Review

pubs.acs.org/CR

Organic−Inorganic Perovskites: Structural Versatility for Functional

Materials Design
Bayrammurad Saparov and David B. Mitzi*
Department of Mechanical Engineering and Materials Science, and Department of Chemistry, Duke University, Box 90300 Hudson
Hall, Durham, North Carolina 27708-0300, United States

ABSTRACT: Although known since the late 19th century, organic−inorganic

perovskites have recently received extraordinary research community attention because
of their unique physical properties, which make them promising candidates for
application in photovoltaic (PV) and related optoelectronic devices. This review will
explore beyond the current focus on three-dimensional (3-D) lead(II) halide
perovskites, to highlight the great chemical flexibility and outstanding potential of the
broader class of 3-D and lower dimensional organic-based perovskite family for
electronic, optical, and energy-based applications as well as fundamental research. The
concept of a multifunctional organic−inorganic hybrid, in which the organic and
inorganic structural components provide intentional, unique, and hopefully synergistic
features to the compound, represents an important contemporary target.

CONTENTS 7.3.2. Optoelectronic Applications for

CH3NH3PbX3 4583
1. Introduction 4558 7.3.3. Optoelectronic Applications for Layered
2. Three-Dimensional (3-D) Organic−Inorganic Per- Perovskites 4584
ovskites 4559 7.3.4. Nonlinear Optical Applications 4584
3. Lower-Dimensional Organic−Inorganic Perov- 7.4. Charge Storage Properties and Applications 4586
skites 4560 8. Conclusion and Vision for the Future 4587
3.1. ⟨100⟩-Oriented Perovskites 4562 Author Information 4588
3.2. ⟨110⟩-Oriented Perovskites 4567 Corresponding Author 4588
3.3. ⟨111⟩-Oriented Perovskites 4568 Notes 4588
3.4. More Exotic Frameworks 4570 Biographies 4588
4. Functional Organic Cations 4571 Acknowledgments 4589
5. Intercalation Systems 4574 References 4589
6. Molecular Perovskites 4576
7. Exceptional Properties and Device Application 4577
7.1. Magnetic and Dielectric Properties and
Application 4577 1. INTRODUCTION
7.1.1. Magnetic Interactions in Hybrid Perov- Perovskite materials, most notably CH3NH3(Pb,Sn)(I,Br)3,
skites 4577 have recently taken a dominant position within the portfolio of
7.1.2. Magnetic and Multiferroic Materials 4578 compounds, offering promise for future high performance and
7.1.3. Dielectric Properties 4579 ultralow-cost-per-watt photovoltaic operation.1−6 This promise
7.2. Electrical Transport Properties and Applica- derives from the confluence of several factors, including
tion 4579 extremely high optical absorption, small effective masses for
7.2.1. Band Structures and Tunable Electrical electrons and holes, dominant point defects that only generate
Properties 4579 shallow levels, and grain boundaries that are essentially benign.7
7.2.2. Application of Sn-Based Conducting The methylammonium cation itself may also play a role in the
Hybrids 4580 special suitability of the hybrid materials for photovoltaic (PV)
7.2.3. Pb- and Ge-Based Semiconductors 4580 application, through a low barrier to reorientation within the
7.2.4. Sb- and Bi-Based Semiconductors 4580 structure and contributions to the dielectric/ferroelectric
7.2.5. Cu-Based Semiconductors 4581 properties.8 While the three-dimensional (3-D) lead- and tin-
7.3. Optical Properties and Optoelectronic Ap- based organic−inorganic perovskites hold great promise for PV,
plications 4581
7.3.1. Quantum and Dielectric Confinement
Received: December 5, 2015
Effects and Excitonic Properties 4581
Published: April 4, 2016

© 2016 American Chemical Society 4558 DOI: 10.1021/acs.chemrev.5b00715

Chem. Rev. 2016, 116, 4558−4596
Chemical Reviews Review

this remarkable class of compounds presents a vast array of

other interesting structural possibilities.9,10 In the current
review we focus beyond the highly studied CH3NH3(Pb,Sn)-
(I,Br)3 systems and explore the unusual degree of structure−
property flexibility afforded by the hybrid perovskites.
We note that there have been a number of previous reviews
on structures and properties in the halide-based perov-
skites.9−13 The current review seeks to examine recent
developments and also consider the coupling between new
structural concepts and potential applications or fundamental
new concepts. As one overarching goal for the broader
structural family, we highlight the idea of a multifunctional
organic−inorganic hybrid (Figure 1) in which unique

Figure 2. Combined ball-and-stick or skeletal (top) and shaded

polyhedral (bottom) representations of the 3-D cubic ABX3 perovskite
structure. The structure is built upon corner-sharing BX6 octahedra,
which are emphasized by cyan-shaded polyhedra, and A cations filling
the 12-fold cuboctahedral voids. A, B, and X atoms are shown as gold,
cyan, and red spheres, respectively.

extended anion. Treating all ions as rigid spheres and

considering close packing yields the Goldschmidt’s Tolerance
Factor concept,9,10,21 namely (RA + RX) = t√2(RB + RX),
where RA, RB, and RX are the ionic radii for the corresponding
ions and the tolerance factor must satisfy t ≈ 1i.e.,
empirically it is found that 0.8 ≤ t ≤ 1.0 for most 3-D
perovskites.
While it is relatively straightforward to assign ionic radii for
elemental inorganic ions, nonspherically symmetric organic
cations and charged complexes pose a greater challenge. With
the assumption of the molecule being free to rotate about its
center of mass, it becomes possible to assign effective radii for
Figure 1. Concept of the multifunctional organic−inorganic hybrid in organic cations, as shown in Table 1.22 Using t = 1 and
which unique attributes of organic and inorganic compounds are essentially the largest values for RB and RX (i.e., Shannon ionic
combined within a single material. It is envisioned that new properties radii RPb = 1.19 Å and RI = 2.20 Å),23 the limit on RA is found
could also arise as a result of the synergistic combination of the two to be approximately 2.6 Å for traditional BX3− frameworks with
components.11 B = divalent metal and X = halogen.10 Referring to Table 1, we
would expect that methylammonium and formamadinium
functionality is afforded to the composite from both the would enable a 3-D perovskite with the PbI3− or the SnI3−
organic and inorganic structural components, to create a framework, whereas ethylammonium would not. Recently,
material that ideally has greater functionality than either of the Kieslich et al. calculated the tolerance factor for over 2500
components on their own.9,11,14,15 We envision that such prospective organic cation/metal halide-based anion ABX3
materials will hold promise for a variety of applications, compounds and determined that >700 have a consistent
including micro- and nanoelectronics, battery and energy tolerance factor with the perovskite structure, with more than
storage, photocatalysis, and photovoltaics. 600 of these being unknown hypothetical compounds.24 It is
important to note that the concept of tolerance factor for ionic
2. THREE-DIMENSIONAL (3-D) ORGANIC−INORGANIC radii represents a necessary condition for the perovskite
PEROVSKITES structure, and it has had significant success in predicting new
Perovskite refers to the mineral CaTiO3 and any structure perovskite structures; however, other space-filling consider-
adopting the same ABX3 three-dimensional (3-D) structural ations also need to be considered and more refined models for
framework (Figure 2). In the case of organic−inorganic hybrid stability have been proposed.25
perovskites, at least one of the “A”, “B”, or “X” ions are organic; Besides ionic radii constraints, charge balance must also be
typically, the “A” cation is organic, while “B” is a metal and “X” achieved; that is, if the “A” cation is monovalent, then the “B”
is a halogen (Cl, Br, or I), e.g., CH3NH3PbI3 or CH- cation must be divalent if “X” is a halogen and all sites are fully
(NH 2) 2SnI3 , which employ the methylammonium and occupied. While typical examples of divalent “B” cations include
formamidinium “A” cations, respectively.16−20 Space filling Ge2+, Sn2+, and Pb2+, divalent alkaline-earth and rare-earth ions
ionic size constraints dictate whether a certain set of “A”, “B”, such as Ca2+, Eu2+, and Yb2+ can also be employed.27−29
or “X” ions may adopt the perovskite framework, which However, this valence assignment rule can be stretched with
involves a corner-sharing network of BX6 octahedra (i.e., BX3), the realization that the +2 charge on the “B” cation can be
with the “A” cations occupying 12-fold coordinated holes achieved by employing equal numbers of +1 and +3 cations (on
within the structure and counterbalancing the charge of the BX3 average yielding a +2 overall charge on this site), as is the case
4559 DOI: 10.1021/acs.chemrev.5b00715
Chem. Rev. 2016, 116, 4558−4596
Chemical Reviews Review

Table 1. Effective Radii of Molecular Cations and Anionsa ferroelectricity.34,36,38 For organic−inorganic perovskites, the
directional hydrogen bonding of the organic cation can also
Cation Effective radius rA,eff (pm)
couple through intervening halogens to the steriochemically
Ammonium [NH4]+ 146 active s2 electron pair, giving rise to a coordinated structural
Hydroxylammonium [H3NOH]+ 216 distortion, as has been discussed for the low temperature phase
Methylammonium [CH3NH3]+ 217 of CH3NH3SnBr3.36 On the other hand, a number of transition
Hydrazinium [H3N-NH2]+ 217 metal ions are also impacted by Jahn−Teller and related
Azetidinium [(CH2)3NH2]+ 250 distortions: for example, AMnO3 (A = Pr, Nd, Dy, Tb, Ho, Er,
Formamidinium [NH2(CH)NH2]+ 253 Y),39 Cs2Au2Br6,40 and KCuF3.41,42 Given the substantial size,
Imidazolium [C3N2H5]+ 258 charge, and chemistry constraints, there are only a limited
Dimethylammonium [(CH3)2NH2]+ 272 number of “A”, “B”, and “X” chemical combinations that can
3-Pyrollinium [NC4H8]+ 272 yield a 3-D organic−inorganic perovskite.
Ethylammonium [C2H5NH3]+ 274 Note that the perovskites based on metal halide frameworks
Guanidinium [C(NH2)3]+ 278 and organic cations are often referred to as “organometal”
Tetramethylammonium [(CH3)4N]+ 292 perovskitesa terminology that is misleading, since there are
Thiazolium [C3H4NS]+ 320 no metal−carbon bonds or direct linkages between metals and
Piperazinium [C4H12N2]2+ 322b organic ligands. These structures can more accurately be
Tropylium [C7H7]+ 333 referred to as “organic-inorganic” or “hybrid” perovskites.
Dabconium [C6H14N2]2+ 339b However, organic−inorganic perovskites with direct bonding
Anion Effective radius rX,eff (pm) between a metal and an organic ligand do exist,43−45 with
Fluoride 129 prototypical examples including [C(NH2)3]M(HCOO)3,
Chloride 181 where M = Mn, Fe, Co, Ni, Cu, and Zn.43 In this example
Bromide 196 (Figure 3) the guanidinium cation occupies the “A+” site in the
Iodide I− 220
Formate HCOO− 136
a
Adapted from ref 22 with permission from The Royal Society of
Chemistry. bRadii calculated from the single crystal X-ray data.26

for the semiconducting inorganic halide perovskite CsAuI3,

wherein the Au disprortionates into +1 and +3 states; that is,
the compound can more specifically be expressed as Cs2Au-
(I)Au(III)I6.30,31 Interest in the mixed-valent metal halide
perovskites further follows from the theoretical prediction32 of
superconductivity in CsTlX3, which features Tl+ (6s2) and Tl3+
(6s0) ions that are isoelectronic to Bi3+ and Bi5+ in BaBiO3. In a
recent experimental work,33 CsTlF3 was prepared as a light
brown powder that adopts a double cubic perovskite Fm3̅m
structure, whereas orange crystals of CsTlCl3 were obtained in
two different polymorphs, a tetragonal I4/m and a cubic Fm3̅m
phase. In all of these phases, charge ordering between Tl+ and
Tl3+ was confirmed to exist. Although resistivity was found to
decrease under pressure, no evidence of a phase transition to a Figure 3. Metal−organic framework (MOF) structure of [C(NH2)3]-
Tl2+ (i.e., delocalized charge) state, which would be required for Mn(HCOO)3.43 In order to show the relationship with the halide
obtaining a superconducting phase, has been observed so far. In perovskites, the oxygen atoms are drawn as red spheres in this figure;
comparison to these inorganic systems, there are only a few C, N, H, and Mn are black, sky blue, light pink, and cyan spheres,
known organic−inorganic mixed-valent perovskites, all featur- respectively.
ing lower-dimensional or 3-D defect crystal structures (see
section 3).
In addition to size and charge, there are also the details of the ABX3 perovskite framework and the formato anion takes the
bonding/coordination preferences for the metal ions involved, role of the X− anion (this time an organic anion). Examples of
which can impact the structural chemistry. For example, in the analogous structures with the guanidinium cation replaced with
related inorganic Cs2Au(I)Au(III)I6 the primary bonding other organic amines are also known.44,45 This family of
around Au(I) and Au(III) can perhaps more accurately be compounds provides a direct link between the traditional
described as square planar for Au3+ and linear for Au1+, with organic−inorganic perovskites based on metal halides and
long Au···I contacts nominally completing octahedral coordi- metal−organic frameworks or “MOFs”: a widely expanding
nation.31 In another example, the lone pair s2 electrons on B = class of compounds with potential application in catalysis, gas
Tl+, Ge2+, Sn2+, Pb2+, Sb3+, and Bi3+ may sterically interfere with storage, purification, and separation.46,47
BX6 octahedral coordination, leading to structural distortions of
the perovskite framework.22,34−37 In the perovskite structure, a 3. LOWER-DIMENSIONAL ORGANIC−INORGANIC
stereochemically active lone pair (or s-orbital hybridization) PEROVSKITES
generally gives rise to a shift of the metal atom away from the While the ABX3 structure described above has fairly rigid
crystallographic center of the metal halide octahedra, resulting structural constraints, one can explore within a broader
in alternating long and short B-X bonds and the prospects of extended family of lower-dimensional perovskites, which then
4560 DOI: 10.1021/acs.chemrev.5b00715
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Figure 4. Schematic representation of the derivation of the lower dimensional organic−inorganic perovskites (lower sections) from different cuts of
the 3-D perovskite structure (top sections). (a) The family of ⟨100⟩-oriented layered perovskites with a general formula of (RNH3)2An−1BnX3n+1 are
obtained by taking n layers from along the ⟨100⟩ direction of the parent structure. (b) Cuts along the ⟨110⟩ direction of the 3-D perovskite structure
provide the ⟨110⟩-oriented family, A′2AmBmX3m+2, which includes 1-D chain (m = 1) and 2-D layered (m > 1) members. (c) The ⟨111⟩-oriented
family, A′2Aq‑1BqX3q+3, is formed by excising along the ⟨111⟩ direction of the 3-D parent, and features 0-D isolated cluster (q = 1) and 2-D layered (q
> 1) members. In each of these layered structures, the perovskite framework is separated by a layer of typically larger organic cations.

allows for a remarkable structural tunability, i.e., from the octahedra that enable greater flexibility for the interaction
parent 3-D structure, based upon corner-shared BX6 octahedra, with interlayer organic cations.
all the way down to isolated, zero-dimensional (0-D) BX6 For the diverse family of 2-D perovskite frameworks,
octahedral clusters.9,10 Note that the dimensionality discussed although there is no definitive restriction for the length of
here refers to the connectivity of the corner-sharing BX6 the interlayer organic cations, there is a restriction for the
octahedra in the crystal structure, as conceptually excised width, which must fit into an area defined by the terminal
from the 3-D parent compound (Figure 4). As the perovskite halides from four adjacent corner-sharing octahedra. This is
structure is cut into slices, the size restrictions, as outlined by important both from the perspective of hydrogen bonding and
the tolerance factor for the 3-D structures, are gradually lifted. electron counting schemes. The charge balance requirement
For example, in two-dimensional (2-D) layered derivatives of dictates the presence of a certain concentration of cations, and
the perovskite structure, there are no known restrictions for the organic molecules that are too large (in terms of their width)
interlayer “A” cation length and, in the 0-D derivatives, size may cause steric hindrance with adjacent organic molecules,
restrictions are not applicable altogether, as MX6 octahedra are which in turn would render impossible fitting this number of
isolated and can readily shift in relative position. This structural cations into the targeted perovskite framework. However, if
flexibility and tunability of the dimensionality provide a rich and they are too narrowi.e., much smaller than the area provided
fertile “playground” for the preparation of interesting crystal by the inorganic substructurethe structure can accommodate
structures with varying physical properties. by allowing organic molecules to tilt. In summary, both the
While the size restrictions may be relaxed for the lower organic cations and the anionic inorganic framework have
dimensional perovskites, there are still other important templating influence on each other, allowing a certain degree of
parameters to consider for the successful design and synthesis control over the final structures and properties.
of a targeted perovskite-derived structure.10 The organic cation As mentioned above, lower-dimensional derivatives of the
“A” must contain terminal functional groups that can ionically perovskite structure can be obtained by making slices along
interact with the anionic inorganic substructure, but without the different crystallographic directions in the parent compounds.
rest of the organic molecule interfering with the inorganic The choice of the organic cation(s) and the reaction
components “B” and “X”. Most of the known layered (2-D) stoichiometry are among the most influential parameters on
perovskite derivatives feature mono- or diammonium cations, the orientation of the resultant inorganic frameworks. It is
yielding the general formulas of (RNH3)2BX4 or (NH3RNH3)- important to note that the dimensional reduction discussed
BX4, where here “R” represents an organic functional group. here has significant impact on the physical properties of the
The presence of ammonium cations leads to various hydrogen compounds. For example, the band gap of the compounds
bonding schemes with the anionic substructure, which are typically increases as the dimensionality of the structure is
important for determining the orientation and conformation of lowered. This is best illustrated by the example of (C4H9NH3)2-
the interlayer organic cations (see ref 10 for details). (CH3NH3)n−1SnnI3n+1 compounds, for which the parent 3-D
Depending on the choice of metal, the inorganic framework perovskite (n → ∞) CH3NH3SnI3 is a dopable small band gap
can be more or less rigid, which also influences the hydrogen semiconductor (even yielding semimetallic character), whereas
bonding schemes. For example, perovskites containing Jahn− the n = 1 compound (C4H9NH3)2SnI4 is a large band gap
Teller ions such as Cu2+ feature highly distorted CuX6 semiconductor.48 In simple terms, this can be rationalized by
4561 DOI: 10.1021/acs.chemrev.5b00715
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Figure 5. Structures of the organic cation bilayers in (C18H37NH3)2PbI4, obtained using molecular dynamics simulations, below (142 °C) and above
(272 °C) the melting transition of Tm = 182 °C.51 Reprinted with permission from ref 51. Copyright 2010 American Chemical Society.

Figure 6. Combined skeletal (top) and polyhedral (bottom, shaded) representation of the crystal structure of (C6H8N4)PbI4, which features
[PbI4]2− sheets that are separated by a monolayer of aromatic biimidazolium (C6H8N4)2+ dications.52 In the right half of the figure, the structure of a
single inorganic [PbI4]2− sheet is shown, viewed along the c-axis (i.e., top down), with the organic cations removed for clarity. The inorganic layers
are remarkably flat, with a Pb−I−Pb angle of β = 174°, and contain regular PbI6 octahedra with the I−Pb−I angles of 87.70−94.83°, and the out-of-
plane distortion of α = 2°.

the fact that the dimensionality of the inorganic framework is skites is that, unlike free lipid bilayers, since the organic cations
reduced by removing the metal “B”, which results in an increase are anchored to the inorganic perovskite lattice, the phase
in purely ionic interactions between “A” and “X”, two transitions are solid-to-solid, which allows investigations of
components with a very different set of electronegativities these transitions through a variety of spectroscopic techniques.
and, consequently, leading to a larger band gap. In the following Depending on the length of the organic chain and the nature of
subsections, we will review some of the recent reports on lower- the B-metal cation, the temperature and the order of the phase
dimensional perovskite derivatives that feature different cuts transitions observed in hybrid perovskites can be different.49 In
from the 3-D structure, including the well-known ⟨100⟩-, addition to the regular dynamic rotational disordering of the
⟨110⟩-, and ⟨111⟩-oriented families as well as more exotic ammonium functional group, the hybrid perovskites containing
possibilities. long chain organic cations undergo “melting transitions” as a
3.1. ⟨100⟩-Oriented Perovskites function of temperature, which are characterized by an
The ⟨100⟩-oriented perovskites are obtained by the ordered increased conformational disorder of the methylene units of
removal of the B-component from the inorganic framework the alkyl groups.50 This large increase in gauche conformational
along ⟨100⟩ in the ABX3 structure. Alternatively, they can be disorder results in the nonuniform distribution of the
thought of as intergrowth compounds with a general formula of orientation of the chains, and consequently, in the increase of
(RNH3)2An−1BnX3n+1, formed from the two end members: i.e., the interlayer lattice parameter. 51 Raman spectra of
the 3-D-parent ABX3 and 2-D-layered (RNH3)2BX4. The (CnH2n+1NH3)2PbI4 (n = 12, 16 and 18) above the melting
⟨100⟩-oriented perovskites currently represent the richest transition are noted to be similar to that of n-alkanes in the
subgroup of the perovskite derivative family, likely in part molten state. These spectra support the idea that, above the
because the coordination of the interlayer RNH3+ cations is melting transition, the alkyl chains of the bilayers are liquid-like
most readily accommodated in these structures. The inter- in two dimensions between adjacent inorganic layers.50
actions between organic cations and the inorganic substructure Molecular dynamics (MD) simulations were used to success-
in general, and the hydrogen bonding schemes in particular, are fully reproduce the experimental data, except for the detailed
important in the perovskite-derivative structures. The majority transition temperatures, for (CnH2n+1NH3)2PbI4 (n = 12, 14, 16
of known hybrid perovskites feature primary mono- or and 18).51 Snapshots of the simulated structures above and
diammonium cations. An interesting example involves long below the melting transition for (C18H37NH3)2PbI4 are
chain alkyl “R” groups (Figure 5). Subject to the constraint of provided in Figure 5.
lateral restrictions imposed by the metal halide layers, these can Recently, several examples of perovskites containing non-
provide a useful model system for the study of lipid primary ammonium cations have also been prepared. In
bilayers.49−51 The advantageous feature of the hybrid perov- (C6H8N4)BI4 (B = Pb, Sn),52 for example, the inorganic
4562 DOI: 10.1021/acs.chemrev.5b00715
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Table 2. Electronic and Structural Parameters for (RNH3)2SnI4 Hybrid Perovskite Semiconductorsa
exciton energy Sn−I−Sn bond angle in-/out-of-plane eq/ax Sn−I bond distortion of SnI6
amine (RNH2) (eV, nm) (deg)b distortion (deg)b length (Å)b octahedronc
4-Chlorophenethylamined 2.02, 615 157.0 22.9/<1 3.139/3.176 0.017
Phenethylamine 2.04, 609 156.5 23.5/<1 3.136/3.161 0.012
4-Fluorophenethylamine 2.04, 609 156.4 23.7/<1 3.135/3.181 0.020
2-Naphthaleneethylamined 2.06, 602 156.6 23.4/<1 3.152/3.204 0.023
3-Fluorophenethylamine 2.07, 599 154.2 25.8/<1 3.136/3.207 0.033
2-Fluorophenethylamine 2.11, 588 153.3 26.7/<1 3.149/3.178 0.013
2-Chlorophenethylamine 2.12, 586 154.8 25.2/<1 3.169/3.156 0.006
Pentafluorophenethylamined 2.17, 572 152.4 27.6/<1 3.169/3.173 0.041
2-Bromophenethylamine 2.23, 557 148.7 25.1/11.3 3.145/3.155 0.005
2- 2.23, 556 149.6 23.2/12.3 3.147/3.162 0.007
Trifluoromethylphenethylamined
1-Pyreneethylamined 2.28, 545 144.1 28.5/12.3 3.124/3.170 0.020
n-Butylamine 2.04, 607 159.6 19.4/6.4 3.136/3.160 0.011
n-Dodecylamine 2.14, 580 155.7 16.7/11.2 3.138/3.152 0.007
2-Trimethylammonioethylamine 1.97, 630 166.9 0.8/11.8 3.162/3.127 0.015
a
Adapted with permission from ref 54. Copyright 2005 American Chemical Society. bValues represent averages for each structure. cBond length
distortion is defined as ∑abs(di − ⟨d⟩)/6, where di is the summation over the six Sn−I distances and ⟨d⟩ represents the average bond length.
d
Unpublished crystal structures.

[BI4]2− sheets are separated by a monolayer of aromatic and 153.66° for (C5H11N3)PbBr4. [(CH3)3NCH2CH2NH3]-
biimidazolium (C6H8N4)2+ dications (Figure 6). The biimida- SnI4 is another compound that contains a primary and
zolium dications are sandwiched within the two adjacent nonprimary (quaternary) ammonium dication, for which the
inorganic sheets, forming a very close approach between the bridging Sn−I−Sn bond angles of 162.3 and 171.5° are
iodide anions of the inorganic layers and the aromatic rings. observed.56 Here, the weaker hydrogen bonding characteristic
Layered perovskite derivatives featuring primary ammonium of the quaternary ammonium group does not prevent the
cations tend to have distorted layers with the B-X-B angles corrugation of the inorganic sheet.
ranging from 140 to 160° (compared to 180° for undistorted The buckling of the inorganic layers and B−I−B bond angles
layers) due to the interactions between the halides of the are important not only from the fundamental chemical bonding
inorganic layers and hydrogens of the ammonium functional and crystallography points of view, but also because they
groups.53,54 In contrast, the inorganic layers are remarkably flat correlate with the band gaps of the materials. Generally, larger
in (C6H8N4)PbI4 and (C6H8N4)SnI4, as indicated by the B−I−B bond angles are observed for the narrower band gap
reported B−I−B angles of 174 and 172°, respectively. The hybrid perovskites.56,57 Theoretical studies54 suggest that the
flatness of the layers in (C6H8N4)BI4 has been attributed to the in-plane Sn−I−Sn bond angle has the greatest influence on the
nonprimary nature of the biimidazolium dications;52 however, band gap of compounds containing a SnI42− framework (up to
several structural parameters play a role in determining the 1 eV tunability), with the equatorial Sn−I bond distances also
degree of distortion. The B-X-B angles (β, Figure 6), having a significant influence (e.g., see Table 2). The degrees of
commonly used to indicate the degree of distortion of the in- and out-of-plane distortions were found to be determined
inorganic framework, can have out-of-plane and in-plane by the relative charge density and steric requirements of the
components. The former, in turn, could be due to cation− organic cations. It is important to note that, in this theoretical
anion interactions or stereochemical activity of metal cation analysis,54 structural parameters such as the in-plane (β) and
lone pairs, which is also reflected in the I−B−I bond angles out-of-plane angles (α) and bond lengths were considered, but
within a given BI6 octahedron. If the distorting influence of a the octahedral coordination around Sn2+ in the SnI42− sheets
lone pair is assumed negligiblei.e. for regular BI6 octahedra was fixed. In fact, the distortions of SnI6 also have a major
the deviation (Figure 6) of the axial B−I bonds from the impact on the band structure. For example, a recent theoretical
normal to the plane of B atoms (α) can be used as a parameter work58 on a family of A2SnI4 salts reports that, through
to evaluate the out-of-plane distortions in the structure.54 In variation of organic cations and associated structural
(C6H8N4)PbI4, the PbI6 octahedra are almost regular as shown distortions, the band gaps can be changed from 1.43 to 4.09
by the I−Pb−I angles of 87.70−94.83°, and the Pb−I−Pb angle eV (>2.5 eV tunability). In this work, the band structure
is β = 174°, with the out-of-plane component measuring α = 2°. calculations were carried out using the atomic coordinates of Sn
In addition to a lower number of H atoms available, and I determined by X-ray diffraction; that is, considered
biimidazolium dications have steric hindrance with respect to compounds have all sets of possible structural distortions,
hydrogen bonding to the BX6 octahedra. Layered ⟨100⟩- including in-plane and out-of-plane distortions, varying bond
oriented perovskites (C5H11N3)PbX4 (X = Br, Cl) feature lengths, and distortions of the SnI6 octahedra. Comparing the
histaminium cations, which contain both primary ammonium structures of two members in the A2SnI4 family, Sn−I−Sn bond
and imidazolium heads.55 As expected, the imidazolium group angles are 155.10 and 169.03° for compounds containing A =
of the organic cation has steric hindrance to hydrogen bonding; pentyl diammonium (C5di) and 3-Iodopyridinium (IPy)
however, when compared to the biimidazolium dications, cations, respectively.58 Based on these Sn−I−Sn bond angles
histaminium cations with their primary ammonium groups alone, one would expect (C5di)SnI4 to have larger band gap
strongly interact with the inorganic layers and distort them, than that of (IPy)2SnI4; however, the band gaps were calculated
with the corresponding distinct Pb−Br−Pb angles of 174.84 to be 1.43 eV for the former, and 4.09 eV for the latter.58 These
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findings are supported by the measured room-temperature

resistivities of 20 Ω cm for (C5di)SnI4 and 107 Ω cm for
(IPy)2SnI4.58 In these two compounds, while the two axial Sn−
I bonds are similar, the four equatorial Sn−I bonds are notably
different. In (C5di)SnI4, the equatorial Sn−I bonds are nearly
equal and range from 3.14 to 3.19 Å, whereas in (IPy)2SnI4,
there are two shorter (∼2.95 Å) and two much longer (3.47
and 3.66 Å) equatorial Sn−I contacts.58 In fact, the Sn−I
distance of 3.66 Å is ∼17% longer than the sum of ionic radii of
the two elements (Shannon ionic radii RSn2+ (estimated)59,60 =
0.9−0.94 Å, RI− = 2.20 Å).23 Six other members of the A2SnI4
family were also considered, and the observed band gap values
follow the above-outlined trend in the Sn−I distances and the
severe equatorial distortions of SnI6 octahedra.58 These results
further highlight the important impact that equatorial Sn−I
distances and SnI6 octahedra distortion can have on electronic
structure (in addition to Sn−I−Sn bond angle).
A convenient way of controlling the in- and out-of-plane
distortions is by employing bifunctional organoammonium
cations such as Y(CH2)2NH3+ (Y = OH, Cl, Br, I, CN) in (Y−
(CH2)2NH3)2PbI4 (Figure 7).13 A large I(CH2)2NH3+ cation
yields highly distorted perovskite layers with an in-plane Pb−I−
Pb angle of β = 147.4° in (I−(CH2)2NH3)2PbI4, but Y = Cl and
Br give relatively undistorted layers in the (Y−
(CH2)2NH3)2PbI4 series with β ∼ 178°.61 The main difference
between the structures lies in the position of the ammonium
cation heads, which are out of the perovskite layers in Y = Cl
and Br and, instead, the ethyl parts are located in the perovskite
layers, leading to a much weaker hydrogen bonding interaction.
In comparison, the ammonium functional group resides in the
perovskite layer for the Y = I compound, whereas the ethyl
parts are located out of the inorganic framework, leading to
stronger hydrogen bonding. As a result of the difference in the
hydrogen bonding and distortions of the inorganic layers, the
relatively undistorted (Y−(CH2)2NH3)2PbI4 (Y = Cl and Br) Figure 7. Crystal structures of (Y−(CH2)2NH3)2PbI4, where Y = Cl, I,
and OH.61,62 The inorganic layers are relatively undistorted in (a) Y =
have band gaps of 2.2 eV and have a distinctly more disperse
Cl, presumably because the ammonium functional groups lie outside
HOMO band compared to the highly distorted (I− of the perovskite layer. In (b) Y = I, the ammonium heads reside in the
(CH2)2NH3)2PbI4, which has a larger band gap of 2.45 eV,61 perovskite layer, leading to stronger hydrogen bonding interactions
thereby further highlighting the critical templating influence and more highly distorted layers. In (c) Y = OH, the ammonium and
that the organic cations have on the electronic properties of the ethyl parts are both located in the inorganic sheets, leading to an
inorganic framework. Another interesting finding is that, upon intermediate case between Y = Cl and Y = I.
heating (Br−(CH2)2NH3)2PbI4 at 50−150 °C, halogen
exchange between the organic and inorganic frameworks occurs attributed to the stereoactivity of the ns2 lone pair, which
yielding (Br−(CH2)2NH3)2−x(I−(CH2)2NH3)xPbBrxI4−x with manifests itself as a distortion of the BX6 octahedra and
xmax ∼ 1.85.63 originates from the mixing of the frontier HOMO (highest
In (HO(CH2)2NH3)2PbI4 (Y = OH), the CH2CH2NH3 occupied molecular orbital)−LUMO (lowest unoccupied
fragment lies within the inorganic layers, with the − OH molecular orbital) orbitals known as a second-order Jahn−
functional group also playing an active role in hydrogen Teller (SOJT) effect.38,64
bonding and with both the inorganic framework and the The SOJT effects are observed for d0 and ns2 d0 cations, and
adjacent organic cation forming supramolecular dimers.62 according to this theory, the distortions of the metal centered
Consequently, the inorganic sheets are less distorted compared BX6 octahedra lead to a stabilization of the HOMO and
to Y = I and many other PbX42−-based layered perovskites, with destabilization of the LUMO, which increases the band gap. As
β = 159.8°, but they are more distorted compared to Y = Cl a result, the HOMO of compounds containing ns2 metal cations
and Br; accordingly, the band gap was measured to be 2.31 eV feature contributions from the s orbitals, and the HOMO−
for this compound. Hydrogen bonding between the cyano and LUMO mixing leads to the stereoactivity of the lone ns2 pairs.
ammonium groups in (CN(CH2)2NH3)2PbI4 (Y = CN) also The PbI6 octahedra are distorted in (CN(CH2)2NH3)2PbI4
leads to the formation of supramolecular dimers of organic with Ieq−Pb−Ieq bond angles of 82.69−100.90° and Pb−Ieq
cations. However, in this case, ethyl fragments are located in the bond lengths ranging from 3.165 to 3.369 Å. In comparison,
inorganic layers, giving larger Pb−I−Pb angles of β = 174.64° almost regular octahedra are found in (Br(CH2)2NH3)2PbI4,
and 177.59°.13 Looking at the β angle alone, one might expect a for example, with the Ieq−Pb−Ieq angles of 88.32−91.76° and
band gap value of ∼2.2 eV, similar to that observed for Y = Cl Pb−Ieq lengths of 3.180−3.280 Å,13 which could explain the
and Br; however, the measured UV−vis data suggest a 2.34 eV lower band gap value for this compound. Together with the
band gap for (CN(CH2)2NH3)2PbI4. The difference has been variation of the functional groups in the bifunctional
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Figure 8. Combined skeletal (top) and polyhedral (bottom, shaded) view of the crystal structures of ⟨100⟩-oriented derivatives (a)
[NH3(CH2)8NH3]2[(AuII2)(AuIIII4)(I3)2] and (b) [NH3(CH2)7NH3]2[(AuII2)(AuIIII4)(I3)2], which feature strongly distorted AuI6 octahedra
(nominal) induced by the presence of mixed-valent AuI/III cations.66 In fact, each layer is made of alternating linear [AuII2]− and square planar
[AuIIII4]− units. Iodide ions that complete the elongated octahedra around the square planar [AuIIII4]− become a part of I3− ions sandwiched between
the inorganic layers. For clarity, hydrogen atoms are omitted, and the elongated Au−I contacts that complete octahedra are shown as blue dashed
lines.

ammonium cations, one can also change the length of the A2Au2I6(I3)2; therefore, in addition to the large interlayer
organic chains and, as the chain length increases in (HO- separation in the hybrid perovskites, the major difference
(CH2)3NH3)2PbI4 and [(ICmH2mNH3)2PbI4] (m = 2−6), less between A2Au2I6(I3)2 and Cs2Au2I6 is the presence of I3− ions
in-plane distortion in the inorganic layer is observed.65 in the former. Interestingly, theoretical calculations67 suggest
In addition to the organic cation-inorganic framework that the linear I3− and [AuII2]− ions are closely related and
interactions, the presence of Jahn−Teller active metal cations exchangeable. This has been demonstrated by the synthesis of
and stereoactive lone pairs, another source of structural ((CH3)3S)2[AuI4][I3], which features a structure similar to that
distortions in the perovskites is the presence of mixed-valent of Cs2Au2I6 (Figure 9); that is, linear [AuII2]− in Cs2[AuI4]-
metal cations in the inorganic framework. Hybrid organic− [AuI2] is replaced by the I3− ions.67 Another interesting finding
inorganic perovskites containing mixed-valent metal cations are is that the iodide confined in the I3− structure can be extracted,
underexplored; that is, ⟨100⟩-oriented derivatives as has been shown for [NH3(CH2)7NH3]2[(AuII2)(AuIIII4)-
[NH3(CH2)8NH3]2[(AuII2)(AuIIII4)(I3)2] and
[NH3(CH2)7NH3]2[(AuII2)(AuIIII4)(I3)2]66 are rare examples
of such systems (Figure 8). Both structures feature layers of
corner-shared AuI6 octahedra (nominal) separated by organic
cations with interlayer distances of ∼15.5 Å. Mixed-valent
AuI/III alternates in each layer as linear [AuII2]− and square
planar [AuIIII4]− units. Iodide ions that complete the elongated
octahedra around the square planar [AuIIII4]− become a part of
I3− ions sandwiched between the inorganic layers. The
structures of these two compounds are largely similar, owing
to the different conformations of the organic cations; that is,
(NH3(CH2)8NH3)2+ dications adopt a gauche conformation,
and (NH3(CH2)7NH3)2+ are in a staggered anti conformation.
This conformational difference between the cations results in
the similar cation lengths of 10.13 and 10.04 Å, respectively.
The organic cation length seems to be important in the
formation of these compounds, as layered derivatives with other
diamine homologues could not be prepared. Different
conformations are also important, as [NH3(CH2)7NH3]2-
[(AuII2)(AuIIII4)(I3)2] forms a denser organic cation-I3− layer,
which in turn leads to a greater corrugation of the inorganic
layer. The optical band gaps of [NH3(CH2)8NH3]2[(AuII2)-
(AuIIII4)(I3)2] and [NH3(CH2)7NH3]2[(AuII2)(AuIIII4)(I3)2]
were measured to be 1.14 and 0.95 eV, respectively, lower Figure 9. Combined ball-and-stick (left) and polyhedral (right,
than the reported value of 1.31 eV for Cs2AuIAuIIII6 (or shaded) view of the crystal structures of (a) ((CH3)3S)2[AuIIII4][I3]
and (b) Cs2Au2I6, i.e., Cs2[AuIIII4][AuII2].67,68 The similarity between
CsAuI3). This is unusual given that, normally, as the the two structures confirms the close relationship and exchangeability
dimensionality of a perovskite is reduced, the band gap of linear I3− and [AuII2]− ions suggested by the theoretical
increases, and Cs2Au2I6 is clearly structurally more 3-D calculations.67 The elongated Au−I contacts that complete octahedra
compared to the hybrid mixed-valent compounds. Note that, are shown as blue dashed lines, with the I-centered distorted octahedra
for the hybrid perovskites, the formulas can be written as formed by I3− ions being shown in red.

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(I3)2] by heating the compound to 85 °C, which resulted in angles of 169.84° and 173.30°. Remarkably, despite such
[NH3(CH2)7NH3]2[(AuII2)(AuIIII4)(I3)(I)]. The nominally distortions, the reported band gap values of 1.53−1.65
interchangeable nature of [AuII2]− and I3− ions, and [AuIIII4]− eV69,70,72,74 for (CH3NH3)2Pb(SCN)2I2 are low for a single
and I5− ions,67 and the unexpected changes these substitutions inorganic sheet hybrid perovskite. For comparison, the above-
bring into the electronic structures of the compounds provide mentioned (Y−(CH2)2NH3)2PbI4 (Y = Cl and Br), which
another layer of flexibility and complexity in designing feature relatively undistorted inorganic layers with Pb−I−Pb
molecular structures with desired properties. angle of ∼178°, have the lowest band gap value of 2.2 eV in this
Recently, another linear ion, the thiocyanate SCN− anion, series;61 yet, these values are still much larger than the reported
has been attracting the interest of photovoltaics (PV) and solid values for (CH3NH3)2Pb(SCN)2I2. In addition, early theoreti-
state chemistry communities.69−72 It was found that incorpo- cal work on (CH3NH3)2Pb(SCN)2I2 indicated that the valence
ration of a small amount of Pb(SCN)2 (5 wt %) into the regular and conduction bands remain fully dispersive along all three
two-step solution deposition of CH3NH3PbI3 films resulted in dimensions,73 a surprising finding given the layered nature of its
better film qualities with larger grain sizes, which resulted in crystal structure. A more recent combined theoretical and
improved power conversion efficiencies (PCE).71 A small ∼80 experimental evaluation75 of (CH3NH3)2Pb(SCN)2I2 suggests
meV increase of the optical band gap and a noticeable that there is almost no dispersion for the states near the
enhancement in the photoluminescence emission quantum conduction band minimum (CBM) and valence band
yield have been reported upon larger incorporation of SCN− maximum (VBM) along the interlayer direction (i.e., T-R
into CH3NH3PbI3, using Pb(SCN)2:CH3NH3I ratios ranging direction in the electronic band structure) and that the band
from 1:1 to 1:5.70 Finally, solar cells with a targeted gap value of the material is actually closer to 2 eV, a more
CH3NH3Pb(SCN)2I composition showed similar PCE values consistent value with the reported red coloration of the crystals
to the CH3NH3PbI3 films, but the films containing thiocyanate and films.69,74,75 Despite the ongoing uncertainty regarding the
ions were reported to provide enhanced stability under moist properties of (CH3NH3)2Pb(SCN)2I2, preparation of a low
air.72 In all of these studies, the authors assumed that the band gap layered hybrid perovskite material is an important
incorporation of SCN− ion takes place through a direct target for potential electro-optical applications (e.g., in solar
substitution of I− ionhence, the “pseudohalide ion” term cells, transistors), because of the likely simpler deposition of
used for the thiocyanate ion in these publications. Unlike the high quality films of layered materials, and the added flexibility
linear I3− ion, however, SCN− is asymmetric, which raises a that the layered structure provides for further chemical and
question regarding the exact bonding pattern and orientation of crystallographic manipulation.
the thiocyanate ion in the 3-D perovskite structure. In fact, one Note that, to this point in this section, we have primarily
possible scenario is that the targeted 3-D perovskite been discussing how the organic cation or choice of halogen (or
CH3NH3Pb(SCN)2I phase does not exist and, instead, crystals pseudohalogen in the “X” site) can impact or template the
of a ⟨100⟩-oriented layered compound (CH3NH3)2Pb(SCN)2I2 distortion of the inorganic metal halide framework. However,
form (Figure 10), as recently confirmed by repeating the the templating influence of the organic cation can also enable
previously reported reaction conditions.69,73,74 the demonstration of layered perovskites with a broader range
of “B” cations than would otherwise be possible, as has been
demonstrated for the (H2AEQT)B2/3I4 (AEQT = 5,5‴-
bis(aminoethyl)-2,2′:5′,2″:5″,2‴-quaterthiophene; M = Bi3+ or
Sb3+) compounds.76 In these particular compounds, the
inorganic perovskite sheets feature a random distribution
of B-metal cations over available sites, which have occupancy
of 2/3 due to the charge balance requirements following
(H2AEQT2+)(B3+)2/3(I−)4. Given the vacancies, the perovskite
structure has to compete against other non-perovskite
structures with no vacancies and, in fact, Bi-based halides
with simple ammonium cations often prefer non-perovskite
alternatives.13 In (H2AEQT)B2/3I4, the perovskite structure is
stabilized through the rigid, rod-like nature of the H2AEQT2+
cations and edge-to-face aromatic interactions among these
quaterthiophene moieties (further discussion of oligothio-
phene-based perovskites can be found in Section 4).76
In the regular definition of ⟨100⟩-oriented perovskite
Figure 10. Combined skeletal (top) and polyhedral (bottom, shaded) derivatives, this group includes only 2-D-layered compounds
view of the crystal structure of (CH3NH3)2Pb(SCN)2I2, featuring with the single sheet (RNH3)2BX4 as the end member;
SCN− anions on axial and I− anions on equatorial positions.69 however, (RNH3)2BX4 can also be further cut into 1-D chain
segments and isolated octahedral 0-D clusters (note that these
0-D and 1-D compounds can also be considered end-members
In (CH3NH3)2Pb(SCN)2I2, SCN− ions coordinate to the of ⟨111⟩- and ⟨110⟩-oriented perovskite families, respectively,
inorganic layer through Pb−S contacts and occupy axial as will be discussed in the following sections). This can occur
positions in the Pb-centered octahedra, extending out in a when the width (cross-sectional area) of the organic cation is
bent fashion with the corresponding Pb−S−CN angle of too large (>40 Å2), as shown in the series of (RNH3)2PbX4 (R
103.5°. The Pb-centered octahedra are distorted, with the I− = cycloalkylammonium; X = Cl, Br, I) (Figure 11).77,78 The
Pb−I and I−Pb−S angles ranging from 81.63° to 98.49°. The ⟨100⟩-oriented layered (RNH3)2PbX4 perovskites are obtained
in-plane distortions are modest but apparent with Pb−I−Pb if small ring organic cations, from r = 3 (cyclopropylammo-
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Figure 11. Crystal structures of (RNH3)2PbI4 compounds, where (a) R = cyclohexylammonium, and (b) R = cycloheptylammonium.77,78 The
⟨100⟩-oriented layered perovskites are obtained if small ring organic cations from r = 3 (cyclopropylammonium) to r = 6 (cyclohexylammonium) are
used, whereas r = 7 (cycloheptylammonium) features inorganic 1-D chains of corner-sharing octahedra. Only a fraction of cycloalkylammonium
cations are shown for clarity.

Figure 12. Crystal structures of the (a) 2-D layered α-[(NH3(CH2)2SS(CH2)2NH3)PbI4] and (b) 1-D chain [(NH3(CH2)2SS(CH2)2NH3)2PbI5·I]
compounds, a mixture of which is obtained from the same reaction.65

nium) to r = 6 (cyclohexylammonium), are used; however, r = 3.2. ⟨110⟩-Oriented Perovskites

7 (cycloheptylammonium) gives 1-D chains of corner-sharing The ⟨110⟩-oriented perovskites, A′2AmBmX3m+2, are less
octahedra in (C7H13NH3)3PbI5 and (C7H13NH3)3PbBr5· common compared to the ⟨100⟩-oriented perovskites, and
H2O.77,78 It should be noted that large cross-sectional area have been mostly limited to compounds obtained using the
organic cations or a geometry that provides steric hindrance are structure-directing iodoformamidinium cation. The special role
not essential for obtaining 1-D compounds. An uncontrolled of the iodoformamidinium cation in the [NH2C(I)NH2]2-
reaction can give a mixture of compounds with differing (CH3NH3)mSnmI3m+2 series80 includes formation of hydrogen
dimensionality for the same cation, such as in the case of 2-D bonds down the channels of the ⟨110⟩-oriented perovskite
layered α-[(NH3(CH2)2SS(CH2)2NH3)PbI4] and 1-D chain layers, and the fact that the iodine atoms of the
[(NH3(CH2)2SS(CH2)2NH3) 2PbI5·I] compounds (Figure iodoformamidinium cation complete the 12-fold coordination
12).65 These compounds were serendipitously obtained using environment around the methylammonium cation. The known
HSC2H4NH2·HCl as a reactant, with the diprotonated m = 1−4 members of the [NH2C(I)NH2]2-
cystamine cation (NH3(CH2)2SS(CH2)2NH3)2+ forming in (CH3NH3)mSnmI3m+2 series include the m = 1, 1-D-chain
situ. Interestingly, the obtained structures are very similar to the structures [NH2C(I)NH2]2ASnI5 (A = NH2C(I)NH2+ or
structures of 2-D layered (cyclohexylammonium)2PbI4 and 1-D NH2CHNH2+), and the m = 2, 2-D-layered structure
chain (cycloheptylammonium)2PbI4 compounds (Figure 11); [NH2C(I)NH2]2(CH3NH3)2Sn2I8.10,80 As m is increased
however, 2-D layered α-[(NH3(CH2)2SS(CH2)2NH3)PbI4] further, the thickness of the perovskite layers also increases,
and 1-D chain [(NH3(CH2)2SS(CH2)2NH3)2PbI5·I] feature with m = ∞ corresponding to the 3-D parent perovskite
identical cations. The difference can presumably be attributed structure. Therefore, this ⟨110⟩-oriented family allows tuning of
to the incorporation of large iodine anions in the 1-D chain the dimensionality of the perovskite structure from the 3-D
[(NH3(CH2)2SS(CH2)2NH3)2PbI5·I] compound, and the parent structure to various-thickness 2-D layers in the m = 2−4
subsequent fragmentation of the layers into chains. By heating members, and to 1-D chains in the m = 1 member.
at 150 °C, 2-D layered α-[(NH3(CH2)2SS(CH2)2NH3)PbI4] The Pb-analogs of the m = 1 members have been synthesized
can further be transformed into its β-polymorph, which is as well, and this demonstrates that the ⟨110⟩-oriented
retained down to 40 °C, indicating a large window of compounds can also be prepared using other metal cations.81
coexistence for these polymorphs.79 The β-polymorph features In addition, another m = 1 compound, [CH3SC(NH2)-
disordered diprotonated cystamine cations in the structure.79 NH2]3PbI5, has been reported, showing that other organo-
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ammonium cations can template this structure.82 However, the monium head, which is capable of templating a perovskite
highly distorted inorganic framework of this compound can structure, and a ternary ammonium cation in the ring, which
also be described as an assembly of loosely coupled 0-D asserts steric hindrance for the formation of a perovskite
clusters;10 as such, a genuine ⟨110⟩-oriented perovskite with framework. Without this combination of somewhat conflicting
other organic cations has remained somewhat elusive. A characteristics, the more symmetric biimidazolium (C6H8N4)2+
breakthrough in this regard has been made with the discovery dications give the common ⟨100⟩-oriented structures in
of the m = 2 ⟨110⟩-oriented perovskite diguanidinium (C6H8N4)PbI4 and (C6H8N4)SnI4 (see Section 3.1). The
tetraiodoplumbate, [C(NH2)3]2PbI4, which, interestingly, substitution position on the heterocylic ring and the length of
undergoes a ferroelastic phase transition at 307 K.83,84 At the alkylammonium chain is also important, as (C5H11N3)-
higher temperatures, cationic disordering and the deformation PbBr4 and (C5H11N3)PbCl4 featuring histaminium cations also
of the inorganic sublattice are coupled in this compound. The adopt the ⟨100⟩-oriented perovskite structures (see Section
authors note that the organic cation’s size, shape and symmetry 3.1). The fact that subtle differences in the organic cations in
are all influential in the observed physical properties in (C5H11N3)PbBr4 and (C6H13N3)PbBr4 lead to the ⟨100⟩-
[C(NH2)3]2PbI4.83 Another example of the m = 2 ⟨110⟩- oriented and the ⟨110⟩-oriented inorganic perovskite frame-
oriented perovskite is (C6H13N3)PbBr4 (or (C6H13N3)2- works, respectively, underlines the importance of fine details in
Pb 2 Br 8 ), which is stabilized by a N-(3-aminopropyl)- the structural preferences exhibited among the oriented
imidazolium (API) cation (Figure 13).85 API, as a substituted perovskite derivatives.
In (C6H13N3)PbBr4, the presence of the API dication
simplifies the structure and composition compared to the
previously known m = 2 members such as [NH2C(I)
NH2]2(CH3NH3)2Sn2I8, which feature 2 distinct cation sites, a
smaller intralayer CH3NH3+ cation site and the larger interlayer
NH2C(I)NH2+ site. Here, in addition to carrying +2 charge,
API accepts dual functionality, combining the roles of
CH3NH3+ and NH2C(I)NH2+ cations. The [PbBr4]− layers
in (C6H13N3)PbBr4 are corrugated, with the Pb−Br−Pb angles
of 162.68 and 171.85°, and the PbBr6 octahedra are distorted
with Br−Pb−Br angles ranging from 86.35 to 96.42°. The latter
suggests that the Pb lone ns pair is relatively stereochemically
active in this compound. As a final thought for this section, the
stabilization of multiple m = 2 members of the ⟨110⟩-oriented
perovskites demonstrates that this family is accessible with
organic cations other than the iodoformamidinium cation. For
example, (C3H11SN3)PbBr4 is stabilized by diprotonated 2-
(aminoethyl)isothiourea.86 In this case, the organic cation
combines a primary ammonium and a formamidinium head on
the two opposite ends of the molecule. The use of such organic
cations leads to contorted inorganic layers with Pb−Br−Pb
angles of as low as 144.23° in (C3H11SN3)PbBr4. The family of
Figure 13. Combined skeletal (top) and polyhedral (bottom, shaded) ⟨110⟩-oriented perovskites has been further expanded by the
view of the crystal structure of (C6H13N3)PbBr4 viewed down the a-
recent synthesis of several new m = 2 members with a potential
axis.85 The ⟨110⟩-oriented perovskite layers are separated by the N-(3-
aminopropyl)imidazolium (API) dications, which feature a propylam- for application in solid-state lighting applications (see section 7,
monium head and a ternary ammonium cation in the ring. Figure 33).87,88
3.3. ⟨111⟩-Oriented Perovskites
imidazole derivative, is an optically active material featuring a The cyclohexylammonium cation appears to be the largest ring
primary amine as a functional group attached to the imidazole cycloalkylammonium cation that allows formation of the ⟨100⟩-
heterocyclic ring. The resultant dication features a propylam- oriented 2-D-layered (RNH3)2PbX4 perovskites (see section

Figure 14. (a) Crystal structure of (H22-AMP)PbBr4 features ⟨100⟩-oriented inorganic 2-D-sheets and 2-(aminomethyl)pyridinium (H22-AMP)2+
cations sandwiched in between the layers. In contrast, 3-(aminomethyl)pyridinium (H23-AMP)2+ and 4-(aminomethyl)pyridinium (H24-AMP)2+
cations give (b) ⟨111⟩-oriented 0-D-clusters and (c) 1-D-chains formed by edge-sharing octahedra in (H23-AMP)2PbBr6 and (H24-AMP)PbBr4,
respectively.89 For clarity, only a fraction of organic cations are shown.

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Figure 15. (a) Crystal structure of the ⟨111⟩-oriented layered perovskite [NH(CH3)3]3Sb2Cl9 viewed down the b-axis.97 Use of larger organic
cations (e.g., N(CH3)4+) leads to a further fragmentation of the layers into 0-D clusters. (b) Crystal structure of [N(CH3)4]3Sb2Cl9, featuring
Sb2Cl93− dimers made of two SbCl6 face-sharing octahedra.95

3.1, Figure 11). Interestingly, six-membered rings seem to carry mentioned (H23-AMP)2PbBr6, mixed-valent [N(CH3)4]2-
similar influence for the compounds formed using aromatic SbIII0.5SbV0.5Cl6, and [N(C2H5)4]2SbIII0.5SbV0.5Cl6 may be rare
heterocyclic cations. By changing the position of the amino- examples of q = 1 members with larger organic cations;
methyl group on the six-membered pyridine ring, Li et al. however, no detailed structural data are available for these
synthesized 2-(aminomethyl)pyridinium (H22-AMP)2+, 3- compounds.93
(aminomethyl)pyridinium (H23-AMP)2+, and 4- Similarly, the known q = 2 members, including (NH4)3Sb2I9,
(aminomethyl)pyridinium (H24-AMP)2+ cations, which were (CH 3 NH 3 ) 3 Bi 2 Br9 , [NH 2 (CH 3 ) 2 ] 3Sb 2 Cl 9 , [NH(CH 3 ) 3 ] 3 -
subsequently used to obtain perovskite structures of different Sb2Cl9, and (CH3NH3)3Sb2I9, to name a few, also feature
dimensionality under similar experimental conditions.89 The small organic cations.94−98 The inorganic q = 2 compounds,
resultant compounds (H22-AMP)PbBr4, (H23-AMP)2PbBr6, which crystallize in the α-Cs3Sb2Cl9 structure type, feature Cs+
and (H24-AMP)PbBr4 feature ⟨100⟩-oriented 2-D layers, and Rb+ cations.91,98 Recently, Cs3Sb2I9 has been examined as a
⟨111⟩-oriented 0-D clusters, and 1-D-chains formed by edge- prospective Pb-free perovskite for use in PV devices.99 In
sharing octahedra, respectively (Figure 14). Although the addition to strong absorption for wavelengths above the band
substituted pyridinium dications used for these compounds are gap, due to the p-like character of both the valence band and
isomers, the subtle differences in the structures of the cations conduction band edges, and relatively small effective masses for
are sufficient to induce large differences in their steric hindrance both electrons and holes, one interesting feature of the band
and hydrogen bonding capabilities. It is somewhat unexpected structure of this material is that the bands appear to be
that the ⟨100⟩-oriented layered (H22-AMP)PbBr4 and ⟨111⟩- reasonably dispersive both parallel and perpendicular to the
oriented 0-D cluster compound (H23-AMP)2PbBr6 have similar plane of the perovskite layers, indicating that the layered nature
band gap values of ∼2.8 eV. One normally would expect a of these systems may not handicap them too much for use in 3-
larger band gap value for the metal poor isolated 0-D D PV devices. Although initial device performance has been
compound; however, one of the reasons for the close band low for Cs3Sb2I9, this early device result shows the possibility of
gap values may be due to the SOJT effect (or stereochemical using these ⟨111⟩-oriented layered perovskites in functional
activity of the Pb lone pair states). The Br−Pb−Br angles range electronic devices.
from 88.73 to 97.63° in the layered (H22-AMP)PbBr4, and Two interesting features are common in all of the known q =
from 86.62 to 93.38(2)° in (H23-AMP)2PbBr6, indicating the 2 members so far: (1) the metal cations are trivalent
presence of the more distorted PbBr6 octahedra in the former, pnictogens, and (2) there is only little difference between the
which should lead to an increased band gap. thickness of the single inorganic sheet and the interlayer
The compositions of the ⟨111⟩-oriented perovskites are distance. The former is due to the simple fact that, for a
given by the A′2Aq‑1BqX3q+3 formula, where A′ and A are structure with monovalent A+ cations, in order to balance the
interlayer and intralayer organic cations. (H23-AMP)2PbBr6 charges, B must be trivalent in the (A + ) 3 (B 3+ ) 2 (X − ) 9
provides an example of the most common q = 1 member of composition. The small interlayer distance is due to the small
the ⟨111⟩-oriented perovskites, which belong to the cubic sizes of the interlayer organic and inorganic cations and, as
K2PtCl6-type structure with a great many known members. The such, these compositions could have also adopted Sb(Bi)-
K2PtCl6-type structure is adopted, for example, by Cs2SnI6, deficient 3-D perovskite structures with a random distribution
which has recently been used as a hole conductor in a solar cell of vacancies. This conjecture is supported by the fact that
device,90 and A2TeX6 (A = NH4+, K+, Rb+, Cs+, Tl+; X = Cl−, cations such as CH3NH3+ can be incorporated into the 3-D
Br−, I−),91,92 featuring Te4+, which is isoelectronic to for perovskite structure, as evidenced by the well-known photo-
example Sn2+ and Pb2+. Since the extended inorganic voltaic material CH3NH3PbI3. Another supporting evidence is
framework is absent in this structure, no clear organic cation that the Sb and Bi vacancies can also be disordered in the
size restrictions can be outlined for q = 1 members, and the ⟨100⟩-oriented layered perovskite framework, as demonstrated
structure should, in principle, be able to accept a wide range of by the above-mentioned (H2AEQT)B2/3I4 compounds76 that
components as long as the charge balance is preserved. feature random distributions of Sb and Bi vacancies in the
However, the majority of the known q = 1 members feature perovskite layers. The preference for forming the q = 2 member
only relatively small cations. In addition to the above- of the ⟨111⟩-oriented A3B2X9 perovskites with a small A+ cation
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(as opposed to a disordered 3-D perovskite), therefore, could

be attributed to a greater stability of this structure (i.e.,
thermodynamic sink) in the energy landscape of the perovskite
compounds.
In principle, there should be no constraints for the interlayer
A′ cation length for the q = 2 members of the ⟨111⟩-oriented
perovskites, if the intralayer “A” site is populated with smaller
cations. However, no q = 2 members with two very different
cations have been reported to date. The q = 2 perovskite
structure collapses when the size of the organic cation is too
big. For example, [NH(CH3)3]3Sb2Cl9 adopts the layered
⟨111⟩-oriented perovskite structure,97 while [N(CH3)4]3Sb2Cl9
features Sb2Cl93− dimers made of two SbCl6 face-sharing
octahedra (Figure 15).95 In this particular example, the
hydrogen bonding abilities of [NH(CH3)3]+ and [N(CH3)4]+
cations are quite different, which may also contribute to the
difference in the observed structural preference. Notwithstand-
ing this fact, we observe that the dimer structure is a competing
phase for many of the q = 2 members, and for compounds such
as Cs3Sb2I9 and (CH3NH3)3Sb2I9, this polymorph is obtained
from solution, whereas the layered modification may be
obtained from solid state or gas phase reactions.98,99 This is
an important observation, as solution synthesis has been the
most common method for the preparation of the perovskite
derivatives. The very high stability of the dimer and the ⟨111⟩-
oriented q = 2 A3B2X9 structures with small A+ cations is
therefore a stumbling block for the preparation of the q = 2
members with two cations of different sizes (A′+ and A+) and
higher order q > 2 members of the ⟨111⟩-oriented series
A′2Aq‑1BqX3q+3. Note that, assuming A′ and A are monovalent
organic cations, the A′2Aq‑1BqX3q+3 formula of the ⟨111⟩-
oriented perovskites requires different metal B cation oxidation Figure 16. In the crystal structure of α-[NH3(CH2)5NH3]SnI4,100 the
states for each q member (in contrast to the ⟨100⟩ and ⟨110⟩ inorganic layers are composed of 4-octahedra long ⟨100⟩-oriented
layer fragments that are interconnected at 45° angles. The resultant
families). In the q = 1 member A2BX6 and q = 2 member zigzag perovskite layers are a combination of the ⟨100⟩-and the ⟨110⟩-
A3B2X9 (A = monovalent cation; X = halide), B is tetravalent oriented fragments that are separated by 1,5-pentanediammonium
and trivalent, respectively, and the parent q = ∞ member ABX3 cations.
features divalent B. This complicates the synthesis of the ∞ > q
> 2 members, because, unless a mixture of organic ammonium
and diammonium cations were to be used, the oxidation state oriented layer fragments that are interconnected at 45° angles
on the B cation must be fractional, i.e. between +2 and +3, and to form a zigzag morphology. Although, the crucial role of a
a mixture of two or more B-cations (or oxidation states for a CH3NH3+ cation in the preferential formation of the α-phase
single B-cation) is necessary. was attributed to a possible formation of CH3NH3SnI3
3.4. More Exotic Frameworks perovskite and subsequent more irregular fragmentation of
the 3-D structure, the detailed formation mechanism still needs
Owing to its flexibility and ease of manipulations, the perovskite to be resolved.
structure offers endless possibilities. Although much has been The fact that the reaction conditions in general, and the
accomplished in terms of syntheses and characterization of addition of uncommon reactants in particular, can influence the
perovskite derivatives, there are a lot of questions remaining way in which the perovskite structure is fragmented can also be
unanswered. The role of “spectator” ions (i.e., species that are exemplified by the 2-D staircase [Pb4I18]10− sheets in
added to the reaction medium but do not feature in the final [(H2en)7(C2O4)2][Pb4I18]·4H2O, where en = ethylendiamine
compound in a measurable concentration), for example, (Figure 17).101 This compound is obtained by a solvothermal
remains under-explored. The fact that foreign chemical species reaction of PbI2, K2C2O4·H2O, and en in a concentrated HI and
can have an important role can be illustrated with the example ethanol solution. The authors note the importance of reaction
of α-[NH3(CH2)5NH3]SnI4, which features zigzag perovskite conditions, including pH ∼ 1 and the K2C2O4·H2O reactant,
layers that are separated by 1,5-pentanediammonium cations which cannot be replaced by H2C2O4. The C2O42− anions play
(Figure 16). Under regular synthetic conditions, the β-phase a pivotal role in the formation of the structure, as they are
containing ⟨100⟩-oriented SnI42− layers is formed, whereas the incorporated with organic cations (H2en)2+ forming supra-
α-phase is obtained when CH3NH3I is added to the reaction molecular assemblies of distinct shapes. The resultant nominal
medium.100 The zigzag perovskite layers of the α-phase, which cationic layer [(H2en)7(C2O4)2]10+ plays, not only a cotemplat-
feature trans- and cis-shared SnI6 octahedra, can be seen as a ing role, but also necessitates an unprecedented charge of −10
combination of the ⟨100⟩-and the ⟨110⟩-oriented layers. In an in the inorganic [Pb4I18]10− sheets. Four PbI6 octahedra share
alternative description of the α-[NH3(CH2)5NH3]SnI4 struc- corners to form tetrameric Pb4I20 building blocks, and these
ture, the layers are composed of 4-octahedra long ⟨100⟩- tetramers further share corners in a staircase fashion to form
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Figure 17. Crystal structure of [(H2en)7(C2O4)2][Pb4I18]·4H2O, featuring staircase [Pb4I18]10− layers built upon corner-sharing tetrameric Pb4I20
units (right).101 Water molecules are not shown for clarity.

the anionic [Pb4I18]10− layers in the structure. The Pb−I−Pb

bond angles of 176.04 and 180.0° are among the highest in the
lead iodide based perovskites, indicating only negligible in-
plane distortions in the structure. The ammonium functional
groups are pointing out of the inorganic layers, toward the
C2O42− anions and, therefore, with only ethyl groups in the
inorganic sheets, the hydrogen-bonding interactions are weak in
this compound. [(H2en)7(C2O4)2][Pb4I18]·4H2O is reported as
a direct band gap semiconductor with an optical band gap of
2.47 eV.

4. FUNCTIONAL ORGANIC CATIONS

Besides basic structural flexibility, organic−inorganic hybrids
enable the combination of useful properties from both the
organic and inorganic chemical palette within a single
molecular-scale composite (e.g., as seen in Figure 1). While
in the above discussion in Sections 2 and 3, for the most part,
the organic cation is playing solely a structural role in Figure 18. Combined skeletal (top) and polyhedral (bottom, shaded)
determining the properties of the full compound, there are view of the crystal structure of AEQTPbBr4, where AEQT = 5,5‴-
now numerous examples wherein the organic cation is more bis(aminoethyl)-2,2′:5′,2‴:5″,2‴-quaterthiophene, consisting of self-
functional (e.g., larger degree of conjugation provides a smaller assembling and ordered organic and inorganic layers.102
HOMO−LUMO separation), therefore enabling a more active
role in the optoelectronic properties of the solid. that interaction between the organic and inorganic structural
A prototypical example, and one of the first in which the components occurs in the hybrid.102,104 One model for the
crystal structure and optoelectronic properties of the photoluminescence quenching observed for AEQTPbX4 as X
compound were analyzed, involved the design and incorpo- transitions to higher atomic number metal halides may be
ration of 5,5‴-bis(aminoethyl)-2,2′:5′,2″:5″,2‴-quaterthio- viewed in light of energy or charge transfer between
phene (AEQT) into a ⟨100⟩-oriented layered lead(II) halide components of the structure (Figure 19).102
perovskite framework (Figure 18).102 Oligothiophenes are Efficient Förster resonant energy transfer between more
particularly useful for electronic structure engineering studies extended Wannier-type excitons from inorganic semiconductor
because the HOMO−LUMO separation can readily be tailored quantum wells and optically active organic molecules in a
relative to the band gap of the inorganic component of the nearby medium (i.e., conversion of Wannier to molecular
structure by changing the length of the thiophene chaini.e., excitations or Frenkel excitons) has been predicted106,107 and
with “n” representing the number of α-linked thiophene rings observed,108 when there is strong spectral overlap between
within the chain, the absorption peak associated with the donor emission and acceptor absorption spectra. While Förster
HOMO−LUMO separation varies from between approx- resonant energy transfer involves energy transfer through
imately 302 nm (4.1 eV) for n = 2 to 432 nm (2.9 eV) for n nonradiative dipole−dipole coupling and is inversely propor-
= 6.103 The quaterthiophene (n = 4) molecule, with its ∼3.2 eV tional to the sixth power of the distance between the donor and
HOMO−LUMO separation, perfectly intersects the band gap acceptor, Dexter charge transfer processes involve the non-
range offered for the lead(II) halide perovskite sheet, as often radiative transfer of an excited electron from one species to the
monitored by the associated exciton absorption peak−i.e., other and has a stronger exponential decay with separation.
approximately 330 nm (3.8 eV) for X = Cl, 400 nm (3.1 eV) for Ema et al. have demonstrated near perfect Dexter-type triplet−
X = Br and 500 nm (2.5 eV) for X = I. Strong triplet energy transfer between the Wannier excitons in
photoluminescence from the AEQT molecule in the X = Cl inorganic PbBr42− perovskite layers and naphthalene molecules
structure and quenching of this luminescence for X = I suggests in the organic layer, with demonstrated exponential depend-
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well (QW), then perhaps the organic and inorganic

components can be selected such that they will enable tuning
between a type I quantum well system and type II. Indeed, for
the AEQTPbX4 hybrid discussed earlier, for X = Cl wherein the
band gap is significantly larger than the HOMO−LUMO
separation of the organic molecule, the lowest energy state for
both electrons and holes may be on the organic cation layer. In
contrast, as the halide is shifted from X = Cl to Br and I, the
Figure 19. Prospective schematic energy level diagrams for the valence band is expected to shift up116 and the lowest energy
(AEQT)PbX4 system with (a) X = Cl and (b) X = I, as determined
state for electrons and holes may then be on different
from the absorption data and literature values for the triplet state
(T1).105 The relevant energy levels include the singlet (S1) and T1 components of the structure. Photoluminescence quenching
states for the organic molecule (note that the cyan box above the S1 of the AEQT molecule in the X = I structure is consistent with
state corresponds to the vibronic progression and higher lying states this model. An important area for further exploration involves
for the organic molecule) and the exciton band (EB) for the inorganic understanding the extent to which this analogy to organic−
framework. GS refers to the ground state for each of the transitions. inorganic QW structures (Figure 21) can be taken, given the
The transitions in (b) that are indicated with the dotted lines are either
not observed (EB → GS) or only weakly observed (S1 → GS). The
zigzag lines correspond to possible nonradiative transitions. The
conduction and valence bands for the lead(II) halide framework have
not been included in the diagram for the sake of clarity. Note that the
spacing between energy levels has not been drawn to scale.102

ence on separation distance, as controlled by the length of the

tethering alkylammonium group linking the naphthalene
moiety to the inorganic layers.109 A number of other examples
in which energy/charge transfer between organic and inorganic
components of the perovskite structure have been explored
include naphthalene and pyrene derivatives within lead(II)
halide frameworks,110−112 3-2-(aminoethyl) indole (C8NH6−
CH2CH2NH2) incorporated in a CuCl42− framework;113
azobenzene associated with CdBr42−,114 mixtures of organic
cations (chromophore and nonchromophore) within a PbBr42−
framework,115 and ⟨110⟩-oriented structures stabilized by n-(3-
aminopropyl)imidazole.85 Such studies involving quaterthio-
phene, naphthalene and related aromatic organic components
display the unique flexibility of the organic−inorganic perov- Figure 21. Several possible energy level schemes for the alternating
skites to allow electronic tunability of both organic and organic−inorganic perovskite structure, highlighting the prospective
inorganic species to create a cooperative response. Optical analogy (still to be confirmed) with multilayer quantum-well (QW)
properties of such complex systems and the properties of structures. The structures represent (a) type I QW structures in which
excitons in these structures will be further explored in Section the organic layer has a much wider HOMO−LUMO separation than
7. the corresponding band gap for the inorganic layer, (b) type I QW
An alternate vision for this type of structure can be found in structures in which the roles of the organic and inorganic layers are
Figure 20.11 Namely, if we view the organic−inorganic reversed, and (c) type II QW structures.11
perovskite structure as a self-assembling multilayer quantum
combination of highly disparate organic and inorganic moieties
and the short length-scales involved. Even et al. show that, for
ultrathin layers, the effective mass model may fail due to the
absence of superlattice coupling and importance of non-
parabolicity, and they propose an alternative model based on
concepts from composite materials.117,118
Inclusion of more complex and larger organic moieties has
also been attempted with other motivations in mind. One
example involves the incorporation of metal-containing clusters
as part of the organic cation. In [Cu(O2C−(CH2)3−NH3)2]-
PbBr4, incorporation of Cu2(CO2)4 “paddle-wheel” clusters,
Figure 20. Proposed scheme to describe the energy level configuration can be accomplished using amino carboxylic acid zwitterionic
of the (a) AEQTPbCl4 and (b) AEQTPbI4 compounds. The relevant molecules, with the anionic part of the molecule complexing to
energy levels include the singlet S0 and S1 states for the chromophore
and the valence band (VB), conduction band (CB), and exciton band
the metal and the cationic part serving to tether onto the
(EB) states for the lead(II) halide sheets. For clarity, the triplet level PbBr4−2 sheets.119 The coordinated metal clusters constitute
(T1) has not been included in the chromophore energy level scheme. “secondary building units” (SBUs) and have been used to
Note also that, to draw this diagram, we have arbitrarily chosen an design porous metal−organic frameworks (MOFs).120 One
offset energy between the chromophore S1 edge and the inorganic special structural feature is that the terminal ligands of the
conduction band edge (CB).102 Cu2(CO2)4 moiety are coordinated by apical bromines from the
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PbBr42− sheets, thereby creating Br−Cu−Cu-Br covalent tight prospective fit within the layered perovskite structure
linkages between nearest-neighbor perovskite layers (Figure (Figure 24). On the other hand, there may be the possibility of
22) and increasing the effective dimensionality of the material

Figure 24. Picture showing four nearest neighbor PbI6 octahedra

sharing corners and the distance between cavities for the organic
cation.122 This proposed structure remains to be confirmed with the
fullerene-based cations. Reprinted with permission from ref 122.
Copyright 2005 Elsevier.

diluting it with long-chain alkylammonium cations to improve

the fit.122 Also, the organic cation is doubly protonated, and it
may therefore be, from a charge balance point of view,
accommodated in the space allotted for two cations from the
proto-typical (R-NH3)2PbI4 structure, in which the cations are
monoprotonated. It will be of great interest when the crystal
structures of the proposed (AmPF-I2)PbI4 hybrids become
Figure 22. (a) Polyhedral representation of the [Cu(O2C−(CH2)3−
NH3)2]PbBr4 structure showing the connection of copper clusters to available to confirm the structure type. In the meantime, it is
adjacent PbBr6 octahedra. Except for two −O2C−(CH2)3−NH3+ important to realize that observation of a layered structure is
molecules, the propylammonium units have been removed for not, in itself, convincing evidence of the perovskite framework
clarity.119 (b) Enlarged view of the copper cluster connected to two (as an example, (n-C12H25NH3)2ZnCl4 comprises a distinctly
lead bromide octahedra via apical bromine atoms of the PbBr42− sheets layered structure, but with layers of isolated ZnCl4−2 tetrahedral
(Cu−Br4 and Cu−Cu distances are 2.643(1) Å and 2.649(2) Å, clusters rather than the extended perovskite sheets).124
respectively). Observation of characteristic exciton features in the absorption
spectrum is a valuable confirmation for systems containing
(at least from a structural point of view). Use of such SBUs may Ge(II), Sn(II), or Pb(II) halide perovskite layers (for the 100%
provide a structured approach to modified electrical transport fullerene-incorporated systems, these features are absent).
and optical response, although this still remains to be Recently, another example of larger organic cation, in this
demonstrated practically. case based on cationic propylammonium-functionalized poly-
Another interesting prospective example involves the hedral oligomeric silsesquioxane (POSS) interlayers, has been
incorporation of the fullerene derivatives N-methyl-2-(4- synthesized and structural studies are underway.125 Organic
ammoniumphenyl)-fulleropyrrolidine iodide (AmPF-I2) and functionalized POSSs themselves are recognized as an
N-(n-dodecyl)-2-(4-ammoniumphenyl)-fulleropyrrolidine io- interesting class of hybrid materials, with the POSS fragment
dide (C12AmPF-I2) (Figure 23) in a lead(II) iodide frame- providing mechanical, thermal and chemical stability, and
work.121 While evidence of layered structure formation from X- rigidity. Insertion of functionalized POSS cations into the
ray diffraction was taken as an indication that the perovskite perovskite framework would enable preparation of materials
structure is being formed with this combination, the fullerene that are positioned in between all-inorganic perovskites and
molecule itself has a diameter of ∼7.1 Å,123 rendering it a very hybrid organic-based perovskites and, as such, it promises a
great number of interesting properties and potential
applications. Successful preparation of [Si8O12(C3H6NH3)8]-
[CuCl4]4 (CuPOSS) has been reported, along with the
analogous derivatives PdPOSS, PbPOSS, and MnPOSS;
however, the structural characterization is incomplete, and the
exact compositions and the intricacies of the crystal structures
are not yet available. In earlier publications,126,127 preparation
of layered perovskites containing silica networks as cationic
layers were reported. For this purpose, the authors used 3-
Figure 23. Structures of fullerene-derived molecules (a) AmPF-I2 and aminopropyltrimethoxysilane NH2(CH2)3Si(OCH3)3 (APS),
(b) C12AmPF-I2.121 and the successful formation of Si−O−Si networks was
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evidenced from FT-IR and 29Si solid-state NMR data. Although exhibits characteristic exciton absorption from the PbBr42−
no single crystal X-ray diffraction data were reported, suggestive layers.132 Another example of this involves combining
(00l) peaks of the prospective perovskite sheets are observed in preformed polyacetylene derivatives within a lead bromide
the powder X-ray diffraction patterns of (APS)2PbCl4 and framework.130,131 Although the X-ray diffraction pattern for
(APS)2PbI4 films. In UV−vis spectra, two absorption peaks at these compounds exhibit broad reflections, indicating relatively
256 and 332 nm for (APS)2PbCl4, and at 382 and 507 nm for poor crystallinity or partial ordering, the long d-spacing from
(APS)2PbI4 are observed, apparently arising from the band gap the lowest angle diffraction peak and additional observation of
absorption and excitonic bands, respectively.126,127 The optical an absorption peak at ∼400 nm, which is characteristic of the
band gap values calculated using these data yield 4.84 eV for lead(II) bromide perovskite sheets (Figure 26), suggests that
(APS)2PbCl4 and 3.25 eV for (APS)2PbI4, which are (if indeed these materials self-assemble into the layered perovskite
confirmed) among the highest reported band gap values for framework (or a closely aligned structural type). The
hybrid lead halide perovskites. For a more systematic photoluminescence (PL) from the polyacetylene component
characterization of the perovskites containing Si-based cations, of the hybrid structure is substantially improved (PL quantum
a series of compounds with well-characterized crystal structures efficiencies of as high as 62% are reported) compared with the
would be helpful to understand structure−property relation- polyacetylene component on its own, presumably because the
ship. interaction among polymer chains is reduced in the hybrid as a
While incorporating targeted relatively complex monomeric result of being sheathed in the lead(II) bromide layers.
cations represents one method to generating functional hybrids, One apparent practical application of perovskites containing
another approach involves incorporation of smaller but polymerized units is the enhanced air- and moisture- stability
polymerizable moieties, so that the end product after provided by the protective polymer layers. For example,
polymerization can impart useful properties.128−131 Polymer- addition of small amounts of polyethylenimine hydrogen
ization under UV light or γ irradiation of the diene functional iodide (PEI·HI) into the regular solution deposition procedure
group within [HOOC−CHCH−CHCH−CH2NH3]2- for methylammonium lead iodide yields films that are stable up
CdCl4 (6-amino-2,4-trans,trans-hexadienoic acid organic com- to 400 h under ambient conditions with a relative humidity of
ponent), for example, results in ordered formation of the 1,4- ∼50%.133 For this purpose, the authors first spin-coated a
trans-polybutadiene (Figure 25).128,129 The impact of the mixture of PbI2 and PEI·HI, followed by a coating of a
CH3NH3I layer with targeted compositions of
(CH3NH3PbI3)1−x[(PEI)2PbI4]x (0 ≤ x ≤ 0.04). Incorporation
of a small amount of 2-D perovskite (PEI)2PbI4 (x = 2%)
improves surface roughness and grain size (up to 1 μm),
resulting in smooth and pore-free films. Higher polymeric
cation content of x = 4% gives films with reduced grain size of
less than 100 nm, although their surface coverage is still better
than the pristine CH3NH3PbI3 films.133 The beneficial impact
of the polymeric protective layer to the stability of
CH3NH3PbI3 was also shown by spin-coating a PEI solution
(0.1 mg/mL in toluene) onto a perovskite layer. 134
Remarkably, devices with PEI coating maintain 85% of their
initial performance after 14 days of exposure to 85% relative
humidity.134 Under these synthetic conditions, however, it is
unclear if the 2-D perovskites form or an unreacted PEI layer
acts as a blocking layer. For this and other systems that involve
incorporation of complex organic cations in hybrid perovskite
structures, growth of single crystals suitable for single crystal X-
ray diffraction measurements and/or detailed structural analysis
of well-characterized thin films remains an important practical
Figure 25. Combined skeletal (top) and polyhedral (bottom, shaded) challenge.
view of the layered structure of the polymerized perovskite (HOOC−
CHCH−CHCH−CH2NH3)2CdCl4 viewed down the b-axis.128 5. INTERCALATION SYSTEMS
Another degree of engineering freedom enabled by the lower-
inorganic lattice in this process, in terms of holding the organic dimensional perovskite structures involves intercalation. In the
cations in an appropriate orientation for polymerization to case of layered 2-D perovskites, the tail-to-tail arrangement of
occur, is evident in the fact that the analogous copper(II) organic R-groups within the (R-NH3)2BX4 structure should,
chloride framework, with its associated antiferrodistortive depending upon the degree of interdigitation, provide a van der
Jahn−Teller distortion, does not enable polymerization.129 Waals gallery or gap into which potentially functional molecules
An alternative approach has also been pursued for may intercalate. Intercalated structures are important, for
incorporating polymeric elements into the structure, which example, in the fields of ionic conductivity and battery
involves first creating polymer chains with tethering ammonium development,135 tailoring of photofunctionality (photocatalysis,
groups and then subsequently incorporating these polymeric photoinduced charge separation, photoluminescence, photo-
moieties into the metal halide framework. One example chromism and nonlinear optics)136 and superconductivity.137
targeting this approach involves dipping a film of the hydrogen Early work on intercalation into 2-D organic−inorganic
bromide salt of poly(3-aminododecylthiophene) in an aqueous perovskites was described by Dolzhenko et al.,138 where the
solution of lead(II) bromide, yielding a composite film that weakly interacting molecules, 1-chloronaphthalene, o-dichlor-
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Figure 26. (a) X-ray diffraction patterns of the spin-coated films of poly(11-phenyl-10-undecyn-1-ammonium bromide) and hybrid poly(1-phenyl-1-
undecyne)ammonium lead bromide, labeled as P5 and H1, respectively. The XRD pattern of the bulk powder of hybrid perovskite n-
butylammonium lead bromide (H12) is shown for comparison.131 (b) Absorption spectrum of H1, with a characteristic peak at ∼400 nm observed
for hybrids containing lead(II) bromide perovskite sheets. The absorption spectra of model hybrid compound H12 and polymer P5 are also
provided.131 Reprinted with permission from ref 131. Copyright 2006 American Chemical Society.

obenzene and hexane were explored within perovskites

comprised of long-chain aliphatic cations. However, the weak
van der Waals type interaction between the proposed
intercalation species and the organic cations made explicit
structural characterization of the intercalated structure (e.g., by
single crystal structure refinement) problematic, due to the
instability of the composite.
The first system where intercalation was unambiguously
demonstrated involved molecular species that were structurally
stabilized through noncovalent fluoroaryl−aryl interaction,
which primarily arises from the relatively large but opposite
in sign quadrupole moments for molecules based on C6H6 and
C6F6 (or other analogous aromatic nonfluorinated and
fluorinated molecules).139 Films of (C6H5C2H4NH3)2SnI4
(where C6H5C2H4NH3+ = phenethylammonium) deposited
Figure 27. Combined skeletal (top) and polyhedral (bottom, shaded)
from methanol solutions yielded a crystal structure with
views of the crystal structures of (a) (C6F5C2H4NH3)2SnI4·(C6H6)
interlayer separation (distance between the SnI4− perovskite and (b) (C6H5C2H4NH3)2SnI4·(C6F6) along the b-axis, showing the
sheets) of 16.3 Å. However, when these films were dipped into details of the stacking of the intercalated molecules within the
a solution containing hexafluorobenzene, the interlayer perovskite framework. For clarity, the fluorine atoms are colored green
separation, as deduced from the (2h, 0, 0) X-ray diffraction and hydrogen atoms are omitted.139
peaks, stretched to 20.6 Å (no long axis structure was achieved
if films were dipped into benzene). Likewise, films of
favorable orientation of the phenyl ring in the copper(II)
(C6F5C2H4NH3)2SnI4 (where C6F5C2H4NH3+ = pentafluor- chloride structure for prospective interaction with fluorinated
ophenethylammonium) deposited from methanol yielded aromatic molecules.139
interlayer separation of 17.5 Å, whereas these same films Intercalation can also be combined with chemical reactivity,
dipped in a solution containing benzene yielded interlayer as is the case for iodine-incorporated (R-NH3)2PbBr4, where R-
separation of 20.7 Å (no long axis structure was observed for NH3 comprises an organic cation with a terminal alkyne or
films dipped into hexafluorobenzene). Single crystal structure alkene−e.g., but-3-yn-1-ammonium (BYA), but-3-en-1-ammo-
determination of the longer-axis structures (Figure 27) nium (BEA), and prop-2-en-1-ammonium (PEA).140 Using a
demonstrated offset face-to-face interaction between the lead(II) bromide framework, the parent layered perovskite
intercalated molecules and the initial perovskite organic cations. undergoes topotactic transformation in the presence of iodine
This offset face-to-face interaction is structurally similar to that vapor, with iodine covalently bonding to the unsaturated
observed in the 1:1 benzene-hexafluorobenzene complex, a hydrocarbons (Figure 28). In the case of PEA, the reaction PEA
prototypical fluoroaryl−aryl compound. Gently heating the ↔ PEA-I2 can be cycled, with addition/removal of two iodine
intercalated systems (∼150 °C) deintercalates the molecular atoms, showing the reversibility of the chemisorption process.
species and leads to recovery of the parent layered perovskite. For the alkyne-based cation (i.e., for BYA → BYA-I2), the
Interestingly, the inorganic framework can be used to control reaction with iodine vapor appears to be irreversible. In each
whether molecules will intercalate or not into the hybrid case the chemisorption of iodine leads to significant expansion
structure. While the tin(II)-based systems show facile and of the structure, particularly perpendicular to the perovskite
stable intercalation, (C6H5C2H4NH3)2CuCl4 crystals were not layerse.g., for BYA2PbBr4 the c-axis lattice parameter expands
successfully intercalated, presumably because of the less by 38% during the reaction, and the gravimetric and volumetric
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Figure 28. Combined skeletal (top) and polyhedral (bottom, shaded)

view of the (a) (BYA)2PbBr4 and (b) (BYA-I2)2PbBr4 structures (BYA
= but-3-yn-1-ammonium) showing the addition of the I2 molecule to
the BYA molecule. For clarity, the iodine atoms are colored purple,
and the hydrogen atoms are omitted.140 Figure 29. X-ray diffraction patterns for (a) a vacuum-deposited PbI2
thin film and (b) a (C4H9NH3)2PbI4 thin film, prepared by dipping the
iodine capacities in the nonporous perovskite frameworks are PbI2 film into a 38 mM butylammonium iodide 2-propanol/toluene
solution for 1 min.141 Reprinted with permission from ref 141.
comparable to what can be achieved with more typical porous Copyright 1998 American Chemical Society.
frameworks used for gas capture (e.g., with gravimetric capacity
of 0.43g I2 per gram for the BYA2PbBr4 perovskite).140 Given
the higher stability of the iodine bonding to the alkyne-based the anionic charge from the framework. In these structures, the
derivative, the perovskite hybrids containing the BYA cations extended metal halide anion is held together with covalent/
are proposed for use as thermally stable compounds for iodine ionic bonding and the organic cations interact via ionic and
capture (e.g., for radioactive iodine). As for the intercalation hydrogen bonding (i.e., charge-assisted hydrogen bonding).
processes involving fluoroaryl−aryl interaction, the ability to However, metals are not a requirement for the “B” site within
conduct the iodine storage reaction depends on the inorganic the ABX3 perovskite structure. The molecular perovskite
frameworke.g., in PEA2CuCl4, no reactivity arises in an C4H12N2·NH4Cl3·H2O, for example, consists of a nonmetal-
iodine-saturated vapor and the unsaturated hydrocarbon containing 3-D corner-sharing network of (NH4)Cl6 octahedra,
cations are therefore presumably held within an unsuitable in a structure held together with charge-assisted hydrogen
configuration for the intercalation/reaction to occur. bonding, interspersed with the divalent piperazinium cations
The van der Waals gallery can also provide a means to and water molecules (Figure 30).143 One unusual feature of this
facilitate thin-film deposition and fabrication approaches ABX3 perovskite is that the +2 ionic charge on the “A” cation is
starting from the metal halide. In the two-step dip processing larger than the +1 charge on the “B” cation, in contrast to
approach,141 for example, a film of PbI2 may be dipped into a previously discussed examples of organic-based metal-contain-
solution of R-NH2·HI and, if the “R” group is selected so that a ing perovskites, in which the charge ordering is reversed. In
layered perovskite will form (e.g., butylammonium), then the
reaction to form the layered perovskite structure will proceed in
a matter of seconds to minutes (Figure 29). On the other hand,
if the organic cation leads to the formation of the 3-D
perovskite (e.g., methylammonium), then the reaction may take
hours (unless conducted on a mesoporous framework that can
significantly increase the surface area for the reaction).141,142
Evidently, when the layered perovskite forms, the organic
cations and iodide species can readily diffuse through the van
der Waals gap formed in the reacted material to reach the
unreacted lead(II) iodide starting materials underneath. If the
3-D perovskite forms, then there is no van der Waals pathway
and the diffusion of the reacting species proceeds much slower.
In summary, as can be seen from each of the above examples,
the particular structural/chemical details of the organic cation
within the perovskite (as also templated by the inorganic
framework) may control the ability to intercalate molecules and
the reactivity of these species with the underlying parent
compound, as well as facilitate molecular transport during the
perovskite film formation.

6. MOLECULAR PEROVSKITES Figure 30. Crystal structure of C4N2H12·NH4Cl3·H2O viewed down

the a-axis. The 3-D anionic network of corner-sharing NH4Cl6
In the preceding sections, we have considered a perovskite octahedra (blue) is interspersed with piperizinium dications and
family that comprises a 3-D or lower-dimensional (2-D or 1-D) water molecules. H atoms are omitted for clarity; O atoms are shown
metal halide framework, with organic cations counterbalancing as green spheres.143

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addition, the structure contains water and can be considered a methylammonium or formamidiniumand on their use in
perovskite hydrate. The family has been further extended to photovoltaic devices. The unprecedented jump in performance
include (C 6 H 14 N 2 )(NH 4 )[BF 4 ] 3 (C 6 H 14 N 2 2+ = 1,4- to >20% PCE (power conversion efficiency) levels in less than
diazoniabicyclo[2.2.2]octane or the “dabconium” dication), five years has been enabled by the unusual confluence of ideal
which consists of a 3-D network of corner-sharing (NH4)- semiconductor characteristics within a single material including:
[BF4]6 octahedral units, in this case without water.144 In each of (1) a tunable direct band gap, Eg, where the value of the Eg can
these structures, hydrogen bonding plays a central role in be tailored within the ideal range for terrestrial PV by the
establishing the global framework and covalent interactions play choice of metal or halogen comprising the perovskite, (2)
little role in the perovskite structure assembly (of course they substantially higher optical absorption than conventional thin-
do play a role within the constituent molecules themselves). film solar cell absorbers due to the specific orbital makeup of
Note that structures have also been reported in which the the valence and conduction band edges (i.e., high joint density
ammonium cation in the above frameworks has been replaced of states due to band edge states that have high p-orbital
by alkali metalsi.e. C4H12N2·KCl3·H2O, C4H12N2·RbCl3· character), (3) significant s-p antibonding coupling in the
H2O, C4H12N2·CsCl3·H2O, C6H14N2·RbCl3, and C6H14N2· absorber leading to strongly dispersing conduction and valence
CsCl3, thereby providing a link between the molecular-based bands and relatively small effective masses for both electrons
perovskites and the main family of metal-containing organic- and holes, (4) dominant point defects that are shallow (i.e.,
based perovskites.26 close to the band edge and therefore not effective as
Although, given the lack of covalent character, the extended recombination centers) and (5) intrinsically benign grain
BX3 frameworks in the above molecular compounds are boundaries with respect to recombination.7 Several reviews
insulating, they may help to template or stabilize non- already outline the outstanding potential for organic−inorganic
centrosymmetric and even chiral structures, and systems with perovskites used for thin-film PV.1−6 This contribution seeks to
ferroelectric properties. The structures are also interesting since highlight the numerous other extraordinary properties and
they provide examples of divalent organic cations that can application possibilities for the broader family of organic−
behave as organic “A” cations in an ABX3 framework (of course inorganic perovskites, given the high degree of structural/
longer doubly charged diammonium cations are regularly used electronic flexibility described in previous sections.
within a layered perovskite framework, as discussed in Section
7.1. Magnetic and Dielectric Properties and Application
3). These add to the collection of monovalent cations such as
methylammonium, CH 3 NH 3 + , and formamidimium, 7.1.1. Magnetic Interactions in Hybrid Perovskites.
H2NCHNH2+, that can fit within the 12-coordinate holes Early interest in properties of organic−inorganic perovskites
provided by the extended BX3 framework. Note that generally, focused on their magnetic properties.145−149 With incorpo-
in figuring out the largest effective radius of a cation occupying ration of Cu(II), Fe(II), Cr(II), and Mn(II) as the metal, long-
the “A” site in a 3-D perovskite, we have used the PbI3− range magnetic ordering has been observed within the layered
framework to deduce the value 2.6 Å.10 In the above examples, perovskite structures.145,146,148−152 Notably, the hybrid Cu(II)
since we see that monovalent “B” ions can also be placed into halides provided the first examples of 2-D ferromagnetic
the structure, when given the possibility of divalent organic insulators.149,153 Since there are no direct metal−metal contacts
cations, then the CsI32− framework (Shannon ionic radii RCs+ in the hybrid perovskites, magnetic superexchange interactions,
(octahedral) = 1.67 Å and RI− = 2.20 Å)23 represents a more J, through the B-X-B linkages, usually determine the magnetism
reasonable largest practical metal-containing framework, there- of these compounds. The primary factors influencing the
by extending the organic cation size to as large as 3.27 Å (i.e., magnetic exchange are the structural parameters, including the
for t = 1) to fit within the “A“ site of metal-containing organic- bond distances and angles.154 In addition, the presence of
inorganic perovskites. Of course, even larger BX3n‑ frameworks Jahn−Teller active metal cations influence the structures and
and “A“ cations are possible when considering molecular magnetism of the hybrid compounds. Note that the Good-
complexes for the “B” and “X” moieties. Note that, using the enough−Kanamori (or Goodenough−Kanamori−Anderson)
cubic perovskite crystal structures described above, we can rules,155,156 which were originally developed and are widely
deduce effective ionic radii for the piperazinium and dabconium used for rationalizing the magnetism of oxide perovskites, also
cations of ∼3.2 Å and ∼3.4 Å (Table 1), which are slightly apply for hybrid halide perovskites. Briefly, the Goodenough−
larger values (at least for dabconium) than the above-calculated Kanamori rules predict a strong antiferromagnetism when the
largest possible size of 3.27 Å for t = 1. The discrepancy may magnetic orbitals on adjacent B atoms are oriented at ∼180°
perhaps be attributed to the less exact nature of the ionic size and B has partially filled d shells, and a weak ferromagnetism
calculation method used for polyatomic ions22i.e., for arises when the magnetic orbitals are at ∼90°.157 For example,
example to uncertainty with regards to the radius of 1.77 Å in the layered A2CuX4 salts, due to their antiferrodistortive
used for C.24 An area for further exploration involves structures, the magnetic interactions within the layers occur
elucidating and expanding the true limits to the collection of through Cu−X···Cu linkages where X···Cu represents the
divalent and monovalent organic cations that fit within the 3-D Jahn−Teller elongated copper-halide bond.158 Intralayer
perovskites, thereby providing a larger set of building blocks coupling for the A2CuX4 salts is ferromagnetic because the
with which to put together functional organic−inorganic bridging Cu−X···Cu angles are in the 160−170° range and the
hybrids. magnetic orbitals on adjacent Cu atoms are nearly orthogonal,
i.e., there is essentially no magnetic orbital overlap.9,158 The
7. EXCEPTIONAL PROPERTIES AND DEVICE magnitude of this intralayer exchange interaction in A2CuX4 is
APPLICATION determined by the orbital overlap between the magnetic
Intense current interest in organic−inorganic perovskites has orbitals on two adjacent Cu atoms, which in turn strongly
centered primarily on one set of materialsi.e., those based on depends on the Jahn−Teller elongated X···Cu contacts. The
APb1−xSnxI3, where “A” is a small organic cation such as magnetic exchange interaction J decreases rapidly with
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increasing X···Cu distance. Note that Cr(II) layered perovskite paramagnetic resonance (EPR) spectroscopy line widths, are
analogs are also ferromagnetic due to the cooperative Jahn− very different, with an order of magnitude larger line widths for
Teller effect, and the resulting structural distortions are similar the Cu- and Mn-based bromides compared to the chlor-
to those observed for the Cu(II) salts.151 On the other hand, ides.161,162 The temperature and angular dependence of the line
most layered perovskites featuring Mn(II) and Fe(II) do not widths are also dissimilar.
exhibit Jahn−Teller distortion, and are antiferromagnetic.9 In 7.1.2. Magnetic and Multiferroic Materials. Recently, an
these compounds, symmetrical B−X−B linkages are nearly unusually high magnetic hardness, which could enable use as a
linear, and consequently, following the Goodenough−Kana- data storage material (although with operating temperatures of
mori rules, the linear superexchange of two magnetic ions with below 100 K), has been demonstrated for (C2H5NH3)2-
partially filled d orbitals is strongly antiferromagnetic. [FeCl4].163 This compound undergoes four structural tran-
The interlayer coupling, J′, is strongly dependent on the sitions associated with tilting and rotation of the octahedra and
interlayer X···X distance, the geometry of the B−X···X−B C2H5NH3+ cations. (C2H5NH3)2[FeCl4] is a 2-D-paramagnet
linkage, and the halide X− ion. As expected, the interlayer above 100 K, and a canted antiferromagnet below 100 K, with a
coupling increases rapidly with decreasing interlayer X···X canting angle of 0.6° toward the c-axis. The related
distance. From the chemical design perspective, since the (CH3NH3)2[FeCl4] also exhibits canted antiferromagnetism
magnetic interactions generally arise in the inorganic perovskite in a field above 200 Oe.150,164 However, unlike (C2H5NH3)2-
layers, varying the length of the organic cation provides a knob [FeCl4], which also demonstrates both ferroelectricity and
to vary the effective dimensionality of the magnetic interaction, ferroelasticity, (CH3NH3)2[FeCl4] does not.163,165 Generally,
from more 3-D to more 2-D with increasing organic cation longer alkyl chains (e.g., ethylammonium vs methylammo-
length, as seen within the (C n H 2n+1 NH 3 ) 2 CuCl 4 and nium) allow more degrees of freedom, subsequently resulting in
(CnH2n+1NH3)2MnCl4 families.149 Structural symmetry also more structural phase transitions. Ferroelectric transitions have
plays an important role in the magnetism of hybrid compounds. also been reported for Cu(II)-based hybrid perovskites
For instance, the (CnH2n+1NH3)2MnCl4 (n = 1, 2, 3···) series, featuring longer alkyl chains.166,167
members of which adopt the tetragonal K2NiF4-type structure, Multiferroic materials combine ferroelectricity with ferro-
has been considered to comprise the “best” 2-D antiferro- magnetism and reports of multiferroic behavior in the layered
magnetsi.e. those with the smallest possible ratio of interlayer 2-D and 3-D perovskites have begun to appear.166,168 As an
to intralayer coupling |J′/J|.147,149 The rationale behind this example, ferroelectric and ferromagnetic ordering coexist in
designation follows from the fact that the magnetic 2-D (C6H5CH2CH2NH3)2CuCl4 at temperatures below 13 K.166
character in the K2NiF4 structure mainly originates from the Multiferroic materials provide interesting possibilities for
tetragonal symmetry, which in the case of an antiferromagnetic materials design because they enable direct control of the
alignment within the NiF2 sheets leads to a cancellation of the magnetism with an electric field, due to coupling between order
interaction between the adjacent layers. 159 In the parameters. Such coupling can enable data to be written in a
(CnH2n+1NH3)2MnCl4 compounds, the tetragonal K2NiF4- storage media electrically and then read magnetically, which
type structure combines with the tunable interlayer distance combines beneficial characteristics of ferroelectric random
(through varying n), leading to |J′/J| values that can be much access memory (FeRAM) and magnetic data storage.169
smaller compared to those in strictly inorganic K2NiF 4 Other potential applications of multiferroics include electric
structures. Supporting this conjecture, even for the n = 1 field controlled magnetic sensors, spin filters or “spintronic”
compound (CH3NH3)2MnCl4, a superexchange interlayer devices for data storage and spatial light modulators for optical
coupling value of J′ = 10−10 J is reported, with J′ occurring switching.167,169−171 A grand challenge, however, is how to
through two CH3NH3+ cations and two Cl− anions.147,149 tailor materials design in such a way that the ferroelectric and
In addition to varying organic cation length and structural ferromagnetic order parameters are strong at room temper-
symmetry, varying the halogen from iodide down to fluoride ature.172,173
allows for changing the exchange interaction among the The high degree of tunability within the perovskite
magnetic ions both in and between the layers, providing framework may help to facilitate achieving this goal in a
further tunability of the magnetic interaction.151,152,160 It has material that can be readily and cheaply processed. In fact,
been shown that both intralayer and interlayer couplings are (C(NH2)3)Cu(HCOO)3,174 (C(NH2)3)Cr(HCOO)3,175 and
weaker in the Cu(II) and Cr(II) chlorides compared to the (CH3CH2NH3)Mn(HCOO)3176 (see Figure 3) have recently
corresponding bromides.151,158 The larger ferromagnetic intra- been theoretically predicted to be multiferroic materials. In
layer couplings in the Cu(II) and Cr(II) bromides are (C(NH2)3)Cr(HCOO)3,175 for example, according to theory,
attributed to the larger extension of the bromide valence the lattice instability is responsible for both ferroelectricity and
electron shell.151,161 Unlike chlorides, it is reported that for the appearance of the weak ferromagnetic ordering with Tc ∼
some bromides, e.g., (ethylenediammonium)CuBr4, the inter- 40 K. Experimental demonstration of multiferroic behavior in
layer coupling is larger than the intralayer coupling, indicating the related [(CH3)2NH2)M(HCOO)3 (M = Mn, Fe, Co, and
that the dominant exchange pathway is between the layers.158 Ni) has also been reported.177 These compounds undergo
The |J′/J| ratio has a central role in the determination of the 3- paraelectric-to-antiferroelectric phase transitions below 160−
D magnetic phase transition temperature, Tc.151 Higher Tc of 185 K. Hydrogen bonding plays an important role in the
the Cr(II) bromides compared to chlorides is ascribed to a associated structural transitions from disordered paraelectric to
greater overlap and polarizability of the bromide ion, which more ordered antiferroelectric phases, which coexist with
results in a more efficient Cr−Br···Br−Cr exchange and, canted weak ferromagnetism below 40 K. Study of chemical
consequently, a stronger interlayer coupling.151 A small XY-like bonding characteristics of a related ferroelectric material,
anisotropy is reported for the chlorides, whereas for bromides (NH3NH2)Zn(HCOO)3, showed that lone pairs located on
the small anisotropic component of the exchange is Ising- oxygen are involved in salt bridge-like interactions with the
like.161 The relaxation properties, as measured by the electron ammonium group of NH3NH2+, similar to those in proteins
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and polymers.178 Both ionic and hydrogen bonding interactions 7.2. Electrical Transport Properties and Application
are present in (NH3NH2)Zn(HCOO)3, resulting in strong 7.2.1. Band Structures and Tunable Electrical Proper-
cation-metal formate interactions and, consequently, a relatively ties. While metal halides are predominantly insulating in
stiff lattice with elastic moduli of E001 = 26.5 GPa and E110 = electrical character, the layered perovskites based on group IV
24.6 GPa and a bulk modulus of K = 19 GPa. metals Ge, Sn and Pb exhibit conductivity, with decreasing
For (CH 3NH3)Co(HCOO) 3, multiferroic behavior is band gaps as the thickness of the perovskite layers is
induced by magnetic ordering (type II multiferroic behav- increased.11,48,58,186−188 One of the first examples of this
ior).179 Due to hydrogen bonding interactions, the metal behavior was found in the family of ⟨100⟩-oriented perovskites
formate inorganic framework is distorted, providing grounds for (C4H9NH3)2(CH3NH3)n−1SnnI3n+1, which consists of “n” layers
anisotropic magnetic and electric behavior and coupling of CH3NH3SnI3 perovskite, separated by bilayers of butylam-
between them. The compound displays canted antiferromagnet monium cations.48 The n = 1 compound (C4H9NH3)2SnI4 is a
behavior below 15.9 K, as confirmed by magnetization semiconductor with a band gap of ∼1.98 eV,189 whereas the
measurements.179 When a pulsed magnetic field is applied band gap progressively decreases for higher order structures
along [101], a clear change in the electric polarization is and the n = ∞ compound CH3NH3SnI3 has a band gap in the
detected. At a critical magnetic field, a spin rearrangement range of 1.2−1.4 eV and can be easily doped to yield
occurs that induces a change in the electric polarization along semimetallic behavior.19,48,60,190 Demonstrating remarkable
[101] and [10−1].179 For another hybrid perovskite with tunability of its electrical properties, CH3NH3SnI3 normally
confirmed multiferroic behavior, (C2H5NH3)2CuCl4, ferroelec- exhibits a heavily doped p-type semiconducting behavior19,48
tricity sets in at a higher temperature of 247 K, and the presumably due to self-doping via the oxidation of Sn2+ to
dominant ferromagnetic interactions emerge below 20 K.167 Sn4+;190 however, targeted chemical manipulations may result
These examples clearly demonstrate that the hybrid perovskites in decreased doping levels, and ultimately, n-type semi-
are a promising class of materials for studying multiferroicity. conductors.60 In the parent CH3NH3SnI3, the top of the
However, the experimental challenge remains for the valence band is composed of Sn 5s and I 5p states, whereas the
preparation of hybrid perovskites with small distances between main contribution to the conduction band comes from Sn 5p
magnetic ions, which would lead to strong exchange coupling states.190−192 The mixing of the Sn lone pair 5s orbital with the
and higher magnetic ordering temperatures, combined with a I 5p orbital via an antibonding s-p coupling in the valence band
significant coupling among strain, electric polarization and maximum (VBM) results in several advantageous optoelec-
magnetism.176 tronic properties.7 First, since the divalent B-metal s orbitals are
7.1.3. Dielectric Properties. Dielectric properties of occupied, there is a direct gap p-p optical transition, which is
organic−inorganic hybrid perovskites can also be promising the main reason for the strong optical absorption properties of
for technological applications. The inorganic framework in these compounds.7 Furthermore, the band dispersion in the
hybrid perovskites may facilitate high dielectric constants and, valence band is strongly enhanced due to the presence of the B-
in the 3-D perovskites such as CH3NH3PbI3, high dielectric metal s states and the antibonding s-p coupling in the VBM,
constant provides an environment where defects are more resulting in relatively small effective masses for holes in this
effectively screened. For CH3NH3PbI3, a high frequency system.7 It is clear that the organic cation, CH3NH3+, has no
dielectric constant value of ε = 6.5 has been reported in the direct contribution to the states around the Fermi level, as
optical energy region.180,181 A more recent study of the expected from simple chemical trends. In these pseudoternary
dielectric properties of high-quality CH3NH3PbI3 thin films systems, the organic cations (or alternative inorganic cations
over a large frequency range showed that the real part of the such as Cs+) mainly act as electron donors since their
static dielectric constant is ε′ ∼70, much higher than previously electronegativities are much lower compared to B-metals such
thought.182 The authors attribute such a high static value to a as Sn/Pb and halogens. Therefore, the states around the Fermi
1/f behavior of the imaginary part of the dielectric constant, ε″, level are dominated by the inorganic framework, which also
which is known as “Jonscher’s Law”, and to the highly ionic applies to the band structures of lower dimensional perovskites
character of the compound. Such a high dielectric constant can (at least for those containing organic cations with large
yield a very low excitonic binding energy value of 2 meV, in HOMO−LUMO separation).
comparison to the binding energy value of 38 meV calculated Although they do not contribute to the states around the
assuming ε = 6.5. This study, therefore, suggests that the Fermi level, organic cations convey indirect influence (see
CH3NH3PbI3 system is mostly nonexcitonic at ambient Section 3 for specific examples) on the electronic structure of
temperatures, and that the advantageous benign defect the (C4H9NH3)2(CH3NH3)n−1SnnI3n+1 (n = 1, 2, 3, etc.) and
properties of CH3NH3PbI3-based solar cells are at least in related materials through crystal structure effects (e.g.,
part due to the associated high dielectric constant.182 For 3-D dimensional reduction, induced tilting and deformations of
chloride perovskites such as the strictly inorganic CsPbCl3, the the inorganic framework, cation size changes, and hydrogen
dielectric constant increases to values ε > 10 (approaching 20), bonding).54,58,192 As mentioned above, in (C4H9NH3)2-
as expected from the trends in electronegativity and ionicity of (CH3NH3)n−1SnnI3n+1 and related layered perovskite series,
halides.183,184 It should be noted that careful characterization of the band gap values increase when going from the 3-D parent
dielectric constants is necessary to study the trends, as film or compound CH3NH3SnI3 to the low-dimensional 2-D layered
crystal quality or even illumination can influence the results of derivatives, in part because of reduction in the valence/
such measurements.185 Based on the available data, it can be conduction bandwidths.58,188,193,194 The observed bandwidth
concluded that, in addition to the advantageous semiconductor narrowing can be attributed to the lack of band dispersion in
defect properties useful in PV applications, such high dielectric the direction perpendicular to the inorganic layer (i.e., decrease
constant values also point to a potential application of hybrid in dimensionality), as well as to structural distortions (e.g.,
perovskites in other electronic devices (e.g., gate insulators in induced by organic cations or the Jahn−Teller effect).193 For
field-effect transistors). example, the band dispersions in the directions perpendicular
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to the inorganic layers are close to zero in (C4H9NH3)2PbI4. small,200 the influence of the electronegativities is secondary to
Additionally, a comparison of band structures of ideal (i.e., structural factors. For example, the measured band gap values
undistorted) and actual (i.e., distorted) (C4H9NH3)2PbI4 for CH3NH3SnI3 are in the range of 1.2−1.4 eV, whereas the
clearly indicates that the valence and conduction bands of the band gap values of CH3NH3PbI3 are reported as 1.5−1.6
actual (C4H9NH3)2PbI4 are narrower and shifted to lower eV.60,201 This trend is expected given the fact that Sn (1.96) has
energies.193 A significant valence bandwidth narrowing by up to a higher Pauling electronegativity compared to Pb (1.87),202
1.95 eV has also been calculated for the A2SnI4 family, where and as such, the Sn states should be located lower in the band
replacement of organic cations results in severe in-plane structure, leading to a smaller separation between the I 5p states
distortions of the SnI42− inorganic sheets.54,58 This is an in the valence band and the Sn 5p states in the conduction
important finding, as the bandwidth narrowing also generally band. In other words, Pb is more metallic compared to Sn and
results in larger charge carrier effective masses and exciton therefore, based on chemical trends, Pb−I bonds should be
binding energies in the 2-D crystals.118,193,194 From the more ionic compared to Sn−I bonds, leading to the larger band
application standpoint, the exciting aspect of the band gap gap of CH3NH3PbI3. These simple ideas are also confirmed by
progression in the series (C4H9NH3)2(CH3NH3)n−1SnnI3n+1 (or the results of ultraviolet photoelectron spectroscopy (UPS)
related layered Ge, Sn and Pb perovskites) is the achievement measurements, which put the conduction band edges of
of a highly tunable semiconductor that can be simply (e.g., CH3NH3PbI3 and CH3NH3SnI3 at −3.90 eV and −4.17 eV,
solution) processed for electronic and energy applica- respectivelyi.e. Sn states are located lower in the band
tions.11,58,195 structure of CH3NH3SnI3.203 This comparison is purely based
7.2.2. Application of Sn-Based Conducting Hybrids. on the electronegativity difference between Sn and Pb, and
The first example of application of the tunable semiconducting ignores the influence of the detailed crystal structures and
character was use of spin-coated (C6H5C2H4NH3)2SnI4 films distortions (as discussed in section 3.1).
(based on the phenethylammonium cation) as channel layers in The dominant influence of detailed structural effects for the
thin-film transistors (TFTs).196 The layered hybrid perovskite 3-D perovskites is exemplified by the case of CH3NH3GeI3,
forms a p-channel transistor, giving relatively high field-effect featuring the smaller Ge2+ cation compared to Sn2+ and Pb2+.
mobilities of 0.55−0.62 cm2/V·s and current modulations Following the observed trends in electronegativites for Pb
greater than 104. Further improvements to the performance of (1.87), Sn (1.96), and Ge (2.01),202 one would expect a lower
the hybrid tin(II) based perovskite transistors have been made band gap for the CH3NH3GeI3 member. However, the reported
through melt processing of the films, yielding mobilities of as band gap for CH3NH3GeI3 is 1.9 eV, much larger compared to
high as 2.6 cm2/V·s in the saturation regime and 1.7 cm2/V·s in that of Sn- and Pb-analogs.204 The larger band gap of the Ge-
the linear regime.197 More recently, there have also been analog can be tied to its substantially different quasi-3-D
examples of hybrid TFTs prepared using vacuum-based hexagonal structure,23 which contains GeI6 octahedra com-
deposition of the perovskites. 198,199 In one example, prised of three short and three long Ge−I bonds (see below for
(C6H5C2H4NH3)2SnI4 films were grown on boron-doped further discussion, Figure 34) due to a second-order Jahn−
silicon (gate)/silicon dioxide (gate insulator) substrates kept Teller (SOJT) effect.35,204 Although the compositions of the
at 60 °C through dual-source vapor deposition of SnI2 and frontier states around the Fermi level are analogous to the Sn
C6H5C2H4NH3I.198 These films were used as p-channel and Pb cases (i.e., the valence band being composed of Ge 4s
semiconductors in field-effect transistors (FET), which showed and I 5p states, and the conduction band arising from
a hole mobility of 0.78 cm2/V·s in the saturation regime, a predominantly Ge 4p states), the stereochemical activity of
threshold voltage of −1.7 V, and a drain current on/off ratio of the Ge 4s2 electrons and the significant sp-hybridization of the
4.2 × 105.198 In the second example, using a similar deposition Ge and I orbitals yield the large band gap of 1.9 eV for
techniquei.e. dual-source evaporation of SnI2 and CH3NH3I CH3NH3GeI3.204
on substrates at 50 °Ca 50 nm-thick CH3NH3SnI3 film was 7.2.4. Sb- and Bi-Based Semiconductors. Hybrid
deposited.199 The resultant film exhibited a low electrical perovskites based on trivalent Sb and Bi are also expected to
resistivity of 8.7 × 10−5 Ω cm. The CH3NH3SnI3 film was used exhibit semiconducting behavior and very similar band
as the source-drain electrodes on top of a vacuum-deposited structures to those of divalent Sn- and Pb-based compounds.
pentacene layer, which acted as the semiconductor channel. This is because Sb3+ and Bi3+ ions are isoelectronic to Sn2+ and
The reported parameters for this FET are a saturation-regime Pb2+, and electronegativities and ionic radii of these elements
hole mobility value of 0.004 cm2/V·s, current modulation value are close in value.23,202 Among the few known hybrid
of 1.2 × 103, and threshold voltage of −7.2 V.199 Note that, in perovskites featuring trivalent Sb and Bi cations are the
each of these examples, devices were made and measured under semiconducting q = 2 members of the ⟨111⟩-oriented A3B2X9
rigorously inert atmosphere conditions. One issue with the perovskites. The layered modification of purely inorganic
Sn(II)-based hybrid materials is the severe sensitivity to air/ Cs3Sb2I9, for example, has a band gap of 2.05 eV, and dispersive
moisture and therefore the need to keep them encapsulated or bands around the Fermi level, mainly composed of Sb 5s and I
isolated from the environment. 5p states in the valence band and Sb 5p states in the conduction
7.2.3. Pb- and Ge-Based Semiconductors. While most band, resulting in relatively low effective masses of charge
of the examples covered in this section so far are focused on Sn- carriers (mh,e* = 0.34−0.91 m0).99 The bromide analogs
based compositions, hybrid perovskites featuring Pb2+ and Ge2+ Cs3Sb2Br9, Cs3Bi2Br9, and Rb3Sb2Br9 have larger band gaps of
also exhibit semiconducting behavior, including the now 2.30, 2.50, and 2.48 eV, respectively.91 Another example of a Bi-
famous CH3NH3PbI3. The band structures of such compounds based perovskite is the compound (AEQT)Bi3/2I4, where
are similar to those of the Sn-based analogs (see above) owing AEQT = 5,5‴-bis(aminoethyl)-2,2′:5′,2″:5″,2‴-quaterthio-
to the fact that all of these cations are isoelectronic. The normal phene. In this example, metal deficient layers of bismuth
chemical trends apply in this family; however, since the iodide octahedra alternate with layers of AEQT molecules, with
differences in electronegativities between these elements is the possibility of tuning the energy levels of both organic
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cations and inorganic framework, as mentioned in section 4.76

Although there are clear advantages in replacing the toxic Pb2+
and unstable Sn2+ with the isoelectronic Sb3+ and Bi3+ in hybrid
perovskite semiconductors, systematic work targeting synthesis
and characterization of the semiconducting Sb- and Bi-
containing perovskites is currently just beginning to be a
center of focus.
7.2.5. Cu-Based Semiconductors. Replacement of Sn2+
and Pb2+ with first row transition metal cations such as Cu2+
has much more dramatic consequences to the band structures,
since the 3d9 4s0 electronic configuration of Cu2+ is very
different than that of the main group metal cations with lone
pair electrons. Several groups have considered copper halide
perovskites as alternative semiconductor absorbers to
CH3NH3PbI3 for use in solar cell devices.205 For example,
Figure 31. Absorption spectra for (a) (C10H21NH3)PbI4, (b)
(p−F-C6H5C2H4NH3)2CuBr4 and (CH3(CH2)3NH3)2CuBr4
(C6H5C2H4NH3)PbI4, and (c) (C6H5C2H4NH3)2(CH3NH3)Pb2I7
are reported to have optical band gaps of 1.74 and 1.76 eV, taken at (A) 300 K and (B) 10 K. A tunable exciton peak is observed
respectively, from the absorption data.205 The devices both at low temperature as well as at room temperature.208 Reprinted
fabricated using FTO/TiO2/Cu-halide perovskites/spiro-MeO- with permission from ref 208. Copyright 1992 American Physical
TAD/Ag structures showed open-circuit voltages (Voc) 0.87− Society.
0.88 V, short-circuit photocurrent densities (Jsc) of 1.46−1.78
mA cm−2, and a fill factor (FF) of ∼0.40, giving PCE (power these effects, for a model system with no dielectric mismatch
conversion efficiency) values of 0.51−0.63%.205 The authors between organic and inorganic layers, the binding energy would
attributed poor performances of the devices to the low be expected to increase from 29 to 116 meV (4 times
conductivities of the layered copper halides, which in turn enhancement) in going from 3-D to 2-D excitons in a lead(II)
derives from the modification of the band structure induced by iodide structure.210 Dielectric mismatch leads to a dielectric
the replacement of Pb2+ with Cu2+. As discussed in section 7.1, confinement effect, also known as the “image charge
Cu(II) halide perovskites are magnetic, which clearly indicates effect.”211,212 In simple terms, due to a much lower dielectric
that Cu 3d orbitals have important contributions to the states constant in the organic cation layer, the effective Coulomb
around the Fermi level.149,206 The presence of the localized Cu interaction between the electrons and holes in the inorganic
3d orbitals in the vicinity of the Fermi level is expected to result well layer increases, which leads to a larger exciton binding
in higher effective masses of charge carriers, and hence, lower energy.213 The relative contribution of the dielectric confine-
mobilities. In addition, (C 6 H 5 C 2 H 4 NH 3 ) 2 CuBr 4 and ment effect depends on several factors, including the dielectric
(CH3(CH2)3NH3)2CuBr4 are layered compounds, and there- constants of the inorganic well and organic barrier layers, and
fore, bandwidth narrowing due to the confinement of the the thicknesses of these layers. For [C5H11NH3]Pb2I5, which is
inorganic framework also applies,188,193 making the bands more a perovskite-related bilayer compound featuring edge- and
flat and further reducing the direction-averaged mobilities, all of corner-sharing PbI6 octahedra, it was estimated that 146.4 meV
which could contribute to the very low Jsc values observed for of the exciton binding energy originates from the dielectric
devices based on layered copper halide perovskites. These ideas confinement effect, and this constitutes ∼64% of the total
are indirectly confirmed by the recent work on exciton binding energy of 230 meV for this compound.210 This
(CH3NH3)2CuClxBr4−x perovskites,207 which feature band report is in agreement with the earlier findings that the
gaps in the 1.8−2.48 eV range and exhibit very high effective enhancement of the exciton binding energies in lead iodide-
masses. In these materials, the DFT calculated effective mass based perovskite hybrids predominantly arise due to the
along the Γ-Z direction, for example, is infinity for holes as a dielectric confinement effects.208
result of the flat bands in the electronic structure.207 As seen from the example above, the exciton binding energy
7.3. Optical Properties and Optoelectronic Applications
can be as large as several hundred meV, much larger than kbT at
room temperature (∼26 meV). The highest reported exciton
7.3.1. Quantum and Dielectric Confinement Effects binding energies for bulk hybrid perovskites are generally in the
and Excitonic Properties. Interest in optical properties and 300−400 meV range,210,213−215 including, for example, 320
potential application of metal-halide-based perovskites can be meV for (C10H21NH3)2PbI4.208 Note that the organic cation
traced to as early as the publication of a 1958 Nature article, in contains a long alkyl chain for this system, which reinforces the
which the tunable photoconductive properties of CsPbX3 were idea that better isolation of the inorganic well layer enhances
noted, with a peak photoconductive response that could be the exciton binding energy. The separation can be further
tailored by changing the halogen, from violet for CsPbCl3 to improved through mechanical exfoliation of the bulk crystals
red for CsPbI3.209 Interestingly, a second, rather unique feature into ultrathin crystalline layers. In nanosheets of
of the layered hybrid perovskites based on germanium(II), (C4H9NH3)2PbI4 crystals prepared this way, the exciton
tin(II), and lead(II) halide sheets (in addition to the tunable binding energy of 490 meV has been measured.216 For
semiconducting electrical properties discussed in the last comparison, measurements on the bulk (C4H9NH3)2PbI4
section), is the sharp and intense exciton resonances in the crystals give an exciton binding energy value of 360 meV.214
optical absorption spectra (Figure 31).208 The strength of the To the best of our knowledge, for the layered organic-inorganic
exciton features at room temperature arises because of the iodide perovskites, the largest exciton binding energy reported
quantum (i.e., dimensional reduction) and dielectric confine- for the organic−inorganic hybrid perovskites so far is 540 meV
ment effects. To evaluate individual contribution of each of for bulk (4-FC6H4C2H4NH3)2PbI4,217 a value that represents a
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more than 2-fold increase in the exciton binding energy by If the interaction between excitons is attractive, biexcitons
simple substitution of a fluorine into the phenyl ring (i.e., the can form219 and, in the case of layered hybrid perovskites, the
exciton binding energy for (C6H4C2H4NH3)2PbI4 is reported as binding energy can be unusually high. In typical semi-
220 meV).218 If confirmed, this dramatic binding energy conductors, binding energies of biexcitons are small (<10
increase would be another indication of the wide tunability of meV); however, binding energies of as large as 65 meV have
excitonic features in the layered perovskites. been reported for (C4H9NH3)2PbBr4.228,229 For the hybrid
Excitons, which correspond to a bound state of one electron bilayer compound (C4H9NH3)2(CH3NH3)Pb2Br7, since the
and one hole, are conventionally classified into the small-radius confinement effect is weaker, the biexciton binding energy is
(comparable to the unit cell dimension) Frenkel excitons, large- twice smaller, 26 meV (still on the order of kbT at room
radius (larger than the unit cell size) Wannier (or Wannier- temperature).230 Such enhanced binding energies in hybrid
Mott) excitons, and charge-transfer excitons typical for perovskite systems are useful for studying the excitonic
interfaces.219 Wannier excitons are typical of inorganic properties of semiconductors, in particular biexciton formation
semiconductors and possess radii on the order of 30−100 Å and relaxation, which are important in nonlinear optical
and binding energies of ∼10−30 meV, whereas Frenkel processes. In addition to the fundamental interest, biexciton
excitons are typical of organic materials and exhibit radii of lasing has been demonstrated at temperatures of up to 40 K
∼5 Å and binding energies of ∼0.5−1 eV.219,220 Excitons in the from a spin-coated 200 nm-thick (C6H13NH3)2PbI4 film
3-D parent hybrid perovskites are Wannier excitonse.g., formed on a Ti-containing glass substrate.231 A lasing threshold
exciton binding energies of up to 50 meV and exciton Bohr of 20 kW/cm2 at 16 K and a maximum pump intensity of 600
radii of 22−38 Å are generally reported for kW/cm2 are reported for this device.231
CH3NH3PbI3.180,181,188,221 However, a clear assignment of In addition to Wannier, Frenkel and hybrid excitons, as well
excitons to either Wannier- or Frenkel-types in the layered as biexcitons, bosonic quasiparticles known as polaritons can
hybrid perovskites has been difficult due to the above-discussed form through a strong exciton-photon coupling.219 In fact,
quantum and dielectric confinement effects. Depending on the under the strong coupling regime, polaritons determine the
organic cations (e.g., length of alkyl chain, presence of optical properties of solids.219 From a practical standpoint, the
functional groups) and inorganic layers (e.g., thicknesses, interest in this area is fueled by the promise of new nonlinear
elemental composition), a large variation in the observed photonic devices and phenomena, including optical transistors,
exciton binding energies (60−540 meV) and radii (22.9−6.2 Å) switching devices, polariton condensation,232,233 and a new
have been reported.188 (C10H21NH3)2PbI4, for example, has an kind of coherent light source, the polariton laser, which could
have lower thresholds than conventional lasers.234,235 By spin-
exciton binding energy of 320 meV and exciton Bohr radius of
coating (C6H5C2H4NH3)2PbI4 on a corrugated quartz substrate
less than 7 Å.221 The exact nature of excitons in 2-D hybrid
with a period of ∼0.7 μm, Fujita et al. fabricated a distributed
perovskites, therefore, has been under debate, with various
feedback microcavity that shows well-separated tunable polar-
research groups proposing that the excitons are of Wannier
iton absorption in transmission measurements at room
type but with a small radius222 and others, conversely, pointing
temperature.218 Due to the large oscillator strength of excitons
to the fact that the observed magneto-optical properties, such
in (C6H5C2H4NH3)2PbI4, a polariton mode splitting (i.e., Rabi
as the anisotropic Zeeman splittings, are better explained using splitting) of as high as 100 meV at room temperature has been
the Frenkel-exciton model.223 recorded. 218 A Fabry−Pér ot microcavity containing
Recent work in this area suggests that, for appropriately (C6H5C2H4NH3)2PbI4 between dielectric and metallic mirrors
tailored organic cations and inorganic frameworks (as discussed has also been fabricated, and shows anticrossing of 140−190
in Section 4) and, as confirmed by electroabsorption and two- meV between the cavity and excitonic modes.236,237 In
photon-absorption spectroscopy, two-dimensional (2-D) Wan- comparison, III−V and II−VI semiconductor quantum wells
nier excitons may be formed in the inorganic layers,213,224,225 in Fabry-Pérot microcavities show polariton splitting energies
along with Frenkel excitons in the organic substructure.109,219 of only 9−18 meV,218 though a recent work using a hexagonal
In fact, these different types of excitons can couple, forming GaN/InGaN core−shell wire reports Rabi splitting energies of
“Frenkel−Wannier hybrid excitons” that have features derived as large as ∼180 meV.232
from both the large radius and nonlinearity of the Wannier The maximum polariton splitting is limited by the oscillator
excitons and the large oscillator strength of the Frenkel strength of excitons in the material and not by the microcavity
excitons.109,219 Hybrid excitons are expected to exhibit unusual effect,218 and therefore, further improvements are possible
properties, including a strong enhancement of the optical through careful tailoring of the hybrid perovskite excitonic
resonance nonlinearity. The optical nonlinearity is limited in properties. The spectral position of the excitonic transition can
materials featuring either Wannier or Frenkel excitons; be tuned, for example, through substitution on the halide ion
however, materials with hybrid excitons can demonstrate an site, with UV polaritonic emission (∼3.5 eV) being observed
increased (by 2 orders of magnitude) nonlinearity.219 An from a (C6H5C2H4NH3)2PbCl4-based one-dimensional Fabry-
efficient energy transfer between the organic and inorganic Pérot microcavity.238 The Rabi splitting value of 230 meV for
substructures is necessary for the formation of hybrid excitons. this system is also among the highest reported. As an added
As previously referred to in Section 4, practical demonstration layer of complexity, hybrid polaritons can be created in a
of nearly perfect (>99%) triplet−triplet Dexter-type energy microcavity containing two different semiconductors that are
transfer from Wannier excitons in PbBr 4 2− layers to both coupled to the same photon mode.220 In one example,
naphthalene has already been shown for (1-Naphthyl- (C6H5C2H4NH3)2PbBr4 was used as the inorganic semi-
CnH2nNH3)2PbBr4.109 Other examples of resonant coupling conductor with Wannier excitons and zinc tetraphenyl-porphrin
between Frenkel and Wannier excitons include studies (ZnTPP) was employed as the organic dye with Frenkel
in v o l v in g ( C 6 H 5 C H 2 N H 3 ) 2 P b C l x B r 4 − x , 1 1 1 , 2 2 6 a n d excitons.219,220 Reflectivity measurements were used to
(C10H7CH2NH3)2PbBrxI4−x.227 demonstrate the formation of hybrid exciton polaritons
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comprised of the cavity photon and the excitons in the organic control over grain size (with the average grain diameter of 99.7
and inorganic parts. The authors suggest that the hybrid nm), uniformity and coverage of the CH3NH3PbBr3 films. The
polaritons can undergo radiative emission, and that these authors note that, for LED applications, smaller grains are
polaritons can act as an intermediate state between excitons in preferred because smaller grains limit the exciton diffusion
the organic and inorganic components.220 length, which in turn reduces the possibility of exciton
7.3.2. Optoelectronic Applications for CH3NH3PbX3. In dissociation before recombination.245 These manipulations
recent years, following the discovery of the PV properties of result in the achievement of a current efficiency (CE) of 42.9
APb1−xSnxI3, interest in hybrid perovskites as photodetec- cd A−1, which is comparable to that of phosphorescent
tors,239,240 LED emitters,241,242 lasers243 and thin-film tran- OLEDs.245
sistors244 has been rekindled.11 Many of these devices employ The beneficial impact of the reduced crystal size of
CH3NH3PbX3 (X = Cl, Br and I) as the active materials and, CH3NH3PbX3 (X = Cl, Br, I) on the luminescence efficiency
given the focus of this review being targeted beyond has also been shown in a separate work.246 In this work, the
CH3NH3PbX3, we will only cover a few examples to control over crystal size and shape has been achieved through
demonstrate the potential of the hybrid 3-D perovskites in mixing octylammonium (OA) cations into the reaction
this regards. In one example, photodetectors based on hybrid medium. Naturally, the presence of lower-dimensional hybrid
lead halide perovskites, with the ability to detect weak signals perovskites is suspected in this scenario; however, a clear
(approaching 1014 Jones), a linear dynamic range of over 100 identification of lower-dimensional perovskites has not been
dB (dB) and a fast photoresponse with 3-dB bandwidth of up carried out. The authors of this work note that photo-
to 3 MHz were recently fabricated, employing a ITO/ luminescence quantum efficiency (PLQE) values increase with
PEDOT:PSS/CH3NH3PbI3−xClx/PCBM/Hole blocking layer the increase of OA:MA (MA = methylammonium) ratio up to
(BCP and PFN)/Al structure.239 The authors note that the 0.6:0.4; however, higher OA content leads to the formation of
performance of this perovskite-based photodetector is signifi- platelets, which have lower PLQE.246 The reported average
cantly better than for most of the organic, quantum dot and PLQE values are 20, 30, 36 and 18% for 1.0 MA:0.0 OA, 0.7
hybrid detectors, and is comparable to inorganic semi- MA:0.3 OA, 0.4 MA:0.6 OA, and 0.1 MA:0.9 OA, respectively.
conductor-based devices. Excellent coherent light emission and the balanced ambipolar
One important advantage of organic−inorganic hybrid charge transport properties of CH3NH3PbX3 may allow their
perovskites for use as low-cost light-emitting diode (LED) use in electrically driven lasing.243 Measurements on a 65 nm
emitters is their very high color purity, with full width at half- thick CH3NH3PbI3 film spin-coated on a quartz substrate show
maximum of ∼20 nm for the electroluminescence spectral that there is a broad spontaneous emission (SE) with a full
peaks.242,245 Unlike conventional inorganic nanomaterials, due width at half-maximum (fwhm) of ∼50 nm, which narrows to a
to their intrinsic quantum-well structure, the high color purity is sharp peak with fwhm of <10 nm with increasing pump fluence,
preserved irrespective of the crystal size.241,242 Therefore, and transitions to an amplified spontaneous emission (ASE).
hybrid perovskites can overcome some of the disadvantages of Concurrently, the average transient photoluminescence life-
organic LEDs (OLEDs) and inorganic quantum dot LEDs, times also decrease and, above the threshold fluence of 12 μJ
including issues with complex synthesis, high cost, poor color cm−2, a superlinear increase in the emission intensity is
purity (OLEDs) and high ionization energy (quantum dot observed with photoluminescence lifetime experiencing a
LEDs).245 To show the potential of perovskite-based LEDs, a sudden shortening. The stable ASE observed for this material
thin (15−20 nm) layer of CH3NH3PbX3 (X = Cl, Br, I) was is attributed to the large absorption coefficient, low bulk defect
used to demonstrate electroluminescence in the near-infrared, densities and slow Auger recombination.243 By manipulating
green and red by tuning the halide composition.241 For the the halide content, the authors were able to demonstrate visible
infrared LED, the perovskite emitter was sandwiched between spectral tunability between 390 and 790 nm. Following these
two larger band gap semiconductors, TiO2 and poly(9,9′- findings, the authors note that organic−inorganic hybrid
dioctylfluorene) (F8) layers, in order to confine electrons and perovskites are a promising class of low-temperature solution-
holes in the lower gap CH3NH3PbI3−xClx perovskite layer for processable materials that show optical gain.243
effective radiative recombination in the ITO/TiO 2 / ASE and lasing behavior from CH3NH3PbX3 films have been
CH3NH3PbI3−xClx/F8/MoO3/Ag structure. The infrared reported from both cavity and noncavity modes by several
radiance for such devices was found to be 13.2 W/(sr·m2) at groups.243,247,248 The great potential of hybrid perovskites for
a current density of 363 mA/cm2, with highest external (EQE) application in solid-state electrical-pump lasers is further
and internal quantum efficiencies (IQE) of 0.76% and 3.4%, underlined by the reports of lasing from planar and spherical
respectively. The green LED with an ITO/PEDOT:PSS/ optical cavities.247,248 In addition, a recent report249 suggests
CH3NH3PbBr3/F8/Ca/Ag structure gave a luminance of 364 that hybrid perovskites can also be used in semiconductor
cd/m2 at a current density of 123 mA/cm2, yielding EQE and nanowire lasers, which are attractive due to their potential
IQE of 0.1% and 0.4%, respectively. In this device, PEDOT:PSS applications in nanoscale optoelectronic devices. Semiconduc-
and Ca were employed as Ohmic hole and electron injectors, tor nanowire lasers notoriously suffer from the high threshold
respectively, and the F8 polymer was used as a spacer layer for carrier density required for lasing. Interestingly,249 single crystal
electron transport and to prevent emission quenching near the nanowire lasers based on CH3NH3PbX3 perovskites demon-
Ca interface. strate low lasing thresholds (220 nJ cm−2) and high quality
Recently, a major improvement has been achieved through factors (Q ∼ 3,600).249 This very low lasing threshold
the demonstration of a green CH3NH3PbBr3 perovskite LED corresponds to carrier densities of as low as 1.5 × 1016 cm−3.
with EQE of 8.53%.245 Minimizing the presence of metallic Pb Other remarkable findings include very low charge carrier
impurity, which was achieved by using a slight 2−7% trapping in the CH3NH3PbX3 nanowires, and estimated lasing
CH3NH3Br excess, was proposed as being central to improving quantum yields approaching 100%. The wavelength tunability
the efficiency of the device. A second key factor was the fine provided by mixing of the halide content, the solution
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processability, and high lasing performance of the upon 380 nm excitation, resulting in a “warm” white light with
CH3NH3PbX3 nanowires make these materials excellent chromaticity coordinates (CIE) of (0.36, 0.41) and a correlated
candidates for a wide range of optoelectronic applications.249 color temperature (CCT) of 4669 K. The chromaticity of the
7.3.3. Optoelectronic Applications for Layered Perov- emission can be tuned through halide substitution in (N-
skites. Interest in light-emission from layered hybrid perov- MEDA)[PbBr4−xClx] (x = 0−1.2). As expected, the emission
skites predates the current work focused on use of 3-D spectra of the halogen-substituted perovskites demonstrate a
APb1−xSnxI3 perovskites as solar cell absorbers.11 Thus, in the systematic blue shift with increasing chloride content. The x =
early 1990s, orange electroluminescence (EL) was observed for 0.5 member possesses CIE coordinates of (0.31,0.36) and a
(C6H5C2H4NH3)2(CH3NH3)Pb2I7 below 200 K by applying a CCT of 6502 K, giving a “cold” white light. It is reported that
10 kV/cm electric field.250 Initial devices250−252 suffered from a the chloride substitution improves color rendering index (CRI),
dramatic reduction in EL efficiency near room temperature due which is a measure of how accurately colors are reproduced in
to thermal quenching of excitons. In an attempt to obtain comparison to a blackbody light source. CRI values of 82 and
room-temperature EL from hybrids, functional organic dye 85 are reported for (N-MEDA)[PbBr4] and (N-MEDA)-
molecules were incorporated between the perovskite layers in [PbBr3.5Cl0.5], respectively. These values are remarkable for
(H 2 AEQT)PbCl 4 (AEQT = 5,5‴-bis(aminoethyl)- single phase materials, as they are higher than the values for
2,2′:5′,2″:5″,2‴-quaterthiophene).253 EL devices based on basic fluorescent light sources (CRI ∼ 65), and are close to the
300-nm-thick (H2AEQT)PbCl4 light-emitting layers produce values for mixed-phosphor light sources (CRI > 90). Finally,
bright green-yellow light (λmax ≈ 530 nm) under ambient the photoluminescence quantum efficiency (PLQE) of (N-
conditions (Figure 32). For these devices, low turn on voltages MEDA)[PbBr4] was measured to be ∼0.5%. For mixed halide
members, the PLQE is improved up to 1.5% for (N-
MEDA)[PbBr2.8Cl1.2]. The PLQE values compare well with
the reported values of 2−3% for white-light emitting CdSe
nanocrystals in suspensions.87
The PLQE value of the layered lead bromide perovskites has
been improved up to 9% in another ⟨110⟩-oriented layered
perovskite (EDBE)[PbBr 4 ] (where EDBE = 2,2′-
(ethylenedioxy)bis(ethylammonium)).88 For (EDBE)[PbBr4],
CIE chromaticity coordinates of (0.39,0.42), a CCT of 3990 K,
which correspond to a “warm” white light, and a CRI value of
84 are reported. Interestingly, a crystalline sample of (EDBE)-
[PbBr4] enclosed in an evacuated quartz container showed
stable emission over 3 months of continuous irradiation with a
4-W (720 μW/cm2), 365 nm lamp. The authors note that the
broad white-light emission is not likely due to deep traps at
surface sites, as they observe similar emission and PLQEs from
larger single crystals.88 The broad emission has been attributed
to excitons trapped through elastic lattice deformations and
inhomogeneous broadening resulting from a distribution of
Figure 32. (a) Cross section of an OILED (organic−inorganic light- trap states.
emitting diode) device structure based on (H2AEQT)PbCl4 as the 7.3.4. Nonlinear Optical Applications. Compared to the
emitter. (b) A picture of the top view of an operational device with the Sn- and Pb-based hybrid perovskites, germanium-based hybrids
nickel on the right providing a scale for size comparison.11 Adapted are much less studied, presumably due to the instability of Ge2+
with permission from ref 11. Copyright 2001 IBM Journal of Research
and Development.
cations, with the divalent state being dictated by charge balance
for the majority of perovskite compounds discussed here. A
recent report on a family of quasi 3-D AGeI3 perovskites (A =
of ∼5.5 V were observed, and the I−V and EL−V curves were Cs+, CH3NH3+, HC(NH2)2+)204 (Figure 34), however, suggests
found to be similar, suggesting a balanced electron and hole that these compounds may not be as unstable as previously
injection.253 The observed electroluminescence spectrum is in thought. For these compounds, the first sign of oxidation was
agreement with the photoluminescence spectra of both detected only after 12 h in air, suggesting more stability than for
(H2AEQT)PbCl4 and the dye salt AEQT·2HCl. This spectral the divalent tin based compounds.60 We note, however, that
agreement indicates that the electroluminescence originates comparisons of stability among different compounds require
from the quaterthiophene moiety. The maximum efficiency of care, and it is important to take into account factors such as
0.1 lm/W at 8 V and 0.24 mA (power conversion efficiency of grain size and shape, as well as storage conditionse.g.,
0.11%) was recorded. environmental humidity, in light or in darkwhen comparing
More recently, lower-dimensional hybrid lead halides have different systems. It was found that AGeI3 compounds
been attracting renewed interest for solid-state lighting crystallize in polar space groups, and have direct band gaps of
applications. Broadband white light emission has been observed 1.6 eV for CsGeI3, 1.9 eV for CH3NH3GeI3 and 2.2 eV for
for (N-MEDA)[PbBr4] (where N-MEDA = N1-methylethane- HC(NH2)2GeI3, with band gaps increasing as the A+ cation size
1,2-diammonium) under ultraviolet excitation (Figure 33).87 increases.
(N-MEDA)[PbBr4] belongs to the family of ⟨110⟩-oriented The AGeI3 family of perovskites demonstrate remarkably
layered perovskites, featuring a corrugated perovskite sheet in strong, type I phase-matchable second harmonic generation
its structure and a band gap of 3.8 eV. (N-MEDA)[PbBr4] (SHG) response with high laser-induced damage thresholds of
shows a broad emission that spans the entire visible spectrum up to ∼3 GW/cm2 (Figure 35). Interestingly, contrary to the
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Figure 33. (a) Combined skeletal (top) and polyhedral (bottom, shaded) view of the ⟨110⟩-oriented layered structure of (N-MEDA)[PbBr4]
(where N-MEDA = N1-methylethane-1,2-diammonium). (b) Absorption (black) and emission (red, excitation at λex = 380 nm) spectra for (N-
MEDA)[PbBr4]. (c) Luminescence from a powder sample of (N-MEDA)[PbBr4] under 380 nm irradiation. (d) Chromaticity coordinates (CIE) of
white-light emitting (N-MEDA)[PbBr4−xClx] (x = 0−1.2) samples. Inset shows overlay of solar spectrum (orange) with the visible region shaded in
yellow and emission spectra of (N-MEDA)[PbBr4] (red, λex = 380 nm) and (N-MEDA)[PbBr3.5Cl0.5] (black, λex = 360 nm).87 Adapted with
permission from ref 87. Copyright 2014 American Chemical Society.

Figure 34. (a) Ball-and-stick representations of the crystal structures of a family of quasi 3-D AGeI3 perovskites with A = (a) Cs+, (b) CH3NH3+, and
(c) HC(NH2)2+. The inorganic framework is made of pyramidal GeI3− units with three regular bonds (thick lines, dGe−I = 2.733−2.772 Å). Three
additional elongated Ge−I contacts (dotted lines, dGe−I = 3.256−3.577 Å) from neighboring pyramidal GeI3− units complete the octahedral
coordination around Ge2+ in the GeI64− components.204

expected decrease of the SHG coefficient (χ(2)) with increasing hybridization of the Ge and I orbitals was confirmed by the
band gap, CH3NH3GeI3 (Eg = 1.9 eV) and HC(NH2)2GeI3 (Eg results of DFT calculations). It is also suspected that the polar
= 2.2 eV) exhibit much higher SHG efficiencies in their nature of the organic cations contributes to the increased SHG
transparent regions compared to that of CsGeI3 (Eg = 1.6 eV). response.
The second-order nonlinear susceptibility, χ(2), was determined As opposed to the polarity caused by the inorganic
to be 125.3 ± 10.5 pm/V for CsGeI3, 161.0 ± 14.5 pm/V for framework in 3-D CsGeI3, the use of chiral disulfide based
CH3NH3GeI3 and 143.0 ± 13.5 pm/V for HC(NH2)2GeI3. cations, such as a diprotonated cystamine cation, could also
These values are much higher than the reference material result in crystals forming in a chiral space group in lower-
AgGaS2 (36 pm/V), and similar to that for the record-holding dimensional systems. For example, α-[(NH 3 (CH 2 ) 2 SS-
(for band gaps >1 eV) chalcogenides KPSe6 (142.8 pm/V)254 (CH2)2NH3)PbI5]·H3O crystallizes in the P21 space group
and γ-NaAsSe2 (337.9 pm/V).255 The observed trends in band and contains only one enantiomeric form of cystaminium
gaps and SHG efficiencies are explained by the fact that larger cation. Note here that this compound features 1-D PbI5 chains
A+ cations result in more stereochemically active lone pairs on of corner-sharing octahedra similar to the chains in
Ge2+, which in turn leads to a widening of the band gap (sp- [(NH3(CH2)2SS(CH2)2NH3)2PbI5·I] (Figure 12). Upon heat-
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Figure 35. Wavelength-dependent second harmonic generation (SHG) scans for (a) CsGeI3, (b) CH3NH3GeI3, (c) HC(NH2)2GeI3, (d)
CH3C(NH2)2GeI3, and (e) AgGaS2. The measurements were carried out between λ = 1000 and 2700 nm, and the corresponding SHG range is λ/2
= 500−1350 nm. The dashed lines indicate the predicted SHG counts in the static limit. The absorption edge is drawn as a black line for each
compound for comparison. The arrows shown in (b)−(d) indicate the spectral ranges in which linear absorption of the input beam results in
significant decreases in the observed SHG counts. (f) Semilog plot of the relative SHG counts.204 Reprinted with permission from ref 204. Copyright
2015 American Chemical Society.

ing, a reversible phase transition to a racemic β-phase occurs at and inorganic structural fragments. A combination of suitable
75 °C.256 Such conformational chirality, which can be organic cations and inorganic perovskite frameworks, contain-
controlled using temperature, provides a convenient route for ing highly polarizable atoms such as iodide atoms, is therefore
preparation of switchable nonlinear optical (NLO) materials, promising for second order nonlinear optical applications.258,259
which has been successfully demonstrated for a related α- 7.4. Charge Storage Properties and Applications
[(NH3(CH2)2SS(CH2)2NH3)BiI5].257 The use of trivalent Bi3+
The layered perovskite structures, which enable facile and
instead of divalent Pb2+ allows preparation of hydronium controllable intercalation (described in section 5), suggest
(H3O+)-free crystals in the noncentrosymmetric space group possible application as battery cathodes. Recently, an organic−
P21cn. The reversible transition to a centric β-phase occurs at inorganic perovskite based on a copper(II) chloride framework
∼37 °C for this compound. The authors note that the material and an appropriately selected organic cation, (EDBE)[CuCl4]
is easy to prepare in thin film form using the drop casting (Figure 36), was cycled over 200 times at a rate of 28 mA g−1,
method, and that it demonstrates promising second (SHG) and as a lithium battery cathode with an open-circuit voltage of 3.2
third harmonic generation (THG) responses, which can be V (Figure 37).260 In order to mimic the temperature
further fine-tuned. fluctuations in large-scale battery installations, the authors
Layered perovskite derivatives with noncentrosymmetric allowed their cell to heat by the sun over a 24-h period. The
crystal structures can also be obtained, as shown by the n = measured average capacities over 225 cycles were 38(6) mA g−1
2 members of the ⟨100⟩-oriented family (C4H3SCH2NH3)2- at 40 °C and 26(4) mA g−1 at 22 °C (Figure 36, inset).260
(CH3NH 3)Pb2I7258 and (HO2C(CH2) 3NH 3)2(CH 3NH 3)- Impressively, capacity degradation was not observed during the
Pb 2 I 7 . 259 Interestingly, the related n = 1 members, cycling, however, the cell failed abruptly during the 227th
(C4H3SCH2NH3)2PbI4258 and (HO2C(CH2)3NH3)2PbI4,259 cycle.260 The authors note that this is indicative of a failure
crystallize in the centric space group Pbca. The difference through a short circuit and not material degradation and,
between the n = 1 and n = 2 members has been primarily therefore, this may be prevented by further optimizing the
attributed to the acentric nature of the Pb2I73− inorganic device structure.
bilayers, which in turn originates from the subtle shifts of the (EDBE)[CuCl4] consists of typical CuCl42− sheets with
apical iodide atoms induced by the organic cation-inorganic Jahn−Teller distortion (antiferrodistortive arrangement) within
framework interactions, leading to a loss of the center of the Cu d9 octahedra. The ether groups were selected to mimic
symmetry.258,259 By extension, the authors note that while the n the coordination environment of Li+ in ethereal solvents and, in
= 3 members such as (C4H9NH3)2(CH3NH3)2Sn3I10 are the solid state structure, adjacent polyether chains cross to
centrosymmetric, the n = 4 members could adopt non- create 0.7 Å-diameter channels (Figure 36).260 These channels
centrosymmetric structures.258 Importantly, these findings are likely involved in the process of lithium intercalation.
demonstrate that noncentrosymmetric hybrid perovskite Analogous structures with the specially targeted polyether
structures can be engineered by manipulating both the organic cation replaced by a simple alkyldiammonium group, with
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interest due to their remarkable light-harvesting properties and

high efficiencies above 20%, achieved in an unprecidented short
time period (∼5 years) using simple low-temperature, low-cost
processing. However, these materials suffer from the presence
of the toxic heavy element Pb and from poor stability in moist
air. Additionally, devices based on lead halide perovskites often
exhibit hysteretic electrical behavior, the magnitude of which
strongly depends on the device structure and fabrication
procedure. Other combinations of metal halides may encounter
similar challenges with regards to stability and hysteresis, given
the “soft” nature of the materials. Manipulation of the highly
versatile chemistry of hybrid organic−inorganic perovskites will
likely play an important role in addressing these issues.
In part due to charge balance requirements, most studies on
hybrid perovskites have focused on monovalent organic cations
on the A-site, divalent metals on the B-site, and a halide ion on
the X-site in 3-D ABX3 and lower dimensional perovskite
Figure 36. Combined skeletal (top) and polyhedral (bottom, shaded) structures. A departure from these constraints might provide
view of the crystal structure of (EDBE)[CuCl4], viewed down the c- one viable path to stabilizing prospective nontoxic-element
axis. Cyan, red, green, sky blue, and black spheres represent Cu, Cl, O, high-performance hybrid materials for electronic/optical and
N, and C atoms, respectively. The channels present in the organic energy applications. For example, partial or full substitutions on
component of the structure are suited to the intercalation of lithium the A-site (with organic cations in higher oxidations states of +2
ions for use in energy storage applications.260
or +3) and the X-site (with anions in more negative oxidation
states of −2 or −3) represents one logical next step for
consideration, and these in turn will allow necessary
substitutions on the B-site.262 Given the air-stability issues,
which at least in part originate from the highly ionic nature of
the hybrid halide perovskites, substitutions on the X-site
leading to more covalent bonding character would be especially
welcome. In fact, mixed-anion perovskites containing halide
and chalcogenide ions on the X-site would bridge two of the
richest classes of perovskites, one based on hybrid organic−
inorganic halide perovskites and the other on all-inorganic
chalcogenide/oxide perovskites.
Although rare, we note that several families of mixed-anion
all-inorganic perovskites are known, including oxychloride
Sr2CuO2Cl2,263,264 oxynitrides AMO2N and RMON2 (A =
Ca, Sr, Ba; R = La, Pr; M = Ta, Nb, Ti),265−268 nitride-fluoride
Ce2MnN3F2−δ,269 and oxyfluorides,270 such as K2NbO3F,271
Sr2CoO3F,272 ASrNb2O6F,273 and RbRTiNbO6F274 (A = Li,
Na, Rb; R = La, Pr, Nd), Sr3Fe2O4F4,275 Bi2TiO4F2, and
Figure 37. Capacity versus cycle number for a cell based on Bi2NbO5F,276,277 to name a few. These examples clearly
(EDBE)[CuCl4] that is cycled between 2.1 and 3.2 V vs Li+/0 at 28 mA demonstrate the wide array of substitutions possible in the
g−1. Inset: Capacity changes as the cell heats (from 22 to 40 °C) over a
24 h period.260 Reprinted with permission from ref 260. Copyright
mixed-anion compounds, suggesting that continued effort may
2014 American Chemical Society. enable the translation of the success in the preparation of
mixed-anion all-inorganic perovskites into prospective hybrid
organic−inorganic systems. When taking on this challenging
simply solid CuCl2 or with stoichiometric (but unreacted) task, however, as seen from examples within this review, one
mixtures of CuCl2 and EDBE, all exhibited lower capacities and has to be mindful about important parameters such as tolerance
unsuitability for cycling. Ultimately, this work shows the factors, ionic radii, electronegativities and preferential coordi-
potential for the organic group in hybrid perovskites to be used nation geometries as, under normal conditions, segregation of
to tailor designer materials for Li+ cycling in relatively nontoxic anions into distinct phases or separation into different
organic−inorganic metal halide electrodes, which can addition- structural segments in the same compound often dominates
ally be prepared with low-cost and abundant elements and the materials formation behavior.262,278 The latter scenario is
using very simple and inexpensive fabrication approaches.260 exemplified by the non-perovskite Sillén-type oxyhalides
ABiO2X (A = Ca, Sr, Ba, Cd; X = Cl, Br, I),279−281 which
8. CONCLUSION AND VISION FOR THE FUTURE despite a promising stoichiometry with regards to perovskite
Over the >100 years that organic−inorganic perovskites have formation exhibit alternating layers of halide and oxide anions
been known,261 a number of highly interesting structural, with metal cations sandwiched in between. In addition, the
magnetic, electrical and optical properties have arisen, primarily hybrid organic−inorganic perovskites exhibit low formation and
as a result of distinct properties of the organic or inorganic decomposition energies;282 therefore, harsh synthetic con-
component of the structure. Most recently, solar cells based on ditions, such as reactions at higher temperatures to induce
lead halide perovskite absorbers have been attracting worldwide mixing of anions, cannot be employed in most cases.
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Beyond PV, the very high degree of structural flexibility, To further reflect on how multifunctionality might be
excellent optoelectronic properties and ease of fabrication could imparted to complex organic−inorganic structures, exfoliation
enable use of hybrid organic−inorganic perovskites in photo- of (100)-oriented (RNH3)2An−1BnX3n+1-type pervskites is
detectors, LEDs, batteries and solid-state lighting applications. facilitated by the fact that each organic (RNH3)−inorganic
In addition, there are several reports of exciting multiferroic and (An−1BnX3n+1)−organic (RNH3) sandwich is typically only
nonlinear optical properties of hybrid perovskites. The full bonded to nearest neighbors through weak van der Waals
potential of the broad class of hybrid perovskites in these forces and can therefore be separated from its neighboring
applications is just starting to be uncovered. In a broader layers through ultrasonication in a suitable nonsolvent. For
context, however, for industrial scale implementation of hybrid example, recently, (C6H9C2H4NH3)2PbI4 and (C4H9NH3)2-
perovskites, demonstration of stable working devices and PbBr4 materials have been exfoliated and the properties of the
materials, at least at near-ambient temperatures, is necessary individual layers have been explored.292,293 The question then
and, in fact, many of the challenges for applications beyond PV comes up, can distinct sets of individual functional perovskite
are largely similar to those described for perovskite PV. One of sheets be reassembled to provide more complex functionality?
the often-cited and important advantages of hybrid perovskites Additionally, while organic−inorganic perovskites constitute a
is the simple low-temperature, low-cost processing, owing to subclass of crystalline hybrid organic−inorganic compounds
their low formation energies. On the flip side, as mentioned formed through corner sharing of metal-centered BX 6
above, the decomposition energies and hence decomposition octahedra; alternative connectivity of BX6 octahedra based on
temperatures are correspondingly low (<300 °C) and edge- or face-sharing is also possible.294 Furthermore, organic−
moisture/UV light can further accelerate the decomposition inorganic compounds based on other types of metal anion
process.9,282−287 Better understanding of the stability limi- polyhedra including tetrahedral BX4 units can also be
tations in the broader class of organic−inorganic perovskites envisioned (and perhaps merged with the perovskite structures
and related halides is therefore an important further research using the exfoliation-reassembly idea discussed above). A
target. systematic study of such types of non-perovskite crystalline
Continuing to look into the future, although there will still be organic−inorganic hybrids is currently lacking; however, it is
great latitude and interest to develop new hybrid perovskites in clear that these changes in the structures will lead to major
which properties of either the organic or inorganic component changes in the properties. The possibility of alternative
are targeted, truly multifunctional organic−inorganic hybrids coordination polyhedra and connectivity scenarios not only
may be the next important frontier. Useful attributes of organic adds another layer of complexity but also provides even more
materials include luminescence and optical response, electrical structural flexibility and tunability that could potentially result
transport, flexible processability and mechanical softness, in the emergence of many new useful applications. Preparative
whereas inorganic components can impart high electrical solid-state chemistry is renowned for a lack of predictability
mobility, tunable conductivity, magnetic and dielectric compared to organic synthesis; however, the continued study of
responsiveness, and thermal/mechanical robustness. Each structure−property relationships in hybrid organic−inorganic
component has a wide range of structural and electronic compounds is an important step for bringing reproducibility
tunability. Hybrid optoelectronic devices, for example, might and predictability to this diverse and interdisciplinary field.
benefit from having strongly absorbing/emitting organic
molecules included in the structure to facilitate light AUTHOR INFORMATION
absorption/emission, while leaving the long-range charge Corresponding Author
transporting function to the inorganic framework. Another *E-mail: [email protected].
possibility might be having transport of electrons and holes
Notes
segregated to different layers within the structure, with the
electronic nature of the interfaces targeted to avoid The authors declare no competing financial interest.
recombination. Third, absorbing/emitting and charge transport Biographies
might be confined to the inorganic layer and the organic
component might be utilized to mechanically or chemically Bayrammurad Saparov is a Department of Energy (DOE) Energy
protect the active layers from degradation (e.g., using the Efficiency and Renewable Energy (EERE) SunShot Postdoctoral
strongly hydrophobic character of a larger organic cation to Fellow at Duke University. He received his Diploma in Chemistry
repel moisture from the structure, as has already been from Lomonosov Moscow State University in 2006 and his Ph.D. in
demonstrated to some extent).288−291 In implementing these Inorganic Solid State Chemistry from the University of Delaware in
and other scenarios, for many applications it may be necessary 2011. Before joining David Mitzi‘s group at Duke in 2014, Dr. Saparov
to appropriately tailor the energy levels of the different was a postdoctoral researcher at Oak Ridge National Laboratory,
structural components and also control film growth so that focusing on the magnetism and superconductivity of transition metal
the layers are nominally perpendicular to the substrate. pnictides and chalcogenides, as well as investigating permanent
Alternatively, applications or device structures will be targeted magnets with reduced rare-earth content. He is currently interested
that favor lateral transport (relative to the substrate) rather than in materials design for energy applications, including affordable
vertical, as for the most commonly used device structure for chalcogenide and hybrid organic−inorganic perovskite solar cell
organic−inorganic field-effect transistors.196 The grand chal- absorbers.
lenge remains to create a self-assembling organic−inorganic David Mitzi is the Simon Family Professor of Engineering at Duke
hybrid with properties substantially greater than the sum of its University, with joint appointments to the Department of Mechanical
parts. One exciting aspect of the hybrid perovskites in this Engineering and Materials Science and the Department of Chemistry.
regards is that they can be prepared in single crystal form, and He received his B.S. in Electrical Engineering and Engineering Physics
therefore, the expected rich structure−property relationships from Princeton University in 1985 and his Ph.D. in Applied Physics
can be studied in great detail. from Stanford University in 1990. Prior to joining the faculty at Duke

4588 DOI: 10.1021/acs.chemrev.5b00715

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Chemical Reviews Review

in 2014, Dr. Mitzi spent 23 years at IBM’s T.J. Watson Research Hybrid Halide Perovskite Solar Cells. Nano Lett. 2014, 14, 2584−
Center, where his focus was on the search for and application of new 2590.
electronic materials, including organic−inorganic hybrids and (9) Mitzi, D. B. Synthesis, Structure and Properties of Organic-
inorganic materials for photovoltaic, LED, transistor, and memory Inorganic Perovskites and Related Materials. Prog. Inorg. Chem. 1999,
48, 1−121.
applications. For his final five years at IBM, he served as manager for
(10) Mitzi, D. B. Templating and Structural Engineering in Organic-
the Photovoltaic Science and Technology Department, where he
Inorganic Perovskites. J. Chem. Soc., Dalton Trans. 2001, 1−12.
initiated and managed a multicompany program to develop a low-cost, (11) Mitzi, D. B.; Chondroudis, K.; Kagan, C. R. Organic-Inorganic
high-throughput approach to deposit thin-film chalcogenide-based Electronics. IBM J. Res. Dev. 2001, 45, 29−45.
absorber layers for high-efficiency solar cells. Dr. Mitzi’s current (12) Cheng, Z.; Lin, J. Layered Organic-Inorganic Hybrid Perov-
research interests are making emerging photovoltaic materials more skites: Structure, Optical Properties, Film Preparation, Patterning and
effective, cost-efficient, and competitive for the energy market. He Templating Engineering. CrystEngComm 2010, 12, 2646−2662.
holds a number of patents, and has authored or coauthored more than (13) Mercier, N.; Louvain, N.; Bi, W. Structural Diversity and Retro-
190 papers and book chapters. Crystal Engineering Analysis of Iodometalate Hybrids. CrystEngComm
2009, 11, 720−734.
(14) Judeinstein, P.; Sanchez, C. Hybrid Organic-Inorganic Materials:
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part by the Office of Energy Efficiency and Renewable Energy Search of Synergic Activity. Adv. Mater. 2001, 13, 163−174.
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(EERE), U.S. Department of Energy, under Award Number
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Research Award administered by the Oak Ridge Institute for (18) Yamada, K.; Kawaguchi, H.; Matsui, T.; Okuda, T.; Ichiba, S.
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managed by Oak Ridge Associated Universities (ORAU) under Perovskite CH3NH3Sn1‑xPbxBr3 and CsSnBr3. Bull. Chem. Soc. Jpn.
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