REVIEWS

Metal halide perovskite nanostructures

for optoelectronic applications and the
study of physical properties
Yongping Fu   1, Haiming Zhu   2, Jie Chen1,3, Matthew P. Hautzinger   1, X.-Y. Zhu4
and Song Jin   1*
Abstract | Nanostructures of inorganic semiconductors have revolutionized many areas of
electronics, optoelectronics and photonics. The controlled synthesis of semiconductor
nanostructures could lead to novel physical properties, improved optoelectronic device
performance and new areas for exploration. Lead halide perovskites have recently excited the
photovoltaic research community owing to their high solar-​conversion efficiencies and ease of
solution processing; they also hold great promise for optoelectronic applications, such as light-​
emitting diodes and lasers. In this Review , we summarize recent developments in the synthesis
and characterization of metal halide perovskite nanostructures with controllable compositions,
dimensionality , morphologies and orientations. We examine the advantageous optical properties,
improved stability and potential optoelectronic applications of these 1D and 2D single-​crystal
perovskite nanostructures and compare them with those of bulk perovskites and nanostructures
of conventional semiconductors. Studies in which perovskite nanostructures have been used to
study the fundamental physical properties of perovskites are also highlighted. Finally , we discuss
the challenges in realizing halide perovskite nanostructures for optoelectronic and photonic
applications and offer our perspectives on future opportunities and research directions.

1
Department of Chemistry,
University of Wisconsin–
Madison, Madison, WI, USA.
2
Department of Chemistry,
Zhejiang University,
Hangzhou, China.
3
International Research
Center for Renewable Energy,
State Key Laboratory of
Multiphase Flow in Power
Engineering, Xi’an Jiaotong
University, Shaanxi, China.
4
Department of Chemistry,
Columbia University,
New York, NY, USA.
*e-​mail: jin@chem.wisc.edu
https://doi.org/10.1038/
s41578-019-0080-9
The properties and functions of semiconductor nano­
structured materials and devices are highly dependent on
dimensionality, which affects the electron–matter and
light–matter interactions1. Over the past three decades,
there has been substantial progress in the synthesis, pro­
cessing and characterization of conventional inorganic
semiconductor (for example, elemental, III–V and metal
chalcogenide) nanostructures, including nanocrystals,
1D nanowires (NWs) and 2D quantum wells. The major
motivation underlying these efforts is to elucidate how
the dimensionality, size, architecture and composition
influence the properties of such nanostructures in order
to design nanostructures with new and/or enhanced
properties and applications2. Semiconductor nanostruc­
tures could potentially revolutionize technological appli­
cations, such as integrated optoelectronic and photonic
devices, biosensors and energy conversion and storage
devices3,4.
Metal halide perovskites have emerged as a class of
semiconductors for high-​performance solution-​processed
optoelectronics, such as photovoltaics5,6, lasers7–10 and
light-​emitting diodes (LEDs). Compared with bulk per­
ovskites and nanostructures of conventional semiconduc­
tors, halide perovskite nanostructures show advantageous
optical and electrical properties, such as high photolu­
minescence quantum yields (PLQYs), strong anisotropic
absorption and/or emission, higher exciton binding ener­
gies and widely tuneable bandgaps, and thus could offer
many exciting and potentially unique opportunities for
optoelectronics. In this Review, we survey the synthesis,
characterization, properties and optoelectronic applica­
tions of perovskite nanostructures and microstructures,
with a focus on 1D nanowires and microwires and 2D
quantum wells. Note that we define a structure as a nano­
structure if it has at least one dimension that is <1 µm and
a structure as a microstructure if the minimum dimen­
sion is >1 µm. We also examine nanostructuring as an
approach to accessing metastable polymorphs of bulk
perovskites and highlight how surface functionalization
can increase the structural stability of perovskite nano­
structures. For discussions on colloidal perovskite
nanocrystals, we refer readers to recent reviews11,12.
Structural chemistry and properties
Owing to their crystal structure (Box 1), halide per­
ovskites (ABX3, where A is a cation, B is Pb2+ or Sn2+ and
X is a halide) have vastly different chemistry and physics
from those of conventional inorganic semiconductors.

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For example, to achieve high performance in semicon­
ductors, it is usually necessary to obtain ultralow den­
sities of impurities and defects by carefully controlled
crystal growth. By contrast, optoelectronic devices can
Box 1 | Crystal structures of 2D ruddlesden–Popper and 3D metal halide perovskites
3D perovskites have the general structural formula aBX3 (see the figure, panel a), where a is
a cation, such as methylammonium (CH3NH3+, Ma+), formamidinium (NH2CHNH2+, Fa+) or
Cs+; B is a metal (typically Pb2+ or sn2+); and X is a halide. the crystal structure consists of a
3D network of corner-​sharing [BX6]4− octahedra with a 12-fold coordinated a cation
occupying the site in the middle of the cube surrounded by 8 octahedra. Compounds with
the aBX3 stoichiometry often have multiple structural polymorphs and complex phase
behaviour, with the crystal structures differing in the connectivity of the [BX6]4− octahedra.
the Goldschmidt tolerance factor (t) provides an empirical rule for predicting the
stability and lattice distortion of perovskite structures: t = (rA + rX) ∕  2 (rB + rX), in which
ra, rB and rX are the effective radii of the a, B and X ions, respectively. a t value between 0.8
and 1 is favourable for cubic (0.9 < t < 1) or distorted (0.8 < t < 0.9) perovskite structures;
however, larger (>1) or smaller (<0.8) t values usually result in non-​perovskite structures
(see the figure, panel b). although there are several aBX3 compounds with various a
cations, only Cs+, Ma+ and Fa+ meet the requirement for the adoption of a 3D perovskite
structure. Other cations are either too small (such as K+ and rb+) or too large (for example,
dimethylammonium (DMa+), ethylammonium (ea+), guanidinium (Ga+) and acetamidinium
(aa+)). Moreover, perovskites at the limit of the tolerance factor requirement, such as
FaPbi3 (t ≈ 1) and CsPbi3 (t ≈ 0.8), are metastable at room temperature.
ruddlesden–Popper (rP) layered perovskites have the general formula (La)2(a)n−1BnX3n+1,
where La+ is a long-​chain alkyl or aromatic ammonium cation and n is an integer (see the
figure, panel c). these structures can be regarded as 2D slabs sliced from the corresponding
cubic 3D perovskite along the (100) crystallographic plane. the extended 2D unit layers of
inorganic sheets consist of corner-​sharing metal halide octahedra interspaced by the large
La+ cations. each inorganic layer of a rP phase has the same thickness, indicated by the n
value. when n is infinite, the structure becomes a 3D perovskite of aBX3. when n is small,
the structure exhibits intrinsic quantum and dielectric confinement effects owing to the
few-​unit-cell thickness of the high-​dielectric inorganic layers, which are separated by
organic layers with a lower dielectric constant. therefore, these rP perovskite phases can
be considered as bulk assemblies of tuneable isolated quantum wells of 3D perovskites.
a b
1.1
1.0
3D perovskite
0.9
structure
t
0.8
0.7
A monium) NWs with a diameter of a few hundred nano­
B K+ Rb+ Cs+ MA+ FA+ DMA+ EA+ GA+ AA+
ABX3 X Size of A cation
c RP layered perovskites 3D perovskite
LA+ ···
n=1
n=2 n=∞
n=3
be easily fabricated from polycrystalline perovskite thin
films deposited from solution at low temperature and
are highly efficient despite the high density of defects. It
appears that intrinsic point defects in perovskites do not
act as detrimental trap states13. This defect tolerance is
one of the most advantageous photophysical properties
of perovskite semiconductors and is attributed to the
unusual defect physics and the highly polarizable crystal
lattice in the presence of charge carriers14–17. Calculations
have revealed that the most dominant defects occur at
energies near the band edges or within the bands18 owing
to the unique antibonding character of the valence band
maximum and spin–orbital coupling. In addition, halide
perovskites have soft and polar lattices19 with Young’s
moduli approximately ten times lower than those of Si or
GaAs (ref.20). The soft, polar lattices exhibit soft phonon
modes, strong anharmonicity and dynamic disordering.
Moreover, the softness of the perovskite lattice results in
strong electron–phonon coupling and leads to the for­
mation of large polarons21, which have been proposed
to screen the Coulombic potential and reduce scattering
with other carriers and charged defects.
Compared with conventional semiconductors, the
distinct surface properties of perovskites that result from
the ionic nature and defect tolerance have considerable
implications for the physical properties of perovskite
nanostructures. Owing to the increased surface-​to-
volume ratio in nanostructures, surface recombination
results in a substantial loss of charge carriers and sig­
nificantly influences the optoelectronic properties of
semiconductor nanostructures. However, the surface
recombination velocities of perovskites are several
orders of magnitude lower than those of conventional
semiconductors22,23. For conventional semiconductor
nanostructures, mid-​gap states created by dangling
bonds on the surface need to be passivated with chem­
ical ligands or protective shells to ensure high perfor­
mance. By contrast, the surface defects of perovskites
formed by undercoordinated lead atoms create only
shallow traps24 and can be readily passivated under
growth conditions. These features minimize the detri­
mental effects of an increase in surface area on the pho­
tophysical properties of perovskite nanostructures. As
an example, single-​crystal MAPbI3 (MA+  = methylam­
metres exhibit long carrier lifetimes (0.1–1 µs) and long
carrier diffusion lengths (on the order of 10 µm)10,25,26,
substantially exceeding those of most conventional
semiconductors27,28. However, although perovskites are
more defect tolerant, they are not defect impervious, as
exemplified by the fact that surface ligand functiona­
lization can enhance the light emission properties of
perovskite nanocrystals.
Despite the simplicity of the crystal structure, halide
perovskites exhibit an enormous variety of structural
modifications and variants with tailored properties.
Bandgap engineering has been a powerful approach
for designing semiconductor nanostructures with
desired optical properties for specific applications.
Compared with conventional semiconductors, one of
the most attractive features of perovskites is their fac­
ile bandgap engineering, which can be achieved by
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controlling stoichiometry and/or dimensionality 29.
For example, changing the halide in ABX3 enables the
emission to be tuned from deep blue to near-​infrared
(IR, 400–820 nm), and changing the metal element
further extends the emission up to 960 nm. Moreover,
2D quantum-​confined perovskites can be obtained in
a bulk form — that is, 2D Ruddlesden–Popper (RP)
phases (Box 1) — through the introduction of larger
ammonium cations, such as butylammonium (BA+).
Quantum confinement can further shift the bandgap
by >1 eV. Therefore, by changing the well thickness and
composition, it is possible to tune the emission across the
entire UV to the near-​IR spectrum. Such broad bandgap
tunability has rarely been demonstrated in conventional
semiconductors.
1D perovskite nanowires
Semiconductor NWs exhibit 1D charge and photon-​
transport properties that can be exploited for next-​
generation optoelectronic and photonic devices. They
are also excellent systems for exploring phenomena at
the nanoscale. To date, semiconductor NWs have pri­
marily been composed of group IV, II–VI and III–V
semiconductors, which have strong and primarily
covalent bonds. The ability to synthesize high-​quality
single-​crystal semiconductor NWs with controlled
diameters, orientation, chemical composition and
phase has enabled breakthroughs in various functional
devices fabricated through bottom-​up approaches3,4.
Central to this success has been the discovery and devel­
opment of vapour–liquid–solid growth, which enables
1D anisotropic growth of various NW compositions2.
In vapour–liquid–solid growth, a catalytic nanodroplet
of a eutectic liquid alloy adsorbs a vapour precursor to
supersaturation levels, subsequently inducing 1D aniso­
tropic growth at the liquid–solid interface between the
catalyst and semiconductor.
Compared with covalent inorganic semiconduc­
tors, ionic perovskite lattices are much softer and more
dynamically disordered. The ionic nature results in high
solubility in water and polar solvents as well as a low
energy barrier for crystal formation30, which enables
low-​temperature synthesis and facile ion exchange. For
example, unlike conventional semiconductors, which
require high-​temperature growth, highly crystalline
perovskites can form within seconds even at room tem­
perature. These unique features of perovskites provide
new opportunities for simple and facile nanostructure
growth. In this section, we review the various synthetic
approaches for growing 1D perovskite NWs and their
arrays with controlled composition and orientation and
discuss the mechanisms that underpin high-​quality 1D
anisotropic growth.
Solution-​phase recrystallization growth. One attrac­
tive feature of perovskites is the possibility of using low-​
temperature solution-​processing methods to prepare
high-​quality single crystals and thin films. Facile solu­
tion conversion of metal halides into organic–inorganic
hybrid perovskites can be achieved by dipping metal
halide films into solutions containing organic halide
salts31. Despite the widespread use of such a conversion
Nature Reviews | Materials
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method for thin-​film preparation, the underlying con­
version pathways have only recently been elucidated10,32.
At low concentrations of the organic halide salt (AX), the
organic halide rapidly intercalates into the metal halide,
resulting in the direct formation of ABX3. However, at
high concentrations of AX, the solution conversion can
also proceed via a slow dissolution–recrystallization
process (Fig. 1a) that involves the formation of a soluble
intermediate:
PbX 2(s) + 2X −(sol) → [PbX 4]2− (sol)
[PbX 4]2− (sol) + A+(sol) → APbX 3(s) + X −(sol)
Mechanistic insight into the dissolution–recrystalli­
zation process enabled the first direct solution growth of
single-​crystal perovskite NWs with suitable dimensions
for NW lasers10. For example, MAPbI3 NWs were syn­
thesized by placing a lead acetate (PbAc2) film in contact
with a highly concentrated MAI solution10. A thin poly­
crystalline layer of MAPbI3 rapidly forms on the PbAc2
surface and serves as the seed to initiate NW growth.
This initial perovskite film also acts as a diffusion bar­
rier that prevents further direct reaction between the
solution-​phase MAI and the unreacted PbAc2 under­
neath. However, slow dissolution of the unreacted PbAc2
and the initial perovskite layer to produce the soluble
complex ion [PbI4]2− is thermodynamically favourable
at high concentrations of MAI. The slow generation of
[PbI4]2− ions thus maintains a low supersaturation con­
dition that promotes 1D anisotropic crystal growth33.
Spontaneous formation of single-​crystal hollow tubes
has also been observed, which suggests that the catalyst-​
free anisotropic growth of perovskite NWs may be
driven by screw dislocations33.
The dissolution–recrystallization NW growth
method is generally applicable to a wide range of per­
ovskites with different cations and/or anions34–36. The
keys to successful NW growth using this approach
include choosing a solvent with a high AX solubility
but low solubility for the perovskite products, ensur­
ing that the concentration of AX is high enough to
chemically transform the solid lead precursors into the
corresponding perovskites and selecting a suitable lead
precursor that can rapidly form an effective perovskite
barrier and seeding layer to help maintain low super­
saturation and induce NW growth. For example, single-​
crystal CsPbBr3 NWs with rectangular cross sections
and well-​defined end facets can be readily grown by
reacting a PbX2 film with a CsBr solution in methanol35
(Fig. 1b,c). By adjusting the ratios of different halides
or A cations in the precursor solutions, it is possible
to obtain alloyed NWs of mixed halides or mixed A
cations with controlled compositions 34,37. Vertical
MAPbBr3 NW arrays can also be grown by depositing
a PbAc2 film on an indium tin oxide–glass substrate
coated with poly(3,4-ethylenedioxythiophene):poly­
styrene sulfonate38. However, with the solution-​phase
recrystallization method, there is limited control over
the morphology and size of the products; for example,
microplates are also produced.
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a Perovskite NW b c

[PbX4]2–

PbAc2
Glass substrate 10 μm 1 μm 1 μm

d e
160

Thickness of PbI2
120

plates (nm)
MAX PbX2 NWs 80
Gas flow or
nanoplates
40

Heating element 40 80 120 160 200 240 280

Thickness of MAPbI3 plates (nm)

f g

)
(100
0)
(01

1]
[00
(110)

10 μm 500 μm

PDMS template
h i

μm
10
Silicon 10
substrate μm

50 nm 0.1 M MABr·PbBr2 50 μm
in DMF

Fig. 1 | Growth and characterization of aPbX3 perovskite NWs and nanoplates. a | Illustration of the growth of
APbX3 (A is an organic cation and X is a halide) perovskite nanowires (NWs) via the dissolution–recrystallization process
(Ac− is acetate). b | Scanning electron microscopy (SEM) image (left) of CsPbBr3 nanostructures grown by the dissolution–
recrystallization process illustrated in panel a. Magnified SEM image (right) showing an array of NWs with flat end facets
and rectangular cross sections. c | Low-​resolution transmission electron microscopy (TEM) image of a representative
CsPbBr3 NW. The inset is the corresponding selected area diffraction pattern along the [110] zone axis (ZA) of the
orthorhombic perovskite structure. d | Illustration of the reaction setup for growing perovskite NWs and nanoplates by
the vapour-​phase conversion method (MA+  = methylammonium). e | Thickness of a series of PbI2 plates before (images
above the line) and after (images below the line) being converted into MAPbI3 using the vapour-​phase conversion method.
The morphology of the nanostructures is preserved after conversion. f | Optical microscopy image (left) of CsPbBr3 NW
networks grown on muscovite mica by vapour-​phase epitaxy. The inset shows a corresponding 2D fast Fourier-​transform
image and demonstrates that these NWs are oriented with a hexagonal symmetry. Illustration of the morphology of these
CsPbBr3 NWs (right). g | SEM image of an array of CsPbBr3 NWs grown on a sapphire substrate. h | TEM image of
colloidal CsPbBr3 NWs synthesized by the hot injection method. The inset shows the emission colour upon UV excitation.
i | Patterned templates can be used to confine perovskite growth and to fabricate perovskite NW arrays on arbitrary
substrates. In the first step (left), a polydimethylsiloxane (PDMS) template with rectangular grooves is pressed into a stock
solution of MABr·PbBr2 in N,N-​dimethylformamide (DMF), which fills the voids. Following evaporation of the solvent, the
PDMS template is removed, leaving the NW array on the silicon substrate. The SEM image (right) shows the morphology
of the resultant horizontally aligned MAPbBr3 NW array. Panel a is adapted from ref.10, Springer Nature Limited.
Panels b and c are adapted with permission from ref.35, ACS. Panel e is adapted with permission from ref.41, Wiley-​VCH.
Panel f is adapted with permission from refs43,48, ACS. Panel g is adapted with permission from ref.52, ACS. Panel h is
adapted with permission from ref.56, ACS. Panel i is adapted with permission from ref.63, ACS.

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Vapour-​phase conversion method. The low formation
energy of halide perovskites implies that they are highly
defective. Schottky-​type defects are exclusively observed
with a predicted concentration of >0.4% in MAPbI3
(ref.39). Such high concentration of vacancies enables
ions to readily migrate in the lattice through a vacancy-​
mediated diffusion mechanism40. Consequently, ion dif­
fusion coefficients in MAPbI3 are remarkably high, for
example, ~10−12 cm2 s−1 for I− at room temperature. The
high ion mobility presents opportunities for designing
innovative synthesis approaches. As a notable example,
MAPbI3 thin films can be easily synthesized by expos­
ing PbI2 films in gaseous MAI at elevated temperatures.
Compared with the solution-​recrystallization method,
a major difference of the gas-​phase reaction is that the
formation of volatile lead iodide complex ions is highly
unfavourable. The solid–gas reaction instead proceeds
by the diffusion of MAI through the perovskite layer
that is initially formed to react with the remaining PbI2
underneath. The reaction temperature is selected to be
below the decomposition temperature of the perovskites,
but sufficiently high pressures of gaseous MAI and fast
ion diffusion kinetics drive the chemical transformation.
Vapour-​phase conversion has been applied to syn­
thesize perovskite nanostructures by reacting pre-​grown
lead halide nanostructures with gaseous MAI (ref.41)
(Fig. 1d). For example, PbI2 nanoplates were grown on
mica by physical vapour deposition and then converted
into MAPbI3 nanoplates by intercalating MAI into the
layered PbI2 structures. After conversion, the thick­
nesses of the nanoplates increased by a factor of 1.8, but
the lateral dimensions and morphology were retained
(Fig. 1e). Perovskite NWs can also be synthesized using the
vapour-​phase approach, with the crucial step being
the growth of PbI2 NWs. Although the single-​crystal
PbI2 NWs are grown by vapour-​phase deposition, the
converted perovskite NWs are polycrystalline with
randomly oriented domains and exhibit much rougher
surfaces than those of solution-​grown NWs, probably
owing to the strain caused by volume expansion during
the conversion42. However, the polycrystalline nature
may in turn facilitate the conversion to the perovskite
by improving ion diffusion through grain boundaries.
Vapour-​phase conversion is also a promising method for
synthesizing heterostructures of perovskites with other
materials
Direct vapour-​phase growth. Traditional semiconduc­
tor NWs formed by high-​temperature vapour-​phase
growth are typically of superior crystalline quality
and have lower defect densities than those grown by
solution methods. Direct vapour-​phase growth of
hybrid perovskites is more challenging because ther­
mal decomposition can occur before vaporization.
However, vapour-​phase synthesis is an attractive option
for growing nanostructures of more thermally stable
all-​inorganic perovskites43–45. CsPbX3 has a lower melt­
ing point (~450 °C) than conventional semiconductors
(for example, ~1,400 °C for Si and ~1,200 °C for GaAs),
which enables CsPbX3 NWs to be synthesized through
a relatively low-​temperature physical vapour deposition
process. Moreover, unlike vapour–liquid–solid NW
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growth, which requires a metal catalyst, NWs of CsPbX3
can be grown by direct vapour growth without a catalyst,
which eliminates concern about metal contamination in
the NW products.
Recently, vapour-​phase growth has enabled addi­
tional control of the orientation of perovskite NWs by
using the epitaxial relationship between the perovskite
lattice and various substrates. Facile heteroepitaxial
growth of perovskite NWs, microwires and nanoplates
on various substrates, such as mica43,46,47, sapphire48,
sodium chloride49,50 and oxide perovskites51, has been
demonstrated. Examples include the heteroepitaxial
growth of horizontally oriented CsPbX3 (X− = Cl−, Br−
or I−) interconnected NW networks with hexagonal
symmetry on mica substrates43,46 (Fig. 1f). The CsPbX3
NWs exhibit a triangular cross section and grow along
the [001] crystallographic orientation of the cubic per­
ovskite phase, exposing side walls that correspond to the
{100} facets. The anisotropic growth of these horizontal
wires may be due to asymmetric lattice mismatch, which
leads to unrestricted growth along the [001] direction
but limits the width in the [110] direction43. The lattice
mismatch between CsPbCl3 and CsPbI3 is as large as
~10%; therefore, the facile epitaxy of various CsPbX3
perovskites on mica suggests that the soft perovskite
lattice can tolerate a larger lattice mismatch than tradi­
tional semiconductors. In addition, the facile synthesis
of large-​scale NW arrays or interconnected networks by
epitaxial growth could facilitate direct integration into
practical devices48,52.
Graphoepitaxy on a faceted sapphire plane is another
approach used to guide the growth of CsPbBr3 NWs with
lengths on the scale of millimetres48,52 (Fig. 1g). Owing to
strain accumulation, conventional NWs (for example,
CdS) grown by graphoepitaxy often have a high degree
of non-​uniformity in their crystallographic orientation
and rougher surfaces than NWs grown on flat surfaces.
By contrast, guided CsPbBr3 NWs have the same crys­
tallographic orientation and surface smoothness as the
analogous NWs grown on flat substrates. Again, this is
attributable to the soft perovskite lattice, which enables
the perovskite NWs to easily compensate for the strain
and hence adapt to different substrate morphologies.
Colloidal nanowire synthesis. Following the success
of the colloidal synthesis of perovskite nanocrystals53,
morphological engineering into 1D NWs has been
achieved by modifying the reaction conditions. These
colloidal perovskite NWs generally have much narrower
diameters than the NWs synthesized by other methods.
NWs of MAPbI3 were first observed among nanocrystals
synthesized by an antisolvent recrystallization method54.
Owing to the ionic nature of perovskites, they are highly
soluble in polar aprotic solvents but almost insoluble in
the less polar antisolvent. Upon adding a perovskite
solution into an antisolvent, the decrease in solubility
leads to high supersaturation and the rapid precipitation
of perovskite nanocrystals. However, with this method,
there is poor control of the morphology of the prod­
uct54. The hot injection method is a more controllable
synthetic route for the preparation of colloidal per­
ovskite NWs55–57, including high-​aspect-ratio CsPbBr3
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NWs with a diameter of ~10 nm and lengths of up to
10 μm (Fig. 1h), as well as quantum wires with a diame­
ter ~2.2 nm less than the exciton Bohr radius (~7 nm).
These ultrathin quantum wires show significantly blue-​
shifted photoluminescence (PL) and a larger Stokes shift
than that of bulk-​like NWs (>10 nm).
Colloidal NWs of perovskites are highly dynamic,
as demonstrated by the morphology evolution during
the reaction55, which is probably attributable to dynamic
ligand binding to the surfaces. In another method,
CsPbX3 NWs were synthesized via transformation of
the CsPbX3 nanocrystals that initially form under pro­
longed ultrasonication of the solid perovskite precursors
in a mixture of solvent and ligand58. Although the NW
growth mechanism in colloidal synthesis is not fully
understood, the surface ligands have a crucial role in
enabling a 1D morphology59. The dynamic structural
transformation between different morphologies implies
a complicated and kinetically driven NW growth mecha­
nism. Recent studies suggest that 1D growth may occur
through self-​assembly and oriented attachment of the
initial cuboidal nanocrystals58. The long-​term retention
of structural integrity and optical properties of these col­
loidal NWs during storage or processing is a problem for
their potential practical application.
Space-​confined nanowire growth. Space-​confined
growth is a promising route to creating arrays of per­
ovskite NWs with controlled dimensions and precise
positions. Dense vertical perovskite NW arrays were
formed inside anodized aluminium oxide templates
by confining the crystallization of perovskites during
either solution-​phase or vapour-​phase deposition60,61.
The templates may further act as stabilizing scaffolds to
protect perovskites from moisture and air. Anodized alu­
minium oxide templates can also be used to extrude the
perovskite solution to yield free-​standing quasi-​vertical
NW arrays by applying a pressure gradient62. Large-​scale
oriented perovskite NW arrays on arbitrary substrates
were fabricated by combining a top-​down microfabrica­
tion technique with bottom-​up solution growth63–65. For
example, a polydimethylsiloxane template with rectan­
gular grooves was used to spatially confine the crystal­
lization of MAPbBr3, leading to directional NW growth
along the grooves (Fig. 1i). The dimensions, positions and
density of the NWs can be controlled by adjusting the
groove templates and the precursor concentration. This
space-​confined strategy has also enabled the growth
of nanoplate arrays 66 and large-​area single-​c rystal
films with up to submillimetre lateral dimensions and
thicknesses of tens to hundreds of nanometres67.
Nanowire growth via intermediate adducts. Aniso­­­tropic
crystallization of MAPbI3 from N,N-​dimethylformamide
(DMF) or dimethylsulfoxide solution is commonly
observed and probably proceeds via formation of an
intermediate adduct. Direct evaporation from a thin
layer of saturated solution of MAPbI3 on a glass sub­
strate often yields microwires and NWs68. By modifying
the crystallization conditions, this inherent anisotropic
growth can be controlled to prepare large-​area aligned
MAPbI3 microwire arrays69,70. Moreover, thin films of
MAPbI3 can be readily converted into NWs by DMF
treatment71,72, and submillimetre-​scale MAPbI3 micro­
wires have been obtained within several minutes by
adding a small amount of DMF during the solution-​
phase recrystallization73. In the latter case, microwires
of an intermediate phase consisting of PbI2–MAI–DMF
adducts rapidly formed and were converted into
the perovskite phase upon isolation from solution. The
resulting MAPbI3 products retain the 1D morphology
of the intermediate adducts. Despite the facile synthesis,
NWs grown via the formation of intermediate adducts
are polycrystalline and exhibit a rough surface and poor
uniformity, which make them less suitable for optical
and photonic applications.
Ion exchange of existing perovskite nanowires. Owing
to the large surface-​to-volume ratio, ion-​exchange reac­
tions in NWs are generally faster than those in bulk
materials. In metal chalcogenide NWs, examples of
complete chemical transformations are limited to NWs
with small diameters (up to several tens of nanometres).
Partial exchange reactions that result in heterogeneity
are very common in NWs74. However, the dynamic
and defective halide perovskite lattice promotes the
ion-​migration kinetics. Consequently, ion-​exchange
reactions in halide perovskites are surprisingly fast,
even at room temperature75, and can occur at solid–
liquid, solid–gas and solid–solid interfaces. For example,
starting from wires of CsPbBr3 (with diameters of up to
1 µm), the conversion into CsPbI3 or CsPbCl3 wires or
mixed halide alloys by anion exchange was completed
within a few minutes35,56. This anion exchange is an alter­
native approach to accessing a series of NWs of metasta­
ble perovskite phases, including CsPbBr3−xIx and CsPbI3,
which are difficult to directly synthesize owing to phase
instability. The NWs formed through anion exchange
showed well-​preserved morphologies and uniform alloy­
ing of halides in the alloyed NWs, which is an indication
of the soft perovskite lattice. Ionic exchange provides a
powerful method for accessing NWs with arbitrary
compositions and for constructing heterostructures.
Nanowire heterostructures. Creating functional het­
erojunctions in perovskite NWs is important for con­
structing advanced optoelectronic and photonic circuits.
The diversity of perovskites could enable facile heteroep­
itaxial integration of multifunctional materials in single
NWs. Moreover, bandgap mismatch at the junction gives
rise to the possibility of controlling and manipulating the
generation, recombination and transportation of charge
carriers. The investigation of charge-​carrier dynamics
across heterointerfaces is also crucial to the design and/or
improvement of solar cells and optoelectronic devices.
Despite the promise of multifunctional perovskite
heterostructures, the facile ion migration in 3D per­
ovskites imposes challenges in creating stable hetero­
junctions. Varying the reactants during growth can yield
stable and sharp heterojunctions in traditional semicon­
ductor NWs2,3. By contrast, 3D perovskites can rapidly
exchange their halide anions with the surrounding ions,
which leads to the formation of homogeneous alloys.
A spatially selective conversion of CsPbBr3 NWs into
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 Reviews

e
100 p–n heterojunction
a c
80
Y-CsSnI3 B-CsSnI3

Current (pA)
60 EC
1.3 eV
40 EF
2.5 eV
20
EV
3 μm 10 μm 0

–3 –2 –1 0 1 2 3
b d Voltage (V)
495 600
– Electron f
+ Hole
490 550 Surface potential (mV)
Height (nm)

485 500 – –
– – – – – – – 5 μm
CB
480 450 VB + + + + + + + + +
400
1 μm
475
Narrow bandgap Wide bandgap
3.0 4.5 6.0 7.5 9.0
Length (µm)

Fig. 2 | Growth and characterization of perovskite NW heterostructures. a | Optical image of a CsPbBr3/CsPbCl3

nanowire (NW) heterostructure with a sharp junction under laser excitation. b | Surface potential profile (red) across the
junction in the NW heterostructure shown in panel a with the corresponding atomic force microscopy height profile
(black). c | Optical image of a CsPbBr3/CsPbCl3 NW heterostructure with a gradient junction under laser excitation.
d | Illustration of the charge-​carrier-funnelling process in a halide-​gradient NW heterostructure. e | Current–voltage curve
of a p–n heterojunction in a CsSnI3 NW, showing current-​rectifying functionality. The p–n heterojunction is formed through
a localized phase transition between a black perovskite phase (B-​CsSnI3, p-​type) and a yellow non-​perovskite phase
(Y-​CsSnI3, n-​type). The inset shows the energy band alignment under thermal equilibrium. f | The p–n heterojunctions within
the CsSnI3 NW described in panel e can be observed using scanning electron microscopy (top) and cathodoluminescence
microscopy (bottom). The dark–bright segments correspond to the Y-​CsSnI3 and B-​CsSnI3 phases, respectively , within a
CsSnI3 NW. EC, energy of the conduction band (CB) minimum; EF, Fermi energy ; EV, energy of the valence band (VB)
maximum. Panels a and b are adapted with permission from ref.76, PNAS. Panel c is adapted with permission from ref.77,
ACS. Panel d is adapted with permission from ref.78, ACS. Panels e and f are adapted with permission from ref.80, PNAS.

CsPbBr3/CsPbCl3 NW heterostructures was achieved by
carrying out a local anion-​exchange reaction76. The het­
erostructure features two-​colour emission with a sharp
interface (Fig. 2a). An abrupt change of ~190 mV in the
relative surface potential is observed across the hetero­
junction interface, confirming that the two segments
have distinct electronic properties (Fig. 2b). However,
solid-​state halide interdiffusion across the heterojunc­
tion can readily occur, and this phenomenon can be used
to produce axial NW heterostructures with a bandgap
energy gradient77,78 (Fig. 2c). For example, a NW with a
halide gradient, MAPbBrxI3−x, was obtained by placing a
MAPbBr3 single crystal in contact with a MAPbI3 NW
at one end. The resulting NW heterostructure forms an
energy funnel along the axial direction, which drives
the unidirectional transport of charge carriers from the
wide-​bandgap region to the narrow-​bandgap region
(Fig. 2d). An interesting approach to creating heterojunc­
tions is to use light-​induced phase segregation in mixed
halide perovskites. For example, under photoexcitation,
a heterojunction forms between the I-​rich and Br-​rich
phases79 that result from the spinodal decomposition
of homogeneous MAPbBrxI3−x alloys. Very recently, a
current-​rectifying p–n junction was created in a sin­
gle CsSnI3 NW (Fig. 2e) through a localized thermally
driven phase transition80. Heterojunction formation
between the yellow non-​perovskite phase and black
perovskite phase of CsSnI3 is readily observed under
cathodoluminescence microscopy (Fig. 2f).
2D quantum wells
2D quantum wells are another type of nanostruc­
ture with promise for optoelectronic applications81,82.
Quantum-​confined perovskites present different opto­
electronic features from those of bulk 3D perovskites,
such as stronger excitonic character and anisotropic
absorption and emission. RP perovskites (Box 1) can be
regarded as self-​assembled quantum wells or superlat­
tices of 3D perovskites with an intrinsic quantum well
thickness of a single or a few unit cells. In this section,
we discuss the chemistry, optical properties and recent
advances in the synthesis of 2D perovskites. Note that the
term 2D can refer here to the intrinsic 2D crystal struc­
tures of RP perovskites or the morphological dimen­
sions, such as nanosheets or nanoplates of perovskite
materials (2D or 3D).
Bulk Ruddlesden–Popper perovskites. The n = 1  RP
perovskites (where n indicates the thickness of the
inorganic layers, Box 1) are the most extensively stud­
ied 2D perovskite structures, with numerous divalent
metal and organic ammonium combinations demon­
strated29. However, the synthesis of phase-​pure RP per­
ovskites with higher n is nontrivial owing to the complex

Nature Reviews | Materials

Reviews

a Confined 2D b 80 c

+ –e– 60

PLQY (%)
E 40
Bulk 3D 2.5
2D perovskite
2.0
Organic emitter

Height (nm)
20 1.5
3D perovskite 1.0
Inorganic (bulk GaN) 0.5
+ – 0 Perovskite CQDs 0.0
–0.5
– Electron 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0 1 2 3 4
E + Hole Diameter (μm)
1/FWHM (100 nm–1)

10 μm

Tune halide composition (PEA)2PbI4 Tune dimensionality (n)

e f h i
572 nm 640 nm 1
Intensity (arb. units)

Order 2 UC
0 1.3nm
1
3 UC
0
2 μm

PL and OD (arb. units)

1

4 UC 0 6 nm
400 500 600 700 800 0
Wavelength (nm) 1
Laser
g annealing 5 UC
0 2.5nm
1
Disorder
6 UC
0
1 2 μm
Cubes
0 10 nm
0
50 nm 350 400 450 500 550 600
Wavelength (nm)

Fig. 3 | Growth and characterization of 2D perovskite nanostructures. a | Illustration of quantum confinement and
dielectric confinement in Ruddlesden–Popper (RP) perovskites or nanoplates versus bulk crystals. Quantum-​confinement
effects increase the bandgap and the exciton binding energy of RP perovskites or colloidal nanoplates compared with
3D perovskites. Moreover, the exciton binding energy is further increased owing to dielectric confinement. In RP
→
perovskites or colloidal nanoplates, the electric field (E ) generated by charges in the inorganic framework (which has a
high dielectric constant) can extend into the organic alkylammonium spacers (which have a much lower dielectric
constant), in which it is screened less effectively. b | Comparison of the photoluminescence quantum yield (PLQY) against
the reciprocal of the full width at half maximum (FWHM) of the emission peak of a 2D (PEA)2PbBr4 (PEA+  = phenylethylam-
monium) single crystal and previously reported blue-​light emitters. c | Atomic force microscopy (AFM) image and height
profile of several (BA)2PbBr4 (BA+  = butylammonium) nanosheets synthesized by solvent evaporation. d | Optical images
of a series of individual microplates of (PEA)2(MA)nPbnI3n+1 (MA+  = methylammonium) with different halide compositions
and thicknesses (n) under laser excitation. The images show that it is possible to tune the emission colour and that
these microplates exhibit a strong waveguiding effect. e | Photoluminescence (PL) from monolayers of (BA)2(MA)Pb2I7
encapsulated by boron nitride. The structural reorganization caused by laser annealing of the (BA)2(MA)Pb2I7 monolayers
induces a shift in the excitonic energy. The black line is the PL of the ordered stage, and the blue line is the PL of the
disordered stage after surface relaxation. f | Illustration showing the order–disorder transition induced in monolayers of
(BA)2(MA)Pb2I7 by laser illumination. g | Transmission electron microscopy image of CsPbBr3 nanoplates with lateral
dimensions of 20 nm and thicknesses of a few unit cells (~3 nm) that emit cyan-​coloured light upon excitation (inset).
h | Optical absorption (dashed lines) and emission (solid lines) spectra of colloidal nanoplates of CsPbBr3 with controllable
thicknesses from 2 to 6 unit cells (UCs) and a CsPbBr3 nanocube. i | AFM topography images of ultrathin MAPbI3 nanosheets
that are a few nanometres thick and were prepared by vapour-​phase conversion of few-​layer-thick PbI2 nanosheets. CQD,
colloidal quantum dot; OD, optical density. Panel a is adapted with permission from ref.82, ACS. Panel b is adapted from
ref.86, Springer Nature Limited. Panel c is adapted with permission from ref.90, AAAS. Panel d (first two images on left-​hand
side) is adapted from ref.91, Springer Nature Limited. Panels e and f are adapted from ref.89, Springer Nature Limited.
Panel g is adapted with permission from ref.98, ACS. Panel h is adapted from ref.99, CC-​BY-4.0. Panel i is adapted with
permission from ref.102, ACS.

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interplay of thermodynamics and kinetics between RP
phases with similar n values. Crystals of RP perovskites
of (BA)2(MA)n−1PbnI3n+1 with n ≤ 5 can be obtained by
using an off-​stoichiometry protocol83,84. This approach
has also been used to obtain a series of Dion–Jacobson
2D perovskites in which the bilayer of monovalent
long-​chain alkylammoniums (LA+) was replaced by a
monolayer of dications85.
Owing to the strong quantum and dielectric confine­
ment (Fig. 3a), stable excitons with large binding ener­
gies of hundreds of meV can form in RP perovskites.
The large exction binding energies give rise to intense
PL with narrow peak widths and high radiative recom­
bination rates at room temperature, making RP per­
ovskites promising light emitters. One notable example
is (PEA) 2PbBr 4 (PEA +  = phenylethylammonium),
which exhibits a PLQY of up to 79% and a linewidth of
20 nm in the deep-​blue region86. These figures of merit
are superior to those of wide-​bandgap semiconductors
(for example, GaN), organic emitters and 3D chloride-​based
perovskites with similar emission wavelengths (Fig. 3b).
The optical bandgap of RP perovskites is mainly dictated
by n, as the band structure is primarily determined by
the inorganic layer. Increasing the quantum well thick­
ness (n) from 1 to 5 progressively decreases the corre­
sponding bandgap of (BA)2(MA)n−1PbnI3n+1 from 2.43 eV
to 1.83 eV. Although the LA+ cations do not contribute
directly to perovskite band structures, they can sub­
tly influence PL properties by distorting the inorganic
lattice29 and through electron–phonon interactions.
Electron–photon interactions are stronger in more rigid
2D perovskites, which results in faster non-​radiative
recombination and a lower PLQY86.
2D nanostructures. RP perovskites with an intrinsic 2D
crystal structure are a new class of solution-​processable
2D materials with excellent optical properties rarely
observed in existing classes of 2D materials, such as
strong PL emission spanning from the UV to the near-​IR
spectral regions. Starting from phase-​pure RP perovskite
single crystals, mechanical exfoliation is a convenient
method for accessing thin nanosheets with precise
n values for fundamental studies87–89. However, the
intrinsic softness of the perovskite lattice makes it diffi­
cult to maintain structural integrity during exfoliation.
Direct crystallization is a more robust method for obtain­
ing high-​quality nanosheets with uniform thickness and
a smooth surface. Ultrathin nanosheets of (BA)2PbBr4
with thicknesses of a few layers and lateral dimensions
of several micrometres (Fig. 3c) were grown in a solvent-​
evaporation process90. A ternary solvent system was used
to tune the solubility and crystallization rate, which is
crucial to the crystal growth. The thinnest nanosheet
obtained had a thickness of 1.6 nm, which corresponds
to one monolayer. In another work, solution-​phase trans­
port growth was used to form nano­plates of (PEA)2PbX4
(X− = Br−, I−) with a well-​defined rectangular geometry,
lateral dimensions of up to several tens of micrometres
and nanoscale thicknesses of several hundred nano­
metres91. The emission colour can be readily tuned by
halide alloying or varying the n value (Fig. 3d). Increasing
the lateral dimensions of these nanosheets would
Nature Reviews | Materials
Reviews
facilitate studies of their properties and their integration
into optoelectronic devices. Therefore, new methods
for the controlled growth of large-​area nanosheets of
2D perovskites that could rival the lateral dimensions
of more traditional 2D materials are needed.
RP perovskites are already inherently 2D quantum
confined, and therefore, a decrease in the nanoplate
thickness is not expected to produce further confine­
ment effects. However, owing to the soft lattice of RP
perovskites, lattice deformation under external pertur­
bations (for example, pressure, strain or temperature)
can lead to varied optical and electronic properties,
especially when the thickness is at the single-​layer
level. For example, a slight blue shift of the emission
peak of (BA)2PbBr4 was observed upon decreasing
the number of layers90, which was attributed to lattice
expansion. A reversible shift in excitonic energies can
be induced by laser annealing of exfoliated sheets of
(BA)2(MA)n−1PbnI3n+1 encapsulated by boron nitride89
(Fig. 3e). This phenomenon was attributed to the revers­
ible structural reorientation of the surface BA+ cations in
the easily deformable lattice (Fig. 3f), which formed free
and bound excitonic states.
Quantum-​confined nanoplates of 3D perovskites
can be obtained by modifying the colloidal synthesis
protocol for perovskite nanocrystals. Analogous to
RP perovskites, colloidal nanoplates can be described
by the formula (LA)2(A)n−1BX3n+1, where LA+ is a sur­
face ammonium ligand. These 2D nanostructures can
be considered as free-​standing monolayers or multi­
ple layers of the RP perovskites with a specific n value.
Decreasing the thickness down to the length of the
exciton Bohr radius leads to quantum-​confinement
effects. Quantum-​confined nanoplates were initially dis­
covered as a side product in the synthesis of MAPbBr3
nanocrystals92. The absorption and emission spectra
of the nanoplates showed multiple blue-​shifted peaks
associated with different values of n. Since these initial
studies, significant progress has been made in con­
trolling the nanoplate dimensions and increasing the
PLQY, and a wide range of perovskite compounds has
been demonstrated93–98. For example, colloidal nano­
plates of MAPbBr3 with varying thicknesses have been
synthesized by tuning the ratio of LA+ to MA+ (ref.93).
According to the proposed mechanism for colloidal
nanoplate growth, LA+ binds to the surfaces, which
confines crystal growth in one dimension after nucle­
ation. All-​inorganic perovskite nanoplates have also
been demonstrated. Modifying the protocol reported for
the growth of cubic CsPbBr3 nanocrystals by lowering the
reaction temperature led to the formation of CsPbBr3
nanoplates with a thickness of a few unit cells98 (Fig. 3g).
However, initial syntheses often produced nanoplates
with different thicknesses, leading to broad PL emis­
sion. Only recently has the synthesis of monodispersed
nanoplates of a single thickness been achieved99. The
PL emission of the CsPbBr3 nanoplates shifts from
greenish-​blue (497 nm) to deep blue (432 nm) when the
thickness is decreased from 6 to 2 layers (Fig. 3h). High
densities of surface defects owing to under-​coordinated
lead atoms result in low PLQYs. However, the PLQY can
be increased to nearly unity by repairing these defects100.
Reviews

In addition to controlling the thickness, introducing based on these films have achieved power conversion
shorter ligands together with the longer ligands and var­ efficiencies (PCEs) of > 12% while exhibiting greatly
ying their ratios enable the growth of nanosheets with increased device stability compared with the 3D
larger lateral dimensions of up to a few micrometres101. MAPbI3-based devices when subjected to thermal, light
Generally, the shape and composition of colloidal nan­ and humidity tests113,114.
oplates evolve over time82, and thus, stabilizing them Another form of structural instability is exhibited
remains challenging. Moreover, the high PLQY and by metastable perovskites such as CsPbI3 and FAPbI3
strong confinement effects are often lost when they are (FA+  = formamidinium; Box 1), which undergo spon­
made into solid-​state films. taneous phase transitions into non-​perovskite poly­
It is nontrivial to prepare ultrathin nanosheets of 3D morphs at room temperature. These non-​perovskite
perovskites owing to the inherent cubic crystal structure. polymorphs are undesirable because their optoelectronic
The presence of LA+ in the growth solution is crucial to properties are inferior to those of the perovskite phases.
break the crystal symmetry of 3D perovskites into 2D RP Nanostructuring is an effective approach to gain access
phases and therefore to promote anisotropic 2D growth. to these metastable perovskite polymorphs because they
Nevertheless, several alternative approaches have been have a lower surface energy than the corresponding
developed that do not require LA+. For example, start­ stable non-​perovskite phases115. When the increasing
ing from PbI2 nanosheets with a thickness of a few lay­ energy contribution from the surface outweighs that
ers as templates, vapour-​phase conversion yielded 2D from the bulk as the size of crystallites decreases, the
quantum-​confined nanosheets of MAPbI3 with con­ metastable phase can potentially be thermodynamically
trollable thicknesses of a few nanometres102 (Fig. 3i). stabilized (Fig. 4c). In the initial report on the colloi­
Ultrathin 2D nanosheets of MAPbCl3 with thicknesses dal synthesis of CsPbI3 nanocrystals, the nanocrystals
of 8.7 nm and lateral dimensions of >20 µm have also formed in the perovskite structure but transformed
been directly synthesized by chemical vapour deposi­ into the non-​perovskite phase within a few days owing
tion103. These vapour-​phase methods have also been to aggregation116. A modified purification approach in
used to create vertical heterostructures of perovskites which the nanocrystals are isolated without full removal
with other 2D materials104,105. of the surface ligands can increase the structural stabil­
ity to several months117 (Fig. 4d). Solar cells containing
Phase stabilization of nanostructures thin films made of stabilized CsPbI3 nanocrystals have
Poor structural stability and chemical stability remain demonstrated PCEs of up to 10.8%. Theoretical calcu­
major concerns for the practical application of halide lations have confirmed that the perovskite structure
perovskites. The susceptibility of 3D perovskites to of CsPbI3 has a lower surface energy than the non-​
chemical and structural degradation stems from the perovskite structure, and nanocrystals of the perovskite
low formation energy and reconfigurable lattice of phase are thermodynamically more stable when their
these materials. The high surface-​area-to-​volume ratio size is <100 nm (ref.118). Similarly, colloidal nanocrys­
of nanostructures can increase the impact of surface tals of FAPbI3 that exhibited bright luminescence were
properties on the chemical properties and phase stabil­ stabilized in the cubic perovskite phase119,120.
ity. However, counterintuitively, nanostructures of halide In addition to the above size effect, surface ligand
perovskites can exhibit enhanced structural and chemi­ functionalization can also contribute to phase stabi­
cal stability owing to a surface energy effect and surface lization by reducing the surface energy of the nano­
ligand functionalization. structures. Through surface functionalization, it is
3D perovskites are particularly susceptible to possible to stabilize pure FAPbI3 in the perovskite phase
moisture-​induced degradation owing to the strong in single-​crystal nanostructures with up to micrometre
interaction between water and the perovskite surface. sizes121 (Fig.  4e). Without surface functionalization,
For example, MAPbI3 complexes with water to form FAPbI3 exclusively forms in the non-​perovskite phase
hydrated phases upon exposure to high humidity lev­ at room temperature. The surfaces of the stabilized
els106. RP perovskites107, colloidal nanoplates108 and nanostructures are terminated by LAI, which is similar
functionalized 3D perovskites109 are more resistant to to RP perovskites. The LA+ cations occupy the surface
humidity than prototypical 3D perovskites because the A sites, and the I− anions coordinate to the surface Pb2+
surface is terminated by long-​chain ammonium cations ions such that all of the [PbI6]4− octahedra are complete.
with the hydrophobic alkyl chains oriented outwards This charge-​balanced surface structure is an intuitive
(Fig. 4a). These surface ligands render the perovskite surface termination for halide perovskites, especially
surface more hydrophobic109 (Fig. 4b) and prevent mois­ in ammonium-​halide-rich environments. Calculations
ture from penetrating into the perovskite lattice. Recent show that surface functionalization can lower the sur­
calculations have confirmed that RP perovskites exhibit face energy of nanostructures (Fig. 4f), which causes the
high positive water adsorption energies, whereas 3D per­ crossover between the metastable perovskite phase and
ovskites have negative (that is, favourable) adsorption non-​perovskite phase to occur at larger crystal sizes
energies110. However, it should be noted that solution-​ (Fig. 4c). The smaller surface energy of the functionalized
processed thin films of RP perovskites (n > 1) consist nanostructures can be attributed to van der Waals inter­
of a mixture of RP perovskites with different n values actions between adjacent ligands on the surfaces. The
along with nanoscale crystallites of 3D perovskite111,112. functionalized FAPbI3 nanostructures did not exhibit
As n increases, the system can be considered as a 3D detectable phase conversion to the non-​p erovskite
perovskite with surface functionalization. Solar cells phase upon storage for several months. In addition to

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 Reviews

a FA+-terminated surface PEA+-terminated surface e

2 μm

Surface functionalization
b

500 nm

10μm

c d f

Formation energy (eV)

–5
Metastable
Free energy

perovskite –6

Surface –7
(FA)2(FA)n–1PbnI3n+1
functionalization –8
6.2 Å
Non-perovskite 5 nm –9 (PEA)2(FA)n–1PbnI3n+1

Surface area or inverse crystal size –10

0 1 2 3 4 5 6 7 8 9
n

Fig. 4 | Chemical and structural stability in perovskite nanostructures. a | Illustrations of the (001) surface of cubic
FAPbI3 (FA+  = formamidinium) terminated by FA+ (left, a prototypical surface) and PEA+ (right, a functionalized surface;
PEA+  = phenylethylammonium). b | Photographs of a water droplet on a pristine MAPbI3 (MA+  = methylammonium) film (left)
and a MAPbI3 film functionalized with hexadecyltrimethylammonium on the surface (right), showing different contact
angles and wetting properties. c | Plot of the total free energy as a function of surface area (or inverse crystal size) for a non-​
perovskite, metastable perovskite and surface-​functionalized metastable perovskite. d | High-​resolution transmission electron
microscopy image of CsPbI3 nanocrystals stabilized in the cubic perovskite phase. e | Scanning electron microscopy images
of hexagonal FAPbI3 nanostructures grown without long-​chain alkylammonium (L A+) ligands (top) and cubic perovskite FAPbI3
nanostructures grown with L A+ ligands (bottom) at room temperature. The insets show the corresponding optical images
of the substrates. f | Calculated formation energies of (FA)2(FA)n−1PbnI3n+1 and (PEA)2(FA)n−1PbnI3n+1 as a function of the thickness of
the inorganic perovskite layer, n. The PEA+-terminated FA+-based perovskites always have a more negative formation energy
than their FA+-terminated counterparts, indicating that the former have a smaller surface energy. Panels a, e and f are
adapted with permission from ref.121, ACS, further permissions related to the material should be directed to the ACS.
Panel b is adapted from ref.109, Springer Nature Limited. Panel d is courtesy of Joseph M. Luther, University of Colorado, USA.

the thermodynamic stabilization effect, the hydropho­
bic surface of the functionalized FAPbI3 nanostructures
could also mitigate moisture-​induced phase transforma­
tion. The phase stability of CsPbI3 perovskite nanocrys­
tals122 and thin films123,124 exhibits strong dependence on
the capping ligands, further indicating the importance
of surface chemistry on phase stabilization. Even more
robust phase stabilization can be achieved through
stronger surface ligand coordination with zwitterionic
molecules or polymers125,126.
Preventing thermal-​induced and photoinduced
degradations are key challenges for the application of
hybrid perovskite nanostructures. Upon above-​bandgap
excitation or heating, hybrid perovskites decompose into
the parent lead halide, gaseous organic amine and HX.
One feasible approach to suppressing the degradation
process is to prevent the organic species from evapo­
ration. For example, encapsulating MAPbI3 microplates
or (PEA)2PbI4 nanosheets with hexagonal boron nitride
thin flakes and/or polycarbonates can greatly improve
their stability127,128.
Optoelectronic applications
The success of 3D perovskites in photovoltaics has moti­
vated the development of various high-​performance
optoelectronic devices129. Single-​crystal 1D and 2D
nanostructures (or microstructures) of perovskites
offer potentially superior optoelectronic performance
and many exciting opportunities in comparison with
nanostructures of conventional semiconductors or the
bulk forms of 3D perovskites.
Perovskite nanowires for photonics and optoelec-
tronics. Single-​crystal semiconductor NWs can serve
as optical gain media and provide the cavity for lasers
that could potentially outperform their thin-​film coun­
terparts4. Since the pioneering work on UV lasing
from ZnO NWs130, optically pumped lasing has been
demonstrated in various semiconductor NWs in the
UV to near-​IR spectral regions4. These NW lasers hold
great promise as miniature coherent light sources for
a wide range of applications. However, the growth of
high-​quality NWs capable of lasing generally requires
high temperatures and a vacuum, and the difficulty of

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Reviews
realizing continuous-​wave operation131–133 and electri­
cally injected lasing hinders potential application of
NW lasers.
Perovskite NWs have demonstrated outstanding
lasing performance, facilitating NW lasers capable of
continuous-​wave operation. The first perovskite NW
laser was demonstrated in NWs made of MAPbI3 grown
by solution-​phase recrystallization10. These single-​crystal
NWs have smooth facets and subwavelength dimen­
sions, which make them efficient nanoscale Fabry−
Pérot cavities. Under pulsed optical excitation, these
MAPbI3 NWs lase at room temperature with low las­
ing thresholds of ~220 nJ cm−2, record-​breaking qua­
lity factors of ~3,600 (Fig. 5a) and broad stoichiometric
wavelength tunability. The lasing threshold values for
single-​crystal MAPbI3 NWs are substantially lower than
those reported for lasing from polycrystalline MAPbI3
thin films and nanostructures9,134 and a family of near-​
IR III–V semiconductor NW lasers135,136. The superior
lasing performance of perovskite NWs is attributed to
exceptionally low rates of non-​radiative recombination
in these single-​crystal nanostructures. Moreover, the
MAPbI3 NWs showed extremely high PLQYs of up
to 87% without any intentional surface passivation.
By contrast, to circumvent the strong non-​radiative sur­
face recombination in GaAs NWs, surface passivation
by core–shell design or a cryogenic temperature is often
required135. Nevertheless, the state-​of-the-​art epitaxial
GaAs–AlGaAs core–shell NW laser has a low PLQY
of ~0.4%136. This suggests that the electronic properties of
MAPbI3 in single-​crystal NWs are much more tolerant
to surface defects than those of GaAs even though their
bulk forms exhibit similar photophysical properties. The
lasing performance from polycrystalline MAPbX3 NWs
synthesized by vapour-​phase conversion137 was poorer
than that of NWs fabricated by direct solution synthesis,
probably owing to the inferior crystalline quality. The
effects of morphology on lasing from perovskite nano­
structures have been established, for which we refer
readers to a recent review138. Furthermore, perovskite
NWs have demonstrated continuous tunability of the
lasing wavelength from 420 nm to 820 nm, which can
be readily achieved by controlling the anionic or catio­
nic stoichiometry of APbX3 (Fig. 5b,c). The emission of
NW lasers mostly comes from the two end facets with
coherent interference under lasing conditions (Fig. 5c).
Interestingly, the wide-​bandgap all-​inorganic perov­
skites CsPbCl3 and CsPb(Br,Cl)3 demonstrate efficient
lasing at room temperature in the violet–blue spectral
region35,36, which is not possible for wide-​bandgap hybrid
perovskites such as MAPbCl3. We suspect that wide-​
bandgap CsPbCl3, in which the ionic radii are favoura­
bly matched in the perovskite structure, could be more
stable and less defect-​prone than MAPbCl3 and FAPbCl3,
thus exhibiting superior light-​emitting properties.
Although MAPbX3 NWs exhibit excellent lasing
performance, they are unstable under prolonged illumi­
nation. In comparison, single-​crystal NWs of FAPbX3
and CsPbX3 grown by either solution-​phase or vapour-​
phase methods show similar lasing performance but
exhibit increased stability34–36. In particular, all-​inorganic
CsPbBr3 NWs were substantially more robust than their
hybrid perovskite counterparts, showing stable lasing
emission with no measurable degradation after at least
7.2 × 109 laser shots and 8 hours (Fig. 5d). The improved
stability of CsPbBr3 NWs under illumination is consist­
ent with their enhanced photostability and thermal sta­
bility compared with those of MAPbX3. Initial perovskite
NW lasers were demonstrated with femtosecond pulsed
excitation to avoid thermal degradation. Recently, under
continuous-​wave pumping and at low temperatures,
lasing emission from CsPbBr3 NWs was observed at an
excitation density of 6 kW cm−2 and with a quality factor
of 2,300 (ref.139). The achievement of continuous-​wave
lasing is a step towards the development of electrically
driven lasers.
In addition to lasing applications, perovskite NWs
can also function as efficient nonlinear emission sources,
electro-​optic modulators and photodetectors. Owing
to the large multiple-​photon absorption cross section
and low threshold required for population inversion,
multiple-​photon pumped lasing from perovskite NWs
has been achieved 140,141. Single-​c rystal perovskite
NWs can also function as active waveguides142, exhib­
iting an ultralow propagation loss of 0.04 dB µm−1. The
combination of the perovskite NW waveguides with
electrical inputs has been explored for potential appli­
cation as electro-​optical modulators (Fig. 5e). The fabri­
cated NW electro-​optical device achieved a PL intensity
modulation of up to 98.4% (Fig. 5f), outperforming most
inorganic and organic NWs. The effective modula­
tion may result from a combined effect of the unique
ion migration and photon recycling in perovskites.
Photodetectors fabricated with MAPbI3 NWs exhibit
responsivities of up to 104 A W−1, detectivities approach­
ing 1012 Jones, a linear dynamic range of >150 dB and a
fast photoresponse with a bandwidth of up to 0.8 MHz
(refs69,143). The high performance mainly originates from
the low doping concentration (nearly intrinsic) and low
density of trap states in high-​quality perovskite NWs,
which result in very low dark current and high gain.
Light-​emitting diodes. 3D perovskites are well known
for their high photovoltaic performance, which is
enabled by the long carrier diffusion lengths and low
exciton binding energies. However, the light-​emitting
efficiency of perovskites is reduced owing to the com­
petition between non-​radiative trapping processes and
slow bimolecular radiative recombination under low
injected carrier densities (that is, <1015 cm−3), which is
the regime that typical LEDs operate in144. High light-​
emitting efficiency can be obtained at high fluences, at
which radiative bimolecular recombination dominates
the carrier dynamics. Because the transition from bulk
3D perovskites to nanostructures or 2D RP perovskites
with reduced dimensionalities introduces confine­
ment effects and increases the probability of radiative
recombination (Fig. 6a), nanostructuring is an effective
strategy to ensure high PL at low carrier densities by sup­
pressing exciton dissociation and promoting radiative
recombination145.
Benefiting from the fundamental understanding of
photophysics and synthetic advances, LEDs based on
solution-​processed 2D RP perovskites have achieved
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 Reviews

excellent performance with high external quantum room-​temperature electroluminescence (EL)147. By con­
efficiencies (EQEs), high brightness, high colour purity verting polycrystalline thin films of (PEA)2PbBr4 into
and broad spectral tunability. The earliest LEDs using single-​crystal micrometre-​sized plates through a sol­
n = 1 perovskites were reported in the 1990s and could vent vapour-​annealing technique, the PLQY increased
function only at cryogenic temperatures146. Improving from 10% to 26%. Furthermore, colour-​pure violet
the crystal quality increased the PLQY and enabled LEDs were demonstrated at room temperature with the

a c

Intensity (arb. units)

40 554 nJ cm–2
3 580nJ cm–2

FWHM (nm)
604nJ cm–2
20 617 nJ cm–2
Intensity (arb. units)

630 nJ cm–2
d
2 0 1.0
400 500 600 700
Pump fluence δλ ≈ 0.22 nm

Lasing intensity
FAPbI3
(nJ cm–2)

(arb. units)
MAPbI3
1 MABr-stabilized
FAPbI3
CsPbBr3

0.1
782 783 784 785 786 787 788 789 0.01 0.1 1.0 10
Wavelength (nm) Illumination time (h)
b
x=3 CsPbClxBr3–x x=0, y=3 CsPbBryI3–y y =3 (MA,FA)Pb(Br,I)3
PL intensity (arb. units)

400 450 500 550 600 650 700 750 800 850
Wavelength (nm)
e f
Laser
12,000

PL intensity (arb. units)

0V 0

Perovs 12,000
k ite
15 V
0
V 12,000
Detector
30 V
0
Electric field

Fig. 5 | High-​performance nanoscale optoelectronic and photonic applications of perovskite NWs. a | Emission spectra
around the lasing threshold of a MAPbI3 (MA+  = methylammonium) nanowire (NW) pumped by a 402-nm-​pulsed laser
excitation (150 fs, 250 kHz). The inset shows the integrated emission intensity (grey circles) and full width at half maximum
(FWHM, blue triangles) as a function of pump fluence, indicating the lasing threshold at ~600 nJ cm−2. The FWHM (δλ) of the
lasing peak at 630 nJ cm2 is ~0.22 nm, corresponding to a quality factor of ~3,600. b | Broad wavelength-​tuneable lasing from
single-​crystal NWs of APbX3 (A+ is Cs+, MA+ or formamidinium (FA+); X− is a halide) perovskites with different compositions.
c | Optical images of CsPbX3 (X− = Cl−, Br− or I−) NW lasers with tuneable colour emission. The images show that emission
mostly comes from the two end facets with coherent interference under lasing operation. d | Integrated emission intensity
of representative MAPbI3, FAPbI3, MABr-​stabilized FAPbI3 and CsPbBr3 NW lasers as a function of illumination time under
continuous illumination of a 402-nm-​pulsed laser excitation at room temperature. e | Schematic of an electro-​optical
modulator device fabricated with a perovskite NW. f | Optical dark-​field images of the electro-​optical modulator device
under different external voltages (V), showing the modulation of the photoluminescence (PL) intensity under an applied
voltage. Panel a is adapted from ref.10, Springer Nature Limited. Panel b is adapted with permission from ref.10, Springer
Nature Limited, and refs34,35, ACS, further permissions related to the material should be directed to the ACS. Panel c is
adapted with permission from ref.35, ACS. Panel d is adapted with permission from refs34,35, ACS, further permissions
related to the material should be directed to the ACS. Panel f is adapted with permission from ref.142, Wiley-​VCH.

Nature Reviews | Materials

Reviews

a b electroluminescence peak centred at 410 nm and with

–2
3D perovskite 2D RP perovskite a narrow full width at half maximum of 14 nm owing
Small n Large n
–3 –– to strong quantum confinement. With perovskites of
– – higher n values (n > 1), multiple-​phase 2D RP per­

Energy (eV)

MoOx/Au
hν – hν –– ovskites with different values of n and 3D perovskite

TFB
–4

ITO
ZnO/PEIE
+
+ hν –
crystallites can be assembled in solution-​processed thin
–5
+ + films to form an energy-​cascade structure148–150 (Fig. 6b).
Perovskite MQWs ++
–6 ++
Spectroscopic studies revealed that these films function
Recombination – Electron
as an energy funnel that can guide the charge carriers
at defect + Hole to the component with the smallest bandgap (Fig. 6c,d)
and enable efficient radiative recombination even at low
c d
0 ns 567 nm excitation densities150,151 (Fig. 6e). The ultrafast energy
0.003 0.5 ns 610 nm transfer from wide-​b andgap to narrower-​b andgap
1 ns 642 nm
5 ns 0.01 695 nm
components occurs on the picosecond timescale. The
0.002 PL (static) energy-​cascade design has enabled high-​performance
LEDs with EQEs of up to 11.7% in the near-​IR region
∆T

∆T

0.001 (~760 nm). Owing to the presence of surface ligands

that stabilize the crystallites and impede ion migration
0.001 under an electric field, these devices based on 2D perov­
0.000
skites also showed greater operational stability than
3D-​perovskite-based devices.
500 600 700 800 0.1 1 10 100 1,000 More efficient LEDs with tuneable emission
Wavelength (nm) Delay time (ps) can be achieved by changing the composition of
e f (LA)2(A)n−1BnX3n+1 and by controlling the value of n
3D FAPbI3 film 1.0
2D (NMA)2(FA)Pb2I7 film (refs151–153). For example, the investigation of a series
of (PEA)2(FA)n−1PbnBr3n+1 films with various n values
60 0.8
showed that the n = 3 system exhibited the highest PLQY.
EL intensity (norm.)

Efficient green LEDs with the n = 3 perovskite achieved

0.6
40 a current efficiency of 62.4 cd A−1 and a high EQE of
PLQY (%)

14.36%152. Moreover, the EL can be tuned across a wide

0.4
spectral range using mixed halide compositions of dif­
20
0.2
ferent ratios149. Note that all of the LEDs fabricated with
stoichiometric (LA)2(A)n−1BnX3n+1 (n > 1) compositions
0.0
exhibit an EL peak close to that of the corresponding
0
10–1 100 101 102
400 600 800 1,000 3D perovskites. This is due to the inevitable formation
Lasing intensity (mW cm–2) Wavelength (nm) of 3D perovskite crystallites when using stoichiometric
synthesis protocols and the rapid energy transfer from
Fig. 6 | High-​performance leDs based on self-​assembled 2D perovskite nanostructures.
a | Comparison of charge-​carrier recombination in 3D perovskites (left) and 2D Ruddlesden– wide-​bandgap components to 3D perovskites. To fully
Popper (RP) perovskite films (right), which are assemblies of multiple quantum wells take advantage of the strong quantum confinement of
(MQWs) with various values of n (where n indicates the thickness of the inorganic perovskite 2D perovskites, excess LAX is needed to suppress the
layers). In 3D perovskite films, defect-​state trapping competes effectively with bimolecular growth of 3D perovskites and to produce small-​n RP
radiative recombination under low excitation densities, resulting in a relatively low perovskites154,155.
photoluminescence quantum yield (PLQY). In RP perovskite films, charge carriers are rapidly Although high-​performance green and red LEDs
localized from wide-​bandgap (small-​n) RP phases to the narrowest-​bandgap phase (large-​n based on perovskites have been achieved, it remains
RP phases or nanoscale crystallites of 3D perovskites), and thus the radiative recombination challenging to obtain the blue LEDs that are required
rate is faster than in bulk 3D perovskite films. b | Schematic representation of the flat-​band for lighting and displays. Mixed halide 3D perovskites
energy-​level diagram and cascade energy transfer in self-​assembled MQWs of a RP
(Br− and Cl−) can exhibit blue emission; however, the
perovskite film. The charger carriers are transferred downstream from the wider-​bandgap
RP phases to narrower-​bandgap phases, and the emission is mainly from the component unavoidable phase separation that occurs under electri­
with the narrowest bandgap. c | Transient absorption spectra of a (PEA)2(MA)2Pb3I10 (MA+ is cal bias and the formation of trap states associated with
methylammonium; PEA+ is phenylethylammonium) perovskite film at different timescales Cl− are limitations for achieving stable emission and high
show that the relative intensity of the four bleaching peaks evolves over time. d | Bleaching PLQY156. RP perovskites and colloidal nanoplates that
kinetics in the (PEA)2(MA)2Pb3I10 film in panel c probed at selected wavelengths, showing a exhibit strong quantum confinement are therefore prom­
cascade on the 100 fs to 100 ps timescale from higher-​energy phases to lower-​energy ising candidates for fabricating blue LEDs. By tuning the
phases. e | Excitation-​intensity-dependent PLQY of a 3D perovskite FAPbI3 film and a RP ratio of LABr:ABr:PbBr2 in the precursor solution, thin
perovskite film of (NMA)2(FA)Pb2I7 (FA+ is formamidinium; NMA+ is 1-(2-naphthylmethyl) films mainly composed of quantum-​confined perovskite
ammonium). f | Electroluminescence (EL) spectrum of a light-​emitting diode (LED) device grains can be obtained. These thin films enabled the fab­
fabricated with CsPbBr3 nanoplates. The inset shows a photograph of the LED device with
rication of tuneable blue–green LEDs with emissions in
blue-​light emission. ∆T, change in transmission; ν, photon energy ; h, Planck’s constant; ITO,
indium tin oxide; PEIE, polyethylenimine ethoxylated; TFB, poly(9,9-dioctyl-​fluorene-co-​ the range 460–520 nm (ref.154). The LED device fabricated
N-(4-butylphenyl)diphenylamine). Panel a is adapted from ref.144, Springer Nature Limited. with colloidal nanoplates of CsPbBr3 (with a thickness of
Panel b is adapted from ref.153, CC-​BY-4.0. Panels c and d are adapted from ref.148, Springer three unit cells) shows pure blue emission with a narrow
Nature Limited. Panel e is adapted from ref.149, Springer Nature Limited. Panel f is adapted peak centred at 460 nm (refs99,100) (Fig. 6f). However, the
from ref.99, CC-​BY-4.0. EQEs of the devices remain quite low (~0.1–1%).

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 Reviews

The study of physical properties removing the uncertainty due to ensemble averaging
Single-​crystal nanostructures offer a platform for inves­ of inhomogeneous polycrystalline samples (Fig.  7b).
tigating the intriguing physical properties of diverse Compared with bulk single crystals (Fig. 7c), optically
perovskite materials. In polycrystalline samples, the thin and flat nanoplates may be more suitable for many
presence of grain boundaries along with the sensitiv­ spectroscopic studies, such as PL measurements, because
ity to preparation conditions may obscure the intrinsic reabsorption of the PL emission can be minimized.
properties of the perovskites157,158. By contrast, each indi­ Moreover, perovskite nanoplates have a submicrometre
vidual perovskite nanostructure is a single crystal with thickness that is similar to the optimal thickness of the
well-​controlled facets and no grain boundaries (Fig. 7a), perovskite layer in thin-​film solar cells. Additionally,

a b d
1D diffusion model
Laser
Emission
APbX3 Delay time
2 μm
2 μm
+ Carrier diffusion +
– –
c

Solid-state ion interdiffusion

10 mm – Electron
+ Hole
10 μm A′PbX′3

e f g h
1.0
k2 x 10–10 cm3 s–1 Excitation
10 3 8 30 1.0
Intensity (arb. units)

h
Delay time (ns)

k1 x 107 s–1

Intensity (arb. units)

25 0.8

Distance (μm)
6 5.3μm
0.5 20
k1 or k2

10 2
7.1 μm 0.6
4 8.8 μm 15
0.4
10.7μm 10
1
10 2 0.2
0.0 5 5 µm
5 μm 0.0
0
2.3 2.4 2.5 2.6 MA+ FA+ Cs+ MA+ FA+ Cs+ 460 480 500 520 540 560
Energy (eV) Cation Wavelength (nm)

i – Electron j UP k
FP cavity + Hole LP
Cavity photon
Exciton 2.32
Energy (eV)

Perovskites 2ħΩ
Energy

+
– Exciton 2.30

Cavity photon

Momentum Intensity 2.6 2.7 2.8 2.9

(arb. units) kz (10–3 Å–1)

Fig. 7 | studies of physical properties using single-​crystal perovskite
nanostructures. a | Optical image of representative single-​crystal perovskite
nanostructures with well-​controlled facets and subwavelength thicknesses
(as highlighted by the scanning electron microscopy image of a single plate
shown in the inset). b | Scanning electron microscopy image of a
polycrystalline thin film. The optically thin nanoplates are typically tens of
micrometres in lateral dimensions and hundreds of nanometres in thickness,
which make them a suitable model system for spectroscopic studies.
c | Photograph of a bulk single-​crystal perovskite. d | Illustration of the
charge-​carrier diffusion process in a perovskite (APbX3, where A+ is Cs+,
methyl­ammonium (MA+) or formamidinium (FA+) and X− is a halide) nanowire
(NW) and the ion interdiffusion process in a perovskite heterostructure.
e | Time-​dependent photoluminescence (PL) spectra from a MAPbBr3 nanoplate,
showing hot PL emission with a lifetime of ~102 ps. f | Comparison of the first-​
order rate constant (k1) or carrier trapping rate constant and the second-​order
rate constant (k2) for electron–hole radiative recombination for MAPbBr3,
FAPbBr3 and CsPbBr3 nanoplates163. g | The PL intensity image reveals carrier
diffusion in a MAPbI3 NW. The inset is an optical image of the NW; the red spot
is the location of laser excitation. h | Normalized PL line mapping of a gradient
CsPbBr3−xClx NW. The y axis indicates the distance from the edge of the
CsPbCl3 microplate that is placed over the CsPbBr3 NW. The inset is a real-​
colour PL image of the NW under broad laser excitation. i | Schematic of an
exciton–polariton microcavity. j | Schematic showing the dispersion of a
cavity photon, exciton, upper polariton (UP) and lower polariton (LP)
branches. The black points indicate Fabry–Pérot modes in perovskite NWs;
these modes are shown on the energy−wavevector diagrams in panels j and k.
k | Emission spectrum of a CsPbBr3 NW (left) and the corresponding energy–
wavevector (kz) dispersion curve along with the exciton–polariton model fit
(red solid line). ħ, reduced Plank’s constant; Ω, Rabi splitting energy ; FP, Fabry–
Pérot. Panels a (inset) and e are adapted with permission from ref.159, AAAS.
Panel b is adapted from ref.157, Springer Nature Limited. Panel c is adapted
with permission from ref.167, AAAS. Panel g is adapted with permission from
ref.25, ACS. Panel h is adapted with permission from ref.77, ACS. Panel k is
adapted with permission from ref.139, Wiley-​VCH.

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Reviews

the 1D geometry of NWs provides directional channels MAPbBr3. Similarly, a minority charge-​carrier diffu­
for charge and/or photon transport and ion migration sion length of up to 21 μm in MAPbI3 NWs under an
(Fig. 7d), which could enable much simpler modelling of electric field has been directly measured with scanning
their kinetics. However, nanostructures have a greater photocurrent microscopy26. The corresponding carrier
surface area than do bulk single crystals. Although the mobility was estimated to be 170 cm2 V−1 s−1 using a PL
greater surface area could be a drawback, the surface lifetime of 1 μs. The diffusion lengths and carrier mobil­
defects are more benign and/or easily passivated in ities for single-​crystal nanostructures are several to tens
nanostructures, and the effect on properties might be of times higher than the values found for polycrystal­
minimized. Therefore, nanostructures with well-​defined line thin films164,165 and are comparable to those of bulk
surface facets can be used as a more sensitive (rela­ single crystals166,167 (that is, on the order of 10 µm and
tive to single crystals) but more controlled (relative to 10–100 cm2 V−1 s−1, respectively), which suggests that
polycrystalline films) material platform to study surface the absence of grain boundaries substantially increases the
effects. carrier diffusion length. In another example of optical
studies on single-​crystal nanostructures, the tetragonal-​
Charge-​carrier properties. To study the charge-​ to-orthorhombic phase transition in a single MAPbI3
carrier properties of 3D perovskites, time-​resolved PL NW was studied using super-​resolution PL imaging168
measurements were conducted on nanoplates of 3D and indicated that the phase transition temperature may
perovskites with different cations (MA+, FA+ or Cs+). depend on the concentration and nature of local defects.
Single-​crystal nanostructures and/or microstructures
of diverse perovskites with different compositions and Ion exchange. Nanoscale heterostructures of perovskites
properties have enabled comparative studies of per­ provide model systems for mechanistic and kinetic
ovskite materials34–36. For example, hot fluorescence studies of solid-​state ion exchange77. The ion interdiffu­
emission at room temperature from energetic carriers sion kinetics of heterostructures fabricated by stacking
with lifetimes of ~102 ps was observed from hybrid CsPbCl3 microplates on top of CsPbBr3 NW networks
perovskites (Fig. 7e) but not from CsPbBr3 (ref.159). This have been visualized using spatially resolved PL meas­
observation suggests that in hybrid perovskites, there urements. Anion interdiffusion readily occurs between
is strong screening of the Coulomb potential owing to CsPbCl3 and CsPbBr3, which results in halide concen­
the formation of large polarons, which are probably of tration gradients in the NWs (Fig. 7h). Quantitative anal­
a ferroelectric nature15. The much reduced Coulomb ysis of the temperature-​dependent composition profiles
potential decreases hot electron cooling through elec­ yields an interdiffusion coefficient of ~10−13 cm2 s−1
tron–longitudinal-​optical-phonon scattering. Large at room temperature and a low activation energy of
polaron formation in MAPbBr3 and CsPbBr3 occurs 0.44 eV. By contrast, the activation energy reported
on timescales of 0.3 ps and 0.7 ps, respectively; only the for InxGa1−xAs/GaAs is 3.0 eV at 900–1,150 °C (ref.169).
former is competitive with longitudinal optical pho­ In contrast to the anions, the interdiffusion of the
non cooling, leading to the partial retention of excess A-​site cations in the MAPbBr3/CsPbBr3 system is much
electronic energy in MAPbBr3 (ref.160). Further cooling slower. These insights provide guidelines for designing
of hot polarons is slowed to the timescale of 100 ps perovskite heterostructures with tailored properties for
owing to the low thermal conductivity of perovskites161. practical applications.
Dynamic disordering of the cations was recently sug­
gested to be responsible for the suppressed thermal Light–matter interactions. Perovskite NWs have
conductivity of MAPbBr3 NWs compared with that of recently emerged as promising platforms for demon­
CsPbBr3 NWs162. In addition, by comparing the band-​ strating and manipulating strong light–matter interac­
edge carrier dynamics of single-​crystal nanoplates of tions. Strong coupling between excitons and confined
different perovskites, similar low carrier trapping rate cavity photons can result in the formation of exciton–
constants (∼107 s−1) and electron–hole radiative recom­ polaritons (Fig. 7i), which are of mixed exciton and pho­
bination rate constants (∼10−10 cm3 s−1) were found and ton character. The mass of an exciton–polariton can be
shown to be independent of the cation type163 (Fig. 7f). as low as 10−5 me (where me is the electron rest mass);
These results suggest that the remarkable properties the corresponding long de Broglie wavelength of these
of photoexcited carriers in perovskites are inherent to bosonic quasiparticles makes them exciting platforms
these materials, triggering intense studies and discus­ to achieve Bose–Einstein condensation at room tem­
sion regarding the mechanisms of their defect tolerance perature170,171. As the exciton–polariton condensate is a
and low recombination rates14–17. macroscopic quantum coherent state, light escaping the
Carrier transport properties in single-​crystal nanos­ cavity is coherent and laser-​like. This can be the basis
tructures of 3D perovskites have been studied using spa­ for low-​threshold lasing without population inversion.
tially resolved optical techniques. Using time-​resolved The robustness of an exciton–polariton is determined
and PL-​scanning imaging microscopy, the carrier dif­ by both the exciton binding energy and the Rabi split­
fusion processes in single-​crystal MAPbX3 NWs and ting energy (Fig. 7j). The latter quantifies the coupling
nanoplates25 were directly visualized and quantitatively strength between an exciton and a cavity photon.
characterized (Fig. 7g). Fitting the PL kinetics with a The spacings of the Fabry–Pérot modes in CsPbBr3
diffusion model yielded a carrier mobility and diffu­ NWs are not identical but decrease as the mode energy
sion length of 80 cm2 V−1 s−1 and 14 μm, respectively, increases44 (Fig. 7k), which is inconsistent with the pho­
for MAPbI3 and 34 cm2 V−1 s−1 and 6 μm, respectively, for tonic model. The decreasing mode spacing with energy

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 Reviews

(that is, the negative curvature in Fig. 7k) can be attrib­ avenues for exploring RP perovskites with improved
uted to strong light–matter interactions. There are two optical properties and stability29. The structural stabili­
interpretations of this strong light–matter interaction. zation by surface ligands further expands the library of
In the classical interpretation, as the emission energy compositions and structural diversity121,123. The chemis­
approaches an electronic resonance, the refractive try of some of these perovskite or perovskite-​like mate­
index increases, which is reflected in the decrease in rials may be quite different from that of the 3D APbX3
mode spacing. In the alternative quantum-​mechanical perovskites. Given the structural diversity, there is much
explanation, for an exciton not in resonance with a cav­ scope for creative new nanomaterial syntheses.
ity photon energy, the two dispersion curves cross at a Considering the advantages of perovskite hetero­
momentum away from zero. The avoided crossing due structures, including greater control of the generation,
to the Rabi splitting energy results in a lower polariton recombination and transport of charge carriers and the
branch and an upper polariton branch (Fig. 7j). The lower possibility of multifunctional properties, we anticipate
polariton branch in the avoided crossing region, called increased efforts and progress in the fabrication of
the bottleneck region, has negative curvature and can functional perovskite heterostructures. Direct growth
account for the nonlinear dispersions139,172,173. Analysis of
of heterostructures of different 3D perovskites remains
the polariton dispersions reveals Rabi splitting energies difficult owing to the fast ion-​exchange kinetics. In par­
of hundreds of meV (for example, up to 656 meV for ticular, fast anion exchange fundamentally limits the
CsPbBr3), and the value increases as the dimensions of fabrication of a stable heterojunction with different hal­
the NWs decrease173. Notably, the Rabi splitting energies ides77. However, solid-​state cation exchange seems to
of perovskites are much larger than those of conventional be much slower. Heterojunctions between perovskites
semiconductor NWs (for example, ~25 mV for GaAs with different cations have not yet been reported,
and CdTe, ~200 meV for CdS and ~150 meV for ZnO), and the long-​term junction stability remains unclear.
which suggests strong light–matter interactions in per­ Heterostructures of RP perovskites are also of interest.
ovskite NWs173. The exciton–photon coupling strength In RP perovskites, ion migration is suppressed along
can be further increased in a MAPbBr3 NW/SiO2/Ag both in-​plane and out-​of-plane directions181,182, which
cavity owing to the strong localized excitation field and presents opportunities to fabricate atomically sharp
reduction in the effective mode volume induced by a junctions in either vertical or lateral arrangements183.
surface plasmon174. Recent studies have also demonstrated the feasibility of
There is, however, a need to be cautious in using the constructing heterostructures of 2D perovskites with
exciton–polariton interpretation. In addition to the usual other 2D-​layered materials184,185. It will be interesting
criteria of threshold behaviour in emission intensity and to explore the integration of perovskites with other
peak width, an exciton–polariton condensate is charac­ inorganic or organic semiconductors and functional
terized by both temporal and spatial coherence. A quan­ oxide perovskites51, and to investigate the emerging
titative measurement of a spatial coherent state should multifunctional properties.
have a characteristic dependence on excitation density Although perovskite NWs have shown great promise
for an exciton–polariton condensate175,176. Unfortunately, in lasing applications, challenges remain to realize the
such measurements have not yet been conducted on ultimate goal of electrically driven lasing. Developing
exciton–polaritons in perovskite nanostructures or new device architectures and fabrication strategies to
microstructures139,172,173,177. improve electrical injection, EL performance and device
stability are high priorities. Arrays of NWs with precisely
Future perspectives controlled orientations and positions could be a more
Many exciting aspects of perovskite nanostructures are practical platform for device integration and could
enabled by their facile crystal growth, soft and ionic enable a thin-​film type of device configuration. In this
crystal lattice, ion migration, surface chemistry, defect-​ regard, strategies need to be developed to grow52,63 or
tolerant nature and ferroelectric-​like large polarons. As assemble NWs into arrays186,187. Another major challenge
the field is still rapidly growing, many new opportunities is the thermal heating associated with high injected
and challenges are ahead of us. current densities, which may cause perovskite degra­
The library of perovskite nanostructures will continue dation. Given the ultralow thermal conductivity in per­
to expand. Replacing or partially substituting lead with ovskites188, strategies should be developed to effectively
non-​toxic metal ions will result in more environmentally dissipate heat from perovskites to substrates. In addition
friendly compounds with new properties and function­ to optoelectronic properties, owing to the soft lattices,
alities. Lead-​free perovskites such as ASnX3, Cs2AgBiBr6 it could also be interesting to explore the mechani­
and A3M2X9 (M = Bi or Sb) have been identified as prom­ cal and thermal properties162,188 of these perovskite
ising semiconductors with lower toxicity178. Another nanostructures.
notable example is germanium halide perovskites, which 2D perovskites are a promising alternative to organic
are a class of non-​centrosymmetric compounds that emitter and inorganic quantum dots for low-​c ost,
exhibit strong second-​harmonic generation179. CsGeI3 high-​p erformance light-​emitting devices. However,
is predicted to have an electro-​optic coefficient that owing to the structural complexity and lability of 2D
surpasses the highest value of LiNbO3 at the telecom­ perovskites, it is important to understand and control
munication wavelength of 1,550 nm (ref.180). Moreover, the composition and phase stacking in these solution-​
within the modular structural framework of perovskites, processed films to further increase device efficiency.
a large library of diverse organic cations offers promising Processing conditions for films with high PLQY and

Nature Reviews | Materials

Reviews

the underlying crystal-​growth mechanism have yet to
be determined. It was recently demonstrated that the
energy-​cascade structure can enhance gain properties
through fast energy transfer, which enables efficient
optically pumped lasing from the smallest-​bandgap
phases189. Considering the rapid increase in EL perfor­
mance, these 2D perovskite films promise the possibility
of realizing electrically driven lasing, which has been an
elusive long-​standing goal in solution-​processed opto­
electronics. Although 2D perovskites and their nanos­
tructures in the strong quantum-​confinement regime
could be especially useful for LEDs in the blue region
of the spectrum147, little progress has been made so far
because the synthesis methods tend to yield 3D-​like
perovskite phases. Creative synthesis with exquisite con­
trol over the RP phase compositions190 and potentially
over heterostructures, either in isolated nanostructures
or microstructures183 or in nanostructured thin films,
would accelerate the advances in efficient light-​emitting
devices.
Single-​crystal perovskite nanostructures will remain
interesting from the perspective of fundamental stud­
ies. For example, there are several proposals on how a
polar A-​site cation contributes to charge screening that
could be studied using these nanostructures. Unlike
the 3D perovskites with a limited number of possible
A cations, the structural diversity of RP perovskites may
enable us to understand the mechanistic role of the
A cation on photophysical properties and to establish
structure–property relationships. The variety of pure
n-​value RP perovskites, if their compositions could
be controlled more precisely, offer a unique platform
to better understand the effects of quantum confine­
ment. More in-​depth investigations on the fundamental
physics of RP perovskites, such as polaron physics and
exciton–photon coupling191–193, might enable increased
solar or LED device performance and new applications,
such as exciton–polariton lasing and polaritonics. As
exciton binding energies are higher in RP perovskites
than in their 3D counterparts, stronger light–matter
interactions and potentially lower lasing thresholds
may be expected in RP perovskites. The opportuni­
ties and applications of 1D and 2D perovskite nano­
structures will be addressed in the years to come, and
the future of metal halide perovskite nanostructures
is bright.
Published online xx xx xxxx

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Acknowledgements
S.J., Y.F. and M.P.H. are supported by the US Department of
Energy, Office of Science, Basic Energy Sciences, Division
of Materials Sciences and Engineering (award no. DE-​FG02-
09ER46664). X.-Y.Z. is supported by the US Department of
Energy, Office of Science, Basic Energy Sciences (grant no.
SE-0000234931). J.C. thanks the China Scholarship Council
for support.
Author contributions
Y.F. and S.J. discussed the content of the article and Y.F.
researched data for the article. All authors contributed to the
writing and editing of the article prior to submission.
Competing interests
The authors declare no competing interests.
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