collection are required. distinction between the effects of defect states and the
The light absorption coefficients of some HOIPs (for effects of potential polaron formation on charge-carrier
example, ~105cm1 for MAPbI3) are among the high- recombination.
est for materials with solar-cell conversion efficiencies The HOIPs used in solar cells can display long dif-
>10%, which significantly reduces the required thick- fusion lengths, from a hundred nanometres to several
ness of the absorber layer to hundreds of nanometres89. micrometres, depending on the form of the thin films
Unexpectedly, these solution-processed materials also or single crystals, for both holes and electrons100. The
demonstrate high radiative efficiencies, >50% in poly- long carrier lifetimes, in combination with high radi-
crystalline thin films90 and 90% in a nanocrystalline ative efficiencies, necessitate a consideration of photon
form91. Such high radiative efficiencies are usually attri recycling when discussing carrier transport in thin films
buted to the interaction of charge carriers with low defect under illumination. It has been reported that initially
densities or to the fast trappingdetrapping of carriers photoexcited carriers can recombine away from the

Box 1 | Representative phase transition mechanisms of hybrid organicinorganic perovskites


In contrast to the octahedral tilting and displacements that are responsible for phase transitions in conventional
perovskites, the transitions in hybrid organicinorganic perovskites (HOIPs) can have additional driving forces. In panel a,
the transition in [TMA][Mn(N3)3] (TMA=tetramethylammonium) is driven by the synergistic association of the off-centre
displacement of the TMA guests, the orderdisorder processes of both the azide ligands and the TMA cations, and a
change in the MnN6 octahedral tilting (from Glazer notation a0a0a0 to a+bc+)34,35. Notably, some adjacent octahedra in the
low-symmetry phase rotate along the same direction, which is not possible in oxide analogues. In panel b, the octahedral
tilting of MnO6 in [AZE][Mn(HCOO)3] (AZE=azetidinium) exhibits trivial changes across the ferroelastic transition (from
ab+a to ab+c), and the main driving forces are the orderdisorder of the Asite AZE cation and associated hydrogen
bonding alterations36. This unique orthorhombic Pnma to monoclinic P21/n transition, which is very uncommon in
perovskite oxides, involves the Xpoint modes in the Brillouin zone in addition to the usual M and Rpoint modes (as seen
in oxides). These examples highlight the complex cooperation of the various driving forces during phase transitions in
HOIPs. Colour scheme: Mn, green and yellow; O, red; N, blue; C, grey and black; H, light grey. The TMA and AZE cations
are equally disordered at eight and two positions in the azide and formate HOIPs, respectively. Hydrogen atoms of the
ethylene and methyl groups are omitted for clarity. Glazer notation describes the distortion of BX6 octahedra about the a,
b and c axes using symbols + and to define whether the tilting between adjacent octahedra along a given axis is
inphase or outof-phase28.

a [TMA][Mn(N 3 ) 3 ] b [AZE][Mn(HCOO) 3 ]

307 K 272 K

_
Pm 3m, a 0 a 0 a 0 P2 1 /c, a + b c + Pnma, a b + a P2 1 /n, a b + c

Nature Reviews | Materials

6 | ARTICLE NUMBER 16099 | VOLUME 2 www.nature.com/natrevmats


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a Vacuum level
b
4

Energy (eV)

Energy (eV)
2.0 eV 1.6 eV 1.5 eV 1.3 eV 2
2.8 eV 1.2 eV
I 5p
4 Pb 6p
MAPbl3 Pb 6s
6 Pbl3 N 2p
MAPbl3 Pbl3
Valence band C 2p
8 H 1s

MAPb 0.5 Sn 0.5 I 3


MAPbCl 3

MAPbBr 3

MAPbI 3

FAPbI 3

MASnI 3
R X M X PDOS

c d
2.5 0.20

Absorbance and luminescence


2
100 J cm
4 J cm2 (scaled x 25)
2.0 PL spectrum 0.15
Counts (x 10 6 )

1.5
0.10
1.0

0.05
0.5

0.0 0.00
1.55 1.60 1.65 400 500 600 700 800 900
Energy (eV) Wavelength (nm)

Figure 4 | Semiconducting, lasing and light-emitting diode properties of solar-cell hybrid Nature organicinorganic
Reviews | Materials
perovskites. a|Energy levels for different solar-cell hybrid organicinorganic perovskites (HOIPs)46,48. b|Bandgap
structures and the projected density of states (PDOS) of the cubic inorganic framework PbI3 and unrelaxed cubic
MAPbI3 (with the organic molecule along the [001] direction; MA=methylammonium), calculated using the Perdew
BurkeErnzerhof functional within the density functional theory framework78. The calculated results for PbI3 and MAPbI3
are depicted in blue and black, respectively. It is clear that the MA cation contributes very little to the band-edge states.
c|Emission spectra of a vertical microcavity from the gain medium of a 500nm MAPbI3xClx film in the laser device90. The
HOIP film was excited using a 0.4ns pulsed laser at 2.33eV and fluences of 4 and 100Jcm2. The mode at 1.6eV is
amplified when the excitation is above the lasing threshold of ~0.2J pulse energy. d|Absorption (grey line),
photoluminescence (dashed green line) and electroluminescence (solid green line) spectra of the MAPbBr3 perovskite
nanofilms107. The normalized electroluminescence spectrum of the MAPbBr2I perovskite is also shown (solid red line) and
indicates that the emissions are colour-tunable. Uniform green and red electroluminescence from the ITO/PEDOT:PSS/
CH3NH3PbBr3/F8/Ca/Ag and ITO/PEDOT:PSS/CH3NH3PbBr2I/F8/Ca/Ag perovskite light-emitting diodes, respectively,
are shown in the inset. PL, photoluminescence. Panel b is adapted with permission from REF.78, American Physical
Society. Panel c is adapted with permission from REF.90, American Chemical Society. Panel d is adapted with permission
from REF.107, Macmillan Publishers Limited.

excitation spot to regenerate photons, which can then as GaAs (REF.106), indicate good transport performance.
be reabsorbed to form charge carriers at significant These attributes are requirements of an optimal material
distances away from the initial excitation point 101. The for a single-junction solar cell and contribute to the high
long transport lengths suggest that these materials can efficiencies of the HOIP-based solarcells.
function effectively in thin films, because charges can be Materials with good performance for converting
transported in the perovskite over long distances. The light to electricity can also be excellent electrically
exciton binding energy (EB), which defines the lowest driven light emitters108. In this context, the outstanding
energy required to dissociate an exciton (electronhole long carrier lifetimes and low non-radiative recombi-
pair), must be small to achieve efficient charge-carrier nation rates of solar-cell HOIPs are useful attributes
separation. Experimental reports agree with the assump- for lasing structures. In 2014, a HOIP-based microcavity
tion that photoexcitations in HOIPs directly form free lasing structure was fabricated90 by simply sandwiching
electrons and holes, rather than bound excitons, because the MAPbI3xClx emitter between two reflective layers
the EB is low enough (25meV) to allow charge separa- (FIG.4c). By reducing the size of the resonator structures
tion at room temperature102105. Furthermore, the elec- to the nanoscale, MAPbX3-based nanowire lasers with
tronhole effective masses of HOIPs86, which are close reduced lasing thresholds have been achieved109, possi-
to those of prototypical inorganic semiconductors, such bly because of the higher Qfactor and single-crystalline

NATURE REVIEWS | MATERIALS VOLUME 2 | ARTICLE NUMBER 16099 | 7


REVIEWS

nature of the nanostructures. More importantly, the has led to disagreement with the above conclusions120,
emitting wavelength can be readily tuned to cover and more compelling experimental evidence is needed
the entire visible light range through alteration of the to validate the theoretical results.
X-site anion110. Further work shows that near-infrared Considering the large SOC inherent to Pb and Sn and
lasing has been successfully realized in planar nanopores, the possible asymmetry of the crystal lattice in these hal-
which is important in distinguishing random lasing ide HOIPs, it is possible that these two phenomena could
from spatially coherent lasing 111,112. Recent develop couple with each other and generate the Rashba effect.
ments have used surfactant micelles as soft templates to The tetragonal phase of MAPbI3 was first explored by
control the growth of MAPbBr3 microstructures, from using DFT and was found to be a possible ferroelectric
1D microwires to 2D microplates. The microwires emit material. In addition, it was demonstrated that the
strong green light with intense spots at the ends, whereas helical direction of the angular momentum texture in
the microplates give bright emissions at the rectangular the Rashba band can be tuned by ferroelectric switch-
edges but very weak emissions from the bodies113. The ing 121. Further work on another possible ferroelectric
demonstration of low-threshold lasing in macroscopic perovskite, FASnI3, revealed that the relatively strong
feedback structures will be crucial for the development SOC in this asymmetric HOIP results in coexistence
of perovskite-basedlasers. of the Rashba and Dresselhaus effects, and it leads to
The broadband colour tunability and high photo a spin texture that can be induced, tuned and switched
luminescence quantum efficiencies of perovskite halides by external electric fields via control of the ferroelectric
also make them promising materials for uses in low-cost state122. As the ferroelectricity in these two materials is
and large-area light-emitting diode (LED) devices. Bulk strongly related to the configurations of the polar Asites,
HOIP-based LEDs, constructed as simple multilayered this study highlights the intriguing interplay between
devices, were shown to emit near-infrared, green and the SOC and the organic dipole ordering, which has not
red light at room temperature, depending on the halide been seen in traditional spintronic materials.
composition in the HOIP emitters107 (FIG.4d). Their bright The mechanical properties of perovskite halides are
electroluminescence benefits from the efficient radiative important as they influence manufacturing and pro-
recombination of injected electrons and holes. However, cessing significantly 123,124. Nanoindentation techniques
the efficiencies of the HOIP LEDs are lower than for were used to probe the fundamental elastic and plastic
conventional organic and quantum-dot LEDs, probably properties of MAPbX3 (X=Cl, Br or I) single crystals125.
because of the poor morphology of the HOIP thin layers. The measured Youngs moduli (~1020GPa) correlate
Followup work demonstrated that the LED performance well with the structural and chemical differences in these
could be improved by embedding the nanocrystalline analogues, in which framework stiffness is proportional
HOIPs into a pinhole-free matrix of dielectric polymer to the PbX bond strength and tolerance factor, as well as
with improved morphology and higher efficiency 114. the electronegativity of the halogen atoms. However, the
Recently, uniform MAPbBr3 nanoplatelets with very hardness properties show an inverse trend (I>Br>Cl),
high crystallinities, prepared through a facile solution with the least rigid system, MAPbI3, having the highest
method, were used to fabricate LEDs. The devices emit resistance to plastic deformation. A later work reported
bright, stable and spectrally narrow 529nm green light, results consistent with the above observations and also
with a remarkably high yield of >85%115. In addition, the discussed the thermal expansion behaviour of these hal-
superior moisture resistance of these LEDs makes glove- ide HOIPs126. Their pronounced thermoelastic response
box preparation unnecessary, thus enabling cheaper and (~3040106K1), as a consequence of octahedral flex-
scalable processing, which is required for industry. ing, might lead to ductility and flexibility, which could
The polar nature and orderdisorder transitions of aid the self-healing of point defects during device oper-
MA and FA cations across phase transitions in halide ation. In contrast, the relatively low hardness properties
HOIPs raise the question of whether HOIPs can align indicate ease of plastic deformation, which could affect
in an ordered way and give rise to ferroelectricity. The the cyclability of flexible cells and devices.
existence of ferroelectric domains in the crystal lattices Hydrostatic deformation and uniaxial stress occur
should enhance electronhole separation and conse- during any manufacturing processes; therefore the
quently lead to higher photovoltaic performance46. The high-pressure behaviour of the perovskite halides has
first potential evidence of the ferroelectric properties of also been explored124,127. The hydrostatic behaviour of
MAPbI3 in the ambient tetragonal phase was the obser- MAPbBr3 was examined, revealing the occurrence of suc-
vation of a hysteresis in the currentvoltage plots64. Soon cessive phase transitions at pressures between ~0.4 and
after, the first direct experimental evidence of ferroelec- ~1.1GPa (REF.128). Recently, it was reported that MAPbI3
tric domains, using piezoelectric force microscopy, was undergoes a tetragonal to orthorhombic phase transi-
reported116. The complex atomic origins were elucidated tion at an even lower pressure of ~0.3GPa (REFS129,130).
using density functional theory (DFT) calculations and Such pronounced transitions involve significant struc-
symmetry mode analysis, and the spontaneous polar- tural and bonding alterations, and corresponding band-
ization was found from the combined contributions gap changes130. Considering the importance of flexible
of the relative movement of MA and the relaxation of devices, if the performance of solar cells could be influ-
the framework, which are coupled through hydrogen enced by phase transitions during significant bending of
bonding 117119. However, further experimental work on the device, this will be a critical issue that must be taken
the MAPbI3 thin films using impedance spectroscopy into account. In addition, the sensitivity to compression

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REVIEWS

of these halide HOIPs indicates some metastable phases to noncentrosymmetric exchange pathways, which per-
could be synthesized under medium pressure. mit the occurrence of DzyaloshinskyMoriya interac-
tions and result in spin-canted antiferromagnetism and
Hybrid formate perovskites weak ferromagnetism156. In addition, interesting hidden
Synthesis and chemical diversity. The limited size of hal- spin-canting, spin-flop, spin-flip and large spontaneous
ide anions only enables the construction of perovskites magnetization phenomena are present in the formate
using smaller A-site cations such as MA and FA; larger HOIPs156. As with conventional perovskite oxides, when
and longer Asite organic cations cannot be accommo- dimagnetic dopants are used, solid solutions such as
dated unless the X-site linkers are extended. The for- [MA][Mn1xZnx(HCOO)3] can be tuned from long-range
mate group is a bridging linker with an effective length order to paramagnetism158. More interestingly, resonant
of ~4.5 (REF.19), which enables it to function as an ideal quantum tunnelling of magnetization was observed in
replacement for halides to accommodate a wide range [DMA][Fe(HCOO)3], in which an intrinsic magnetic
of organic amine cations. Accordingly, perovskite-like phase separation occurs because of the coexistence of
metal formate frameworks have been synthesized under long-range-ordered spin-canting and isolated single-ion
mild solution conditions using this strategy 5,131. Using quantum magnetism159 (FIG.5a,b). This unusual phen
various protonated-amine cations (from the smallest, omenon arises because the long-distance superexchange
ammonium, to the largest, tetramethylammonium between adjacent divalent Fe centres, mediated by the
(TMA)) and six-coordinated divalent metals, about 45 formate group, shows significant dependence on the
different formate-based perovskites have been discov- hydrogen-bonding geometry. These striking discover-
ered, making them the largest subclass of hybrid per- ies highlight the important role of hydrogen bonding in
ovskites5,2224,42,132154 (TABLE1). The formate linker adopts influencing the remarkable properties of formateHOIPs.
an antianti coordination mode in most cases (but anti Phase transitions in conventional perovskites are
syn in a few compounds2224) and bridges adjacent met- mainly driven by displacements of the Asites and/or
als to form cubic or pseudocubic cavities in which the Bsites and the tilting of the BX6 octahedra. However, the
amine cations, with effective radii from 1.46 to 2.92, are origins of structural transitions in most known formate
located5,136. Changing the divalent metals for a combina- HOIPs are from the orderdisorder behaviours of the
tion of mono- and trivalent metals (for example, Na+ and Asite organic amines (occasionally the Xsite formate
Fe3+) gives rise to a subclass of formate HOIPs possessing group is also involved)36. Such orderdisorder and the
hybrid double perovskite structures11,17. associated changes in the hydrogen bonding give rise
Although the perovskite architecture is adopted for all to spontaneous polarization in prototypical ferroelectric
these formate HOIPs, the crystal symmetries and guest materials, such as NaNO2 and KH2PO4, and this has
host interactions depend on the size, shape and nature stimulated a search for ferroelectricity in these order
of the organic cations, leading to abundant and tunable disorder-type formate HOIPs161,162. The first report
physical properties. In general, the Asite organic cations concerning electric ordering in formate HOIPs was on
and formate linkers, with lower symmetries compared [DMA][M(HCOO)3] (M=Mn, Fe, Co, Ni or Zn), and
with the spherical metal ions in oxides, assemble into the structural findings showed that the DMA cation is
architectures with monoclinic, orthorhombic or trigonal threefold disordered at ambient conditions but ordered
space groups, and rarely assemble into tetragonal or cubic at lower temperatures39,155. Further experimental charac-
space groups for their ambient phases5,11,17,2224,42,132154. terization revealed a significant anomaly in dielectricity
It is noteworthy that there are abundant hydrogen bonds at ~160K for the Zn compound, along with differing
in these formate HOIPs, for which the amine hydrogen diffraction patterns above and below this critical temper-
atoms on the Asite organic cations function as hydro- ature obtained from synchrotron Xray powder measure-
gen-bond donors and the oxygen atoms in the formate ments. Further heat capacity measurements confirmed
ligands act as acceptors. The hydrogen-bonding modes the above phase transition, although the entropy change
and strengths can be tuned by selecting organic amines across the transition (1.1JK1mol1) is much lower
with different symmetries and bonding sites. Most than the value expected for switching between three-
importantly, the Asite organic cations are disordered fold order and disorder (9.1JK1mol1). Motivated by
at high temperatures, but usually become ordered on these results, the structure of the Mn analogue was
cooling 5,11,42,137140,145,148,150. This results in a variety of characterized in detail, and it was found that the phase
intriguing phase transitions including ferroelectric131,155, transition is indeed triggered by the switching of the
ferroelastic36 and multiferroic transitions155. DMA cation from three orientations to one, at ~190K
(REF.163). Although the_ reported symmetry change from
Properties. Magnetism was the first property to be non-polar trigonal R3c to polar monoclinic Cc suggests a
explored in the formate perovskites, and their magneto- probable ferroelectric transition, a definitive conclusion
structural relationships have been extensively investi- was not drawn at that time. Further work on the deu-
gated156,157. The long distance spanned by the formate terated cobalt compound, [(CD3)2ND2][Co(DCOO)3]
linker can only mediate weak magnetic coupling and, (REF.160) (FIG.5c,d), reproduced the non-polar to polar
hence, formate HOIPs only exhibit long-range magnetic symmetry change seen in earlier work, and independ-
ordering below 50K, making them less attractive in terms ent measurements of second harmonic generation fully
of practical applications. The tilting of the adjacent MO6 supported such results. Furthermore, dielectric hys-
octahedra bridged by the antianti formate linkers leads teresis was recorded below the transition temperature

NATURE REVIEWS | MATERIALS VOLUME 2 | ARTICLE NUMBER 16099 | 9


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a d g
1.2

0.8

0.4

P (C cm 2 )
0.0 136 K
138 K
H 0.4
140 K
C 0.8 145 K
O 148 K
N 1.2 163 K
Superexchange
Fe SIQM CAFM magnetism 30 20 10 0 10 20 30
E (kV cm 1 )

Current (pA)
b 40 0T
3 30 7T
0.2 2K 20
10
0
Current (nA)
M ( B /Fe)

150
160
170
180
0.0
Temperature (K)

1
0.2

0.0
4 2 0 2 4 150 160 170 180 190 200 210
H (T) Temperature (K)
c h [GUA][Mn(HCOO)3]
f 2.0 [AZE][Mn(HCOO)3]
30

E (GPa)
1.5
20
P (C cm 2 )

159 K 1.0
10
13 T H (GPa)
0.5 7T 2
0T 1
0.0 0 _
150 160 170 180 190 (110) (101) (101)
Temperature (K) Orientation

Figure 5 | The physical properties of formate hybrid organicinorganic perovskites. a,b|Long-range canted antiferromagnetic Nature(CAFM)
Reviews | Materials
order and
isolated single-ion quantum magnetism (SIQM) coexist in [DMA][Fe(HCOO)3] (DMA=dimethylammonium). In panel a, the grey arrows depict the spin of
the Fe2+ centres, the small box indicates that the Fe2+ centre exhibits SIQM, and the bigger box shows that two Fe2+ centres are coupled via a formate
ligand to exhibit CAFM159. The CAFM order originates from the superexchange interactions between adjacent Fe2+ centres, and the isolated SIQM
occurs when the superexchange coupling is broken by the NHO hydrogen-bonding between the formate group and the DMA cation. In panelb,
the magnetizationfield strength (MH) hysteresis loops show step-shaped characteristics, indicating the occurrence of resonant quantum tunnelling
magnetization. c,d|Ferroelectric phase transition of [(CD3)2ND2][Co(DCOO)3] (REF.160). The transition, shown in panel c, is mainly triggered by the
orderdisorder of the DMA cation and the associated variations in hydrogen bonding at ~159K. The polarizationfield strenght (PE) hysteresis loops
collected below the transition temperature (Tc) with a fixed frequency at 50Hz are displayed in panel d. The black line represents the fit obtained using
the Landau theory. e,f|The electric polarization modulated by a magnetic field in [DMA][Mn(HCOO)3] (REF.40). The pyroelectric current as a function of
temperature under 0 and 7T magnetic fields is shown in panel e. The electric polarization normal to the (012) plane under 0, 7 and 13T magnetic fields is
shown in panel f; both the magnetic and electric fields were applied along the same direction. g,h|Mechanical properties of [AZE][Mn(HCOO)3] and
[GUA][Mn(HCOO)3] (AZE=azetidinium, GUA=guanidinium)44. Panel g displays the framework structures of the two formate HOIPs, and Youngs
modulus (E) and hardness (H) values are shown in panel h. The green and blue points correspond to mechanical data from [GUA][Mn(HCOO)3] and
[AZE][Mn(HCOO)3], respectively. Colour scheme: Fe, yellow; Co, light magenta; Mn, wine or olive; O, red; N, blue; C, black; H, light grey. Hydrogen atoms
of the ethylene, methyl and some formate groups are omitted for clarity. Hydrogen bonds are represented as purple lines. Panels a and b are adapted
with permission from REF.159, American Physical Society. Panel d is adapted with permission from REF.160, Wiley-VCH. Panels e and f are adapted with
permission from REF.40, Macmillan Publishers Limited. Panel g is adapted with permission from REF.44, American Chemical Society.

at ~159K, and the unambiguous hysteresis loops dielectric permittivities are characteristic of a Debye-
undoubtedly confirm the intrinsic ferroelectricity of like relaxation behaviour, with an activation energy
this formate HOIP. The spontaneous polarization was (Ea) of 464Jmol1 and a relaxation time of 1.021015s.
saturated at ~1.02Ccm2, which is more than 5 times This ferroelectric behaviour resembles that of proto
that of the prototypical hybrid ferroelectric, Rochelles typical orderdisorder type ferroelectric materials,
salt (0.2Ccm2)161. Moreover, the frequency-dependent such as NaNO2, and opens up avenues for creating

10 | ARTICLE NUMBER 16099 | VOLUME 2 www.nature.com/natrevmats


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new ferroelectric relaxors with perovskite architectures curve with respect to the electrical field could be a possi-
beyond oxides162. Interestingly, by replacing the divalent ble reason for the onset of these giant dielectric anomalies
first-row transition metals (Mn2+, Fe2+, Co2+, Ni2+ and between 270 and 280K.
Zn2+) with an alkaline earth metal, Mg 2+, the transition The existence of magnetic centres on the Bsites
temperature can be tuned towards ambient temperature and the orderdisorder nature of the Asites in formate
(~270K), which makes [DMA][Mg(HCOO)3] promis- HOIPs raise the question as to whether these properties
ing for future applications164. The harder Lewis acidity of can couple with each other to generate multiferroicity 174.
the Mg 2+ ion compared with other divalent metal ions Following a pioneering study on this topic155, the search
gives the MgO bonds more ionic character and local- was continued by looking for magnetoelectric coupling
izes the negative charge on the formate oxygen atoms. in the deuterated formate [(CD3)2ND2][Co(DCOO)3]160.
As a result, the strength of the NHO hydrogen bonds Although the material is both ferroelectric and ferromag-
increases, which leads to a higher critical temperature. netic, the dielectric permittivities remain unchanged,
Further theoretical work revealed the additional possi- even under a 5T magnetic field. Subsequent work175 on
bility of tuning ferroelectricity through alteration of the the non-deuterated cobalt formate, using resonant ultra-
Asite amine in a manganese formate HOIP, in which the sound spectroscopy, focused on the interplay between
polarization can be increased to ~6Ccm2 by replacing magnetism and ferroelasticity; a slight elastic anomaly
EA (EA=ethylammonium) with a heavier analogue, eth- below the magnetic ordering temperature at ~15K, in
ylphosphonium (C2H5PH3+)165. In another study, DFT the form of softening, indicates the existence of weak
calculations demonstrated that the ferroelectric polar- magnetoelastic coupling, giving the first evidence for
izations of [GUA][Cr(HCOO)3] (GUA=guanidinium) multiferroicity in these formateHOIPs.
and [EA][Mn(HCOO)3] could be increased by more Inspired by these observations, the manganese ana-
than 300% via compressive strains, which is ascribed to logue, [DMA][Mn(HCOO)3], was examined, and it was
the high flexibility of the framework constructed by the found that the magnetic state varies at the onset of the
bent formate linkers166. As with perovskite oxides, solid ferroelectric phase transition40 (FIG.5e,f). However, the
solution formation can be used to control the electrical ferroelectric polarization can be significantly enhanced
properties of these formate HOIPs. The mixed Asite by >20% on application of a strong magnetic field of
formate HOIPs, [HAZxMA1x][Mn(HCOO)3] (HAZ= 13T. Although these results are still being debated176,
hydrazinium; x=1.000.67), have been synthesized by the authors claimed that a possible interpretation is
dispersing non-polar [MA][Mn(HCOO)3] into ferro- that magnetoelectric coupling in the paramagnetic state
electric [HAZ][Mn(HCOO)3] (REF.167). In this exam- occurs because of a magnetoelastic effect that modu-
ple, the Asite composition and framework distortions lates both the superexchange and the hydrogen-bonding
were successively engineered, resulting in para- to interactions. Subsequently, it was shown that cross cou-
ferroelectric transitions with diverse characteristics. pling between electric and magnetic orders exists in iso
Moreover, the amine dynamics have recently been stud- structural [DMA][Fe(HCOO)3] (REFS177,178); it has also
ied by solid-state NMR spectroscopy in a closely related been demonstrated that the tunnelling magnetization
Asite solid solution168. can couple with the ferroelectric ordering in this mat
In addition to ferroelectricity, dielectricity is of con- erial, extending the distinct hydrogen-bonding effect to
siderable interest owing to its intriguing dependence another dimension by inducing a very unusual resonant
on orderdisorder transitions. The azetidinium series, quantum magnetoelectric effect 179. Recently, magnetic
[AZE][M(HCOO)3] (AZE=azetidinium; M=Mn, Cu ordering-induced ferroelectricity and the corresponding
or Zn), was found to exhibit extraordinarily large die- multiferroic behaviour in [MA][Co(HCOO)3] (REF.180)
lectric permittivities () of >104 over a broad tempera- have been reported. Meanwhile, significant compu-
ture range near to room temperature169,170. Specifically, tational efforts have been made to help interpret the
the Cu and Mn compounds show giant values of experimental findings165,181,182. Using first-principles cal-
>105 and >106, respectively, at 1kHz and ~280K, and culations, it was discovered that in [GUA][Cu(HCOO)3]
a maximum >106 for the isomorphous zinc phase the cooperation between the JahnTeller antiferro-
occurs at 270K and at a frequency of 0.1kHz. Such distortions and the Asite GUA cation through hydrogen
enormous values have only been found in some highly bonding induces ferroelectricity. In addition, this ferroe-
polarizable perovskite oxide relaxors171 (for example, lectricity can couple with the weak ferromagnetism to give
BaTiO3) and conjugated polymers172 (for example, the rise to magnetoelectricity 181. This discovery is unprece-
2chloroanthraquinone and tetrachlorophthalic anhy- dented because the non-polar structural distortions
dride polymer). Detailed structural analysis revealed (that is, antiferro-distortions), which are unable to break
that the dynamic puckering and conformational insta- inversion symmetry in traditional inorganic perovskites,
bility of the azetidinium cation have an important role can generate switchable polarization through dispersion
in leading to the huge dielectric anomalies across the interactions with the Asite in HOIPs. This hypothesis
phase transition. Proton NMR spectra indicate that was later confirmed by experiment, and an interesting
ring-puckering of the azetidinium cations dominates resonance switching model of the Lewis structures of
the spinlattice relaxation of the high-temperature GUA was proposed, which supports the microscopic
phase, and the potential energy for the transition state mechanism for the occurrence of hybrid improper
of the ring-puckering decreases with lowering tempera- ferroelectricity 183. Theoretical methods have also been
ture173. Therefore, the high susceptibility of the potential used to investigate another JahnTeller analogue,

NATURE REVIEWS | MATERIALS VOLUME 2 | ARTICLE NUMBER 16099 | 11


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[GUA][Cr(HCOO)3], which is yet to be synthesized182. but have distinct modes of hydrogen bonding between
In this case, the rotational modes of the Asite GUA cat- the Asite amine cations and the perovskite framework.
ion and the JahnTeller distortion of the Cr 2+ metal ions The crosslinking hydrogen bonds in the guanidinium
are hybridized to generate ferroelectricity by coupling compound lead to substantially stronger constraints and
with the secondary non-polar modes. In such a hybrid correspondingly higher mechanical strengths, in marked
improper ferroelectric perovskite, the JahnTeller effect contrast to the azetidinium case. Such huge disparity
is mainly responsible for the interplay between electric results in a difference of ~100% in elastic modulus and
polarization and weak ferromagnetism. hardness, as well as a difference of ~400% in thermal
The mechanical properties of formate HOIPs have expansion. Moreover, the applied hydrostatic pressure
been explored from several interesting perspectives44,184. needed to induce the orthorhombic to monoclinic phase
Youngs moduli of four isomorphous metal formate transition in the guanidinium framework is about twice
perovskites, [DMA][M(HCOO)3] (M=Mn, Co, Ni or that required in the azetidinium analogue. These results
Zn), were measured using single-crystal nanoindentation demonstrate that mechanical engineering can be achieved
techniques184. The resulting modulus values (~1925GPa) by simple modification of the hydrogen bonding in these
are in the sequence of Mn,Zn<Co<Ni, which does not formate HOIPs. It must be remembered, however, that
show any direct link with the radii of the metal cations. their mechanical properties are about an order of magni-
However, the cation-dependent behaviour can be well tude lower than perovskite oxides, which is disadvanta-
explained by taking into account their different ligand- geous for applications in industrial environments (as are
field stabilization energies. The large ligand-field stabili- their low thermal stability and high moisture sensitivity).
zation energy of the Ni cation causes the higher resistance
to MO6 octahedral deformation, thus leading to the stiffer Other hybrid perovskites
nature of the framework. The intriguing influence of Azide hybrid organicinorganic perovskites. This sub-
hydrogen bonding on the elastic and plastic properties class of HOIPs can be obtained with a variety of organic
of two formate HOIPs, [AZE][Mn(HCOO)3] and [GUA] amines using the bridging linear azide group (N3)
[Mn(HCOO)3], has also been examined44 (FIG. 5g,h). on the Xsite9,14,34,185187 (TABLE1). In 1986, the synthe-
These two HOIPs possess similar anionic frameworks sis and structural characterization of [TEA][Ca(N3)3]

a b 3.75

3.4
CH3NH3+
M T (cm 3 mol 1 K)

3.70
(CH3)3NH+

M T (cm 3 mol 1 K)
3.3
296 K
3.65

3.2 (CH3)2NH2+ (CH3)4N+

3.60
P21/c C2/c 3.1
260 280 300 320 340 360 380
Temperature (K)
c d
36 0.5 kHz 50 kHz
1 kHz 100 kHz
30 5 kHz 250 kHz
25 kHz 1000 kHz
24
174 K

18

12

6
_ _
R3 (-phase) P1 (-phase) 0
100 150 200 250 300
Temperature (K)
Figure 6 | Phase transitions and associated properties of azide hybrid organicinorganic perovskitesNature Reviews
(HOIPs). | Materials
a,b|Phase transition and magnetic bistability of [TrMA][Mn(N3)3] (TrMA=trimethylammonium)34. The symmetry breaking of
the framework structure from P21/c to C2/c at ~296K is shown in panel a. Magnetic hysteresis loops are depicted in panelb
for [MA][Mn(N3)3], [DMA][Mn(N3)3], [TrMA] [Mn(N3)3] and [TMA][Mn(N3)3] (MA=methylammonium, DMA=dimethylammonium
and TMA=tetramethylammonium). The molar magnetic susceptibility is represented by M. c,d|Ferroelastic phase
transitions and_associated dielectric
_ properties of [DMA][Cd(N3)3] (REF.187). In panel c, the pseudocubic framework unit
evolves from R3 (-phase) to P1 (-phase) at ~174K, and in panel d the real part of the dielectric permittivity () is
illustrated as a function of temperature. Colour scheme: Mn and Cd, red; N, blue; C, black. Hydrogen atoms are omitted for
clarity. Hydrogen bonds are denoted as dotted purple lines. Panel b is adapted with permission from REF.34, American
Chemical Society. Panel d is adapted with permission from REF.187, Wiley-VCH.

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(TEA=tetraethylammonium), which crystalizes in a mon- have interesting properties, it should be noted that exper-
oclinic distorted perovskite architecture, was reported9. imental precautions are required because of their toxicity
Subsequently, another azide HOIP, [TMA][Mn(N3)3], and the risk of explosion of both the starting materials and
formed from a smaller organic amine cation and mag- products. These disadvantages may preclude their use in
netic Mn2+ ion, was synthesized and shown to undergo industrial applications.
a monoclinic to pesudocubic phase transition at ~305K
(REF.185). Although the endtoend coordination mode Dicyanamide hybrid organicinorganic perovskites.
of the azide group can usually mediate ferromagnetic The dicyanamide (DCA) ligand, N(CN)2, has a Vshape
interactions, this manganese compound exhibits long- molecular configuration, but the long spacing between
range antiferromagnetic ordering at ~70K. This relatively the two ends of the molecule makes it a suitable bridg-
high magnetic ordering temperature has stimulated fur- ing linker for constructing frameworks, suggesting the
ther efforts to design and synthesize azide HOIPs with possibility of creating perovskite structures. In 2003
potential magnetic applications (FIG.6a). For example, a and 2004, three perovskite-like compounds, [BTBA]
series of azide compounds, [(CH3)nNH4n][Mn(N3)3], has [M(DCA)3], [BTEA][M(DCA)3] and [SPh3][Mn(DCA)3]
been prepared by successively increasing the size of the (BTBA=benzyltributylammonium, BTEA=benzyltri-
Asite amine cations from MA, DMA, TrMA, to TMA34. ethylammonium; SPh3+=triphenylsulfonium; M=Mn,
These four compounds show remarkable structural phase Co or Fe), were synthesized using dicyanamide as the
transitions between 260 and 310K, and their transition Xsite linker 13,188. As deduced from the Goldschmidt
temperatures are strongly dependent on the Asite cat- tolerance factors, the accommodation of significantly
ions. More strikingly, the increase in symmetry of the larger Asite amine cations is attributed to the much
organic amine cations is translated into the thermally longer DCA linker, in marked contrast to other Xsite
driven lattice changes, whereby the ambient monoclinic anions in HOIPs. This results in a substantially big-
structures of all four compounds transform into higher ger pseudocubic perovskite unit cell, about three times
symmetries in sequence from MA to TMA. In addition, that of the formate HOIPs. A further work described
the MnN3Mn magnetic-coupling pathways and cor- another family of dicyanamide HOIPs with the smaller
responding long-range ordering can also be modulated, but more isotropic tetrapropylammonium (TPrA) cation,
which give rise to hysteretic magnetic bistability induced [TPrA][M(DCA)3] (M=Mn or Ni)45. In the latter case, the
by structural phase transitions in a controllable manner magnetic properties were the focus of the study, although
(FIG.6b). It is worth emphasizing the use of symmetry other phase transitions were observed in these DCA
induction by the alteration of the Asite amine cations compounds. Recently, these compounds were revisited,
in these azide HOIPs, because this simple and effective and their complex phase transition mechanisms were
strategy can be readily used to modify other host-guest extensively studied189,190 (FIG.7a). In addition to the role of
framework systems. off-centre displacements of the TPrA cations and order
Further exploration of azide perovskites focused on disorder of the pendant propyl groups, as well as the MN6
their ferroelastic and dielectric properties186,187. A cad- octahedral tilting, orderdisorder associated with the
mium compound, [TMA][Cd(N3)3], was synthesized DCA bridging ligands is involved in the complex phase
and found to undergo three successive phase transitions, transitions. The involvement of the Xsite linker in phase
which leads to significant ferroelasticity above room tem- transitions has rarely been found in other HOIPs. In
perature (TC320K)186. By using size-matched bimetallic addition, very high anisotropic thermal expansion with
Bsite ions, a series of double perovskite azide HOIPs, a magnitude of 104K1 was observed for the ambient
[TMA2][BB(N3)6] (B=Cr 3+ or Fe3+; B=Na+ or K+) was phase of the manganese compound189. High-pressure
prepared; these show strong first-order phase transitions calorimetry studies revealed that the phase transitions
above room temperature (TC303320K) and are associ- of the manganese and cobalt analogues are highly sen-
ated with large entropy changes14. In both cases, the meas- sitive to external hydrostatic stimuli, with giant values of
ured dielectric permittivities are low (<6.5 at 100kHz, dT/dp=242 and 184KGPa1, respectively190 (FIG.7b). Such
near to phase transition), which indicates that the behaviour indicates significant framework flexibility in
non-polar TMA cation in the Asite needs to be replaced these HOIPs, arising from the long DCA ligands, which
by a polar organic amine, in order to generate more show a substantial response to compression.
dipoles into the crystal lattice. Recently, the azide HOIP,
[DMA][Cd(N3)3], was synthesized by introducing the Cyanide, dicyanometallate and borohydride hybrid
polar DMA cation into the Asite, and the of this mate- organicinorganic perovskites. Introducing organic
rial is higher (15 at 100kHz, near to transition), as components into cyano-elpasolites results in another
expected187. This HOIP undergoes a notable ferroelastic interesting subclass of HOIPs with a double perovskite
phase transition at ~174K, which is triggered by the syner- structure8,15,16,191. An imidazolium (HIM)-templated
gistic motion of the DMA guest cation and deformation of cyanide, [HIM]2[KFe(CN)6], was synthesized using
the [Cd(N3)3] framework (FIG.6c). The rotational energy potassium ferricyanide as a precursor 8. This material
barrier of the guest cation shows a marked change when undergoes two successive phase transitions at ~158
crossing the transition temperature on heating, which and 187K owing to the orderdisorder of the Asite
results in a marked decrease in the dielectric permittivity imidazolium cation (FIG.7c). As the organic cation is
and makes it a possible candidate material for thermo polar, its switching from free motion to ordered align-
sensitive dielectrics (FIG.6d). Finally, although azide HOIPs ment induces significant anomalies in the dielectric

NATURE REVIEWS | MATERIALS VOLUME 2 | ARTICLE NUMBER 16099 | 13


REVIEWS

a b 6 P

4 Polymorph 1 Polymorph 2

Heat ow (mW)
Cooling
2
329 K
0 Heating
P = 1.0 bar
P = 17.9 bar
2
P = 34.5 bar
P = 68.9 bar P
4
Polymorph 1 Polymorph 2 327 328 329 330 331 332 333
Temperature (K)
c d 30
(0001)
_
25 (1210)
d c
20 b
a
158 K 15


10

5
0
_ 0 50 100 150 200 250
R3 C2/c Temperature (K)
Figure 7 | Phase transitions and corresponding properties of diacyanamide and cyanide hybrid organicinorganic
Nature Reviews | Materials
perovskites. a,b|The phase transition and pressure effect for [TPrA][Mn(DCA)
_ 3] (TPrA=tetrapropylammonium) . The
189

crystal structure transforms from I4/mcm (polymorph 1, left) to P421c (polymorph 2, right) at ~329K, as shown in panel a.
The differential scanning calorimetry curves recorded under different pressures (P) are depicted in panel b. c,d|Dielectric
phase transitions of [HIM]2[KFe(CN)6] (HIM=imidazolium)
_
8
. The double perovskite structure, shown in panel c, switches
between the high-temperature disordered (left, R3) and low-temperature ordered (right, C2/c) phases at ~158K, and the
disordered HIM is equally distributed at six positions, which are highlighted using red, blue, yellow,
_ grey, violet and green
colours; in panel d the temperature dependence of the dielectric permittivity () along the [1210] and [0001] direction is
illustrated. Mn, pink; K, magenta; Fe, green; N, blue; C, black. Hydrogen atoms are omitted for clarity. Panel b is adapted
with permission from REF.189, American Chemical Society. Panel d is adapted with permission from REF.8, Wiley-VCH.

permittivity (FIG.7d). By replacing Fe3+ with diamagnetic Both the geometric descriptor of the tolerance factor
(low spin) Co3+, another switchable dielectric cyanide, and the tilting indicator of the Glazer notation can be
[HIM]2[KCo(CN)6], was prepared, and the nature of well exemplified in all four Aubased dicyanometallates.
the dynamics of imidazolium through the phase tran- However, the solvated Ag compound exhibits inphase
sition was established by solid-state 1H NMR spectro tilting of neighbouring octahedra perpendicular to the
scopy 191. Based on these results, a cation more polar than rotation axis, which is not possible in conventional per-
HIM, namely DMA, was incorporated into the double ovskites. Such features resemble those in the azide HOIP
perovskite framework, and the resulting compound, analogues35, again highlighting the additional frame-
[DMA2][KCo(CN)6], showed a prominent dielectric work flexibility associated with the longer Xsite anions.
increase at the phase transition, associated with the order Moreover, the existence of intra- and inter-molecular
disorder behaviour of the DMA cation15. Moreover, the interactions involving the PPN cations introduces a new
pronounced pre-transitional fluctuations of the DMA bonding feature into the HOIP structure.
dipoles in this HOIP result in tunable dielectricity over Finally, we should mention a unique example of a
a wide temperature range, which makes it a promising perovskite-like borohydride HOIP, [MA][Ca(BH4)3], in
candidate for a multifunctional molecularswitch. which the Ca2+ ions and the tetrahedral BH4 linkers, with
Extending the cyanide ligand to the linear dicyano- a size of ~2.03, are templated by MA10. The calculated
metallate linker generates another family of cyano-based tolerance factor is ~0.98, which indicates _good stability
HOIPs. There are five known dicyanometallate perov for this framework with the aristotype Pm3m symmetry.
skites, which include four Aubased compounds, [PPN] Analogous to its inorganic analogues, this borohydride
[M{Au(CN)2}3] (PPN=bis(triphenylphosphoranylidene) HOIP could find potential use in hydrogen storage due to
ammonium; M=Mn, Co, Ni or Cd), and one Agbased the abundance of hydrogen in its crystal lattice.
compound, [PPN][Cd{Ag(CN) 2 } 3 ]3CH 3 CH 2 OH
(REFS 192,193) . The much longer [Au(CN) 2] Xsite Conclusions and future perspectives
anion gives the largest observed pseudocubic perovskite For many decades, conventional oxide perovskites have
cell with a volume of ~1,0003, which is ~4 times the had a central role in condensed-matter physics and sol-
volume within perovskite halides. The large PPN cation id-state chemistry, with important examples including
(~6.8) is able to fit into the perovskite cavity without titanate ferroelectric materials, high-temperature cuprate
causing a reduction in the dimensions of the framework. superconductors, magnetoresistive rare-earth manganates

14 | ARTICLE NUMBER 16099 | VOLUME 2 www.nature.com/natrevmats


REVIEWS

and ferromagnetic metals such as strontium ruthenate. It is interesting to consider some of the future chal-
It is therefore exciting that hybrid perovskites have opened lenges and opportunities in this exciting area. In the
up an entirely new chapter of discovery. We have shown realm of the hybrid perovskite halides, the challenges are
that HOIPs exhibit much chemical and structural diver- well known and are largely related to toxicity (especially
sity, and the range of their properties is reminiscent of with Pb) and chemical and thermal stability. However,
oxide perovskites. Semiconductivity combined with excel- these issues are being addressed, especially in terms of
lent light-harvesting properties are found in several of the encapsulation and the exploration of double perovskite
hybrid perovskite halides, and this has led to an impor- materials. We note that the hybrid double perovskites that
tant advance in the development of solution-processable have been reported so far involve chloride and bromide
photovoltaic devices. However, new features that can be ions, rather than iodide, offering another direction for
present in HOIPs, but are absent in their inorganic ana- future study. Double perovskite materials also present
logues, result in properties beyond those of conventional an opportunity to incorporate magnetic transition metal
perovskite oxides. In particular, the use of amine cations and rare-earth ions at the trivalent cation site, which
on the Asite introduces hydrogen bonding that can give could lead to very interesting magnetic and optical
rise to orderdisorder transitions and provides a differ- properties. For non-halide systems, there are challenges
ent mechanism for introducing electrical ordering, espe- in terms of their relatively poor mechanical stability and
cially ferroelectricity. It can also lead to an extremely high their rather low magnetic ordering temperatures owing
dielectric permittivity, which is not yet fully understood. to the long superexchange pathways. In terms of opportu-
Furthermore, the combination of such electrical ordering nities, other bridging Xsite linkers, such as SCN, OCN
with magnetic ordering, as a consequence of the presence and azolate, could be used to form new classes of HOIPs.
of transition metal ions on the Bsite, has resulted in a new Another interesting avenue would be the study of caloric
class of multiferroic materials. Notably, magnetoelectric effects, because the phase transitions in HOIPs are often
coupling appears to persist well above the magnetic order- associated with large entropy changes, about an order of
ing transition, which reveals another phenomenon that magnitude higher than those in oxides195,196. The order
has yet to be fully understood. disorder behaviour and framework flexibility could be
The chemical diversity and concomitant structural easily perturbed by external fields, thus leading to large
variability of HOIPs offer substantial opportunities for caloric effects. In a different area, the use of diamines on
fine-tuning their physical properties by facile chemical the Asite enables alkaline metals and other monovalent
modification194. For example, incorporating organic com- cations to occupy the Bsite and merits further explora-
ponents on both the Asite and Xsite confers additional tion. Beyond the 3D HOIP materials, there are many low-
functionalities and structural flexibility on the perovskite er-dimensional perovskite-related systems that have yet
architecture, and the role of organic components in phase to be explored197. In the case of the halide HOIPs, there
transitions of HOIPs, along with synergistic octahedral has already been extensive work in this area (as is the case
tilting, can lead to very complex behaviour. We have with oxides), but for systems involving other linkers there
shown that the well-known solar-cell halide perovskites has been little progress. The marriage of inorganic and
inhabit only a small corner of the HOIP landscape and organic components, and the integration of order and
that the existence of formate, azide, dicyanamide, cyanide, dynamics198200 in these hybrid perovskites, will certainly
dicyanometallate and borohydride HOIPs illustrates the present many academic and technological opportunities
many opportunities beyond the halideHOIPs. in the years tocome.

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