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Invited Feature Article

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Synthetic Evolution of Colloidal Metal Halide Perovskite

Nanocrystals
Chun Kiu Ng, Chujie Wang, and Jacek J. Jasieniak*
ARC Centre of Excellence in Exciton Science, Department of Materials Science and Engineering, Faculty of Engineering, Monash
University, Clayton, VIC 3800, Australia

ABSTRACT: Metal halide perovskite semiconductor nano-

crystals have emerged as a lucrative class of materials for many
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optoelectronic applications. By leveraging the synthetic

toolboxes developed from decades of research into more
traditional semiconductor nanocrystals, remarkable progress
has been made across these materials in terms of their structural,
compositional, and optoelectronic control. Here, we review this
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progress in terms of their underlying formation stages, synthetic

approaches, and postsynthetic treatment steps. This assessment
highlights the rapidly maturing nature of the perovskite
nanocrystal field, particularly with regard to their lead-based
derivatives. It further demonstrates that significant challenges
remain around precisely controlling their nucleation and growth
processes. In going forward, a deeper understanding of the role of precursors and ligands will significantly bolster the versatility
in the size, shape, composition, and functional properties of these exciting materials.

■ INTRODUCTION
The accelerated global reliance on optoelectronic devices
requires the development of faster, more efficient. and cheaper
optoelectronic materials.1,2 Colloidal metal halide perovskite
nanocrystals (PNCs) have emerged as one of the most exciting
nanoscale optoelectronic material candidates.3 Since being first
reported in 2014,4 the field of PNCs has advanced quickly by
leveraging the progress in the material design of their bulk
counterparts5,6 and synthetic developments in traditional
semiconductor nanocrystal (e.g., II−VI or III−V) systems.7−9
This can be seen by the dramatic growth in the number of PNC
publications and the concomitant decline of those focused on
more traditional semiconductor nanocrystals (Figure 1a,b). As a
result of this activity, PNCs with reasonable synthetic control of
size, shape, and composition have been demonstrated in only a
few years.10,11 This synthetic control has led to PNCs with
tunable absorption and photoluminescence (PL) across the
entire visible spectrum,12,13 photoluminescence quantum yields
(PLQY) approaching unity,14,15 short radiative lifetimes of ∼10
ns,16,17 narrow PL full-width at half maxima (fwhm) of 12 to 45
nm,4,18 and suppressed PL blinking statistics.19 These appealing
characteristics have further led to PNCs being successfully
harnessed within numerous optoelectronic applications, includ-
ing light-emitting diodes (LEDs),20,21 lasers,22,23 photodetec-
tors,24,25 amplified spontaneous emitters,26 and photovoltaics
(Figure 1c−f).27,28
Metal halide perovskites have the generalized chemical
formula of ABX3, where A and B are cations and X is a halide
anion. Their precise crystal phase can be gauged by the
Goldschmidt tolerance factor, t = (rA + rX)/[(√2)rB + (√2)rX],
where rA, rB, and rX are the radii for the A (e.g., MA+, FA+, and
Cs+), B (e.g., Pb2+ and Sn2+), and X (Cl−, Br−, and I−) ions,
respectively.29 When t ≈ 1, the perovskite will possess a highly
symmetrical cubic phase (Figure 1g) phase, while for t > 1 and t
< 0.8, a hexagonal or tetragonal (Figure 1h)phase and a
rhombohedral or orthorhombic (Figure 1i) phase, respectively,
will be favored. This structural framework provides great
flexibility for tuning the composition of metal halide perovskites
and their resulting properties.
The PNC field has closely followed the advances in
compositional control arising from bulk perovskite films. As a
result, most attention to date has been placed on lead-based
candidates. These exhibit a distinct electronic structure
compared to the more typical tetrahedrally coordinated
semiconductors (e.g., CdSe or GaAs), with the lead halide
perovskite conduction and valence bands being dictated by
antibonding Pb(6p) and hybridized X(p)−Pb(6s) orbitals.10
This entails that they have rather benign defect states, which is a
key reason for their exceptional optoelectronic properties.
Moreover, it indicates that the modification of the X and B sites
provides the most suitable strategies for modifying the band gap.
Of these, the modification of the halide composition has
emerged as the most facile for tuning the optical properties of
PNCs across the visible spectrum,16 with the larger halides (i.e.,
rCl− = 1.81 Å, rBr− = 1.96 Å, rI− = 2.20 Å) yielding higher band
gaps owing to their energetically deeper bonding p orbitals.10,31
In contrast, A-site modification has exhibited limited band gap
tunability but has opened up hybrid and inorganic perovskite
Received: April 24, 2019
Revised: June 2, 2019
Published: June 4, 2019

© 2019 American Chemical Society 11609 DOI: 10.1021/acs.langmuir.9b00855

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Figure 1. (a) Accumulative and (b) per annum bibliometrics of various semiconductor nanocrystal/colloidal/quantum dot systems from 1992 to 2018
(from the Web of Science database). (c) Scanning electron microscopy (SEM) cross section of a CsPbBr3 photovoltaic device, adapted with
permission from ref 28. Copyright 2016 Springer Nature. (d) Schematic of a colloidal CsPbBr3 green-emitting LED and (e) photographs of their 2 × 2
mm2 active area operating at 5 V. Reproduced from ref 20. Copyright 2018 American Chemical Society. (f) Ultrastable amplified spontaneous emission
of a CsPbBr3 PNC film with improved passivation. Reproduced from ref 26. Copyright 2015 American Chemical Society. Unit cell of general (g) cubic,
(h) tetragonal, and (i) orthorhombic ABX3 structures where A+ cations are green spheres and purple BX6 polyhedral comprise steel blue B2+ and purple
X− spheres. Reproduced with permission from ref 30. Copyright 2015 American Physical Society.

classes, which respectively use organic (e.g., MA+ or FA+) and
inorganic (e.g., Cs+) cations.12,32 Both of these classes exhibit
promising optoelectronic properties; however, the all-inorganic
perovskites have tended to exhibit improved thermal, chemical,
and photostabilities.33−36 These appealing properties have led to
inorganic metal halide PNCs being the most studied to date,
with CsPbX3 emerging as the archetypal system.
B-site modification has been motivated by its potential for
optoelectronic modification and the removal of lead, which is
inherently toxic.37 Lead’s closest analogue, Sn2+, is readily used
as a substituent in bulk perovskite counterparts to reduce the
band gap but has proven difficult to integrate within PNCs
because of its tendency to readily oxidize to Sn4+ within
nanocrystalline systems.38 As a result, the more redox-stable Bi3+
and Sb3+ cations, which are also notably isoelectric with Pb2+ and
Sn2+, respectively, have emerged as promising candidates for
achieving Pb-free PNCs.37 In addition to these direct band-edge
recombination materials, new optoelectronic functionality has
been further introduced through B-site doping. The dual
emission observed for Mn/CsPbCl339,40 and sensitized
lanthanide emission for La/CsPbX3 are the most common
examples of these.41
Beyond their enhanced optoelectronic properties, PNCs also
provide greater structural flexibility compared to their bulk
counterparts.16 This is most clearly demonstrated for CsPbI3, for
which the bulk nonperovskite polymorph is a nonfunctional
(nonluminescent, large band gap) orthorhombic γ-phase under
ambient conditions42 and transforms into its desired functional
cubic α-phase above ∼310 °C.43 However, in its colloidal form,
11610
the functional phase can be metastabilized under ambient
conditions through a reduction in grain size and appropriate
surface passivation to modify its surface energy.44,45 Access to
such metastable structural regimes provides an important
avenue for expanding the structure−property landscape of
perovskites.
These developments in the composition and phase engineer-
ing of colloidal PNCs have been underpinned by synthetic
developments across both injection and noninjection techni-
ques.4,16,46 Injection methods involve the mixing of precursor
solutions to induce supersaturation and drive the formation of
PNCs. Meanwhile, noninjection methods involve the controlled
reactivity of precursors during a thermal heating profile to
control the nucleation and growth dynamics. Across each of
these synthetic routes, the rapid nucleation and growth
processes of PNCs have made their synthetic windows
extremely sensitive to factors such as the reaction temper-
ature,47,48 reaction time,49 solvent properties,50,51 acid−base
equilibria,52−54 reagent species,55−57 ligand species17,58 and
mixing rates.59 Studies have shown that adjustments to even one
of these parameters can modify the structural properties of the
resulting PNCs among quantum dots (QD), nanocube (NCu),
nanoplatelet (NPL), nanosheet (NS), nanowire (NW), and
nanorod (NR) morphologies.51,60,61 While this demonstrates
versatility, it also highlights the challenges in achieving structural
control within these emerging materials.
The progress within the field of colloidal perovskite
nanocrystals has been rapid but is still maturing, with many
imminent research questions. In this timely review, we provide a
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detailed synopsis of the developments that have been made
toward synthesizing and postprocessing colloidal perovskites. As
a way of focus, here we do not go into detail regarding the
photophysics and applications of such materials but consider
only nontemplated synthetic methods because these have been
shown to be more suitable for the synthesis of homogeneous
PNC dispersions.
■ NANOCRYSTAL FORMATION
Nucleation. According to the classical LaMer model, the
formation of colloids involves the conversion of precursors to
reactive monomers that can form metastable clusters, some of
which ultimately exceed the critical radius and grow to form the
final nanocrystal.62 The conversion rates of the precursors
govern the dynamics of the system achieving supersaturation,
which are dictated by the specific precursor chemistry. Generally
speaking, the nucleation and growth events of PNCs can be
distilled down to a double-displacement or salt metathesis
reaction given by eq 1.
A+ + B2 + + 3X− → ABX3 (1)
For low-temperature PNC injection reactions (<90 °C), a
supersaturated state is achieved through solvent control, in
which the addition of an antisolvent drastically reduces the
solubility of the precursors down to 10−7 g/mL.63 Within an
appropriate synthetic window, PNCs precipitate and are
concurrently stabilized by ligands during mixing, commonly in
the form of oleic acid (OA) and oleylamine (OLA) and their
conjugates oleate (OA−) and oleylammonium (OLA+),
respectively.59 The stoichiometric reaction for a typical low-
temperature reaction is described by eq 2.
AX + BX 2 + OA + OLA → ABX3 + OA− + OLA+ (2)
Meanwhile, the hot-injection (HI) method for PNCs uses
reaction temperatures typically ranging from 90 to 240 °C. It
harnesses a rapid injection process to effectively “decouple” the
nucleation and growth stages to result in more homogeneous
colloidal nanocrystal dispersions.64 Its success relies on the
nucleation and growth dynamics being slower than the effective
mixing times of the precursor solution. For PNCs, this has
proven to be difficult because nucleation has been exper-
imentally verified to occur within 0.4 s (Figure 2a).18 Recent
theoretical works have further suggested that the nucleation
processes themselves occur on submicrosecond time scales.65
These fast kinetics have made for detailed experimental
investigations into the early formation stages of perovskites
limited to date. Despite this, for a typical PNC HI synthesis, the
generalized conversion of precursors into their reactive species
follows eqs 3 and 4, with the overall formation reaction given by
eq 5.
Cs 2CO3 + 2OA → 2CsOA + H 2O + CO2 (3)
PbX 2 + 2OA + 2OLA → PbOA 2 + 2OLAX (4)
CsOA + PbOA 2 + 3OLAX → CsPbX3 + 3OA− + 3OLA+
(5)
Across these reaction mechanisms, the intricacies of the
underlying nucleation mechanism remain unclear. One model of
PNC formation involves the initial formation of corner-sharing
PbX6 polyhedra as nuclei, which then have their interstitial voids
gradually filled with A+ ions,66 akin to intramolecular exchange
processes in bulk perovskite.34 An alternative mechanism
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Invited Feature Article
Figure 2. (a) Evolution of CsPbI3 absorption spectra between 0.4 to 2.4
s from 580 to 670 nm, corresponding to PNC sizes of 8−12.5 nm and
(b) the estimated particle size found over a range of different reaction
temperatures. Reproduced from ref 18. Copyright 2016 American
Chemical Society. (c) TEM micrographs of CsPbI3 PNC as a function
of reaction time and (d) concurrent evolution of the PL spectrum as it
changes with the size distribution of the PNCs, as reproduced with
permission from ref 74. Copyright 2016 Royal Society of Chemistry.
involves heterogeneous seeding by Pb0 nanoparticles within
the reaction mixture. This is supported by the observation of
such seeds within Pb2+ precursor solutions prior to PNC
nucleation50 and Pb-rich67 or even Pb0 50 “dark particles” within
the PNCs synthesized using low-temperature injection,32,52,58
high-temperature injection,60,68,69 and multiple noninjection
methods.55,70,71 The existence of Pb0 seeds is consistent with
Pb2+ being easily reduced (E0 = −0.13 V)72 and the fact that
most synthetic methods use aliphatic amines for stabilization,
which are also mild reducing agents. However, further research
is required to unambiguously validate this mechanism of
nucleation, particularly because PNCs have also been observed
to degrade under an electron beam during characterization,
yielding similar structural characteristics.73
Growth. A key synthetic challenge of PNCs is that their
nucleation and growth stages are difficult to decouple. The
depletion of available free monomers during growth is complete
within ∼5 s of reaction time for HI (Figure 2b).18 According to
the classical LaMer model, under these reaction conditions the
predominant growth mode is expected to rapidly transition from
that involving free monomer consumption on the very early time
scales to Ostwald ripening. Studies on CsPbI3 PNCs have shown
that size focusing of nucleated NCu occurred within the first few
seconds of the reaction (Figure 2c,d).74 This was followed by
defocusing of the colloidal ensemble through diffusion-driven
growth, which is consistent with the Ostwald ripening process.
Similarly, the growth stage of PNCs in low-temperature
injection syntheses has been estimated to be mostly complete
after 10−20 s.28 The lowered reaction kinetics compared to that
of HI methods likely stems from the decreased monomer
diffusion rates and reactivities at lower temperatures. As-
synthesized PNC dispersions from low-temperature synthetic
methods can contain 10−30% by volume polar solvent, such as
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Figure 3. UV−vis absorption and PL spectra of CsPbI3 PNCs synthesized with (a, b) OA or (c, d) TMPPA paired with OLA, with the latter exhibiting
enhanced stability under ambient conditions. Reproduced with permission from ref 45. Copyright 2017 Royal Society of Chemistry. (e) DFT
modeling of oleylammonium ion pairs and sulfobetaine interactions with CsPbBr3 surface (Cs, gray; Pb, orange; Br, magenta). Reproduced from ref 81
Copyright 2018 American Chemical Society.
dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or
isopropanol (IPA).28,63 Owing to the solubility of the perovskite
lattice in such polar solvents, Ostwald ripening is enhanced
compared to syntheses where only nonpolar solvents are used.75
It has been suggested that the presence of these solvent mixtures
makes for PNC formation subject to classic micellar formation
theory, where the electrostatic and hydrophobic interactions
dictated by the specific precursors, solvents, and ligands
influence the final PNC morphology.76
Following the initial, rapid growth stage of nanocrystal
formation, orientated attachment is the other noteworthy
growth mechanism that is prevalent in PNC systems.77 This
growth mechanism is believed to occur when the extent of
surface ligand passivation is poor or is destabilized to allow for
coalescence. It is considered to be the dominant mechanism for
the formation of larger PNC structures, such as NWs, NPLs, and
NSs.50,78
Ligand Interactions with Perovskite Nanocrystals.
Ligand species used for PNCs have often been adopted from
more traditional semiconductor colloids, with primary aliphatic
amines and carboxylic acid species being the most favored.48,57
Surface investigations of synthesized PNCs using these ligand
combinations have unambiguously confirmed that the aliphatic
ammonium and carboxylate species are the dominant surface
binding ligands.79,80 These form in solution when ligand pairs
undergo simple acid−base reactions, such OLA and OA reacting
to form oleylammonium−oleate (OLA+−OA−).53 Density
functional theory (DFT) modeling has further indicated high
ligand-to-surface interaction energies of these reacted species,
with that for OLA+ and OA− ranging from −1.73 to −1.95 eV for
OA−81 and to −1.14 eV for OLA+.15 In comparison, the binding
energy of neutral Cs-oleate and Pb-oleate is approximately half
that of the oleate or an alkylammonium-alkanoic acid pair, thus
demonstrating that the charged species are more favorable
surface passivants.79
Investigations into alkylamine−alkanoic ligand pairs of
different chain lengths have further shown that lengthier ligand
species (octyl- or higher) yield better-stabilized and higher-
quality colloidal dispersions.82−84 This stems from the improved
steric stabilization provided by the longer-chained ligands,75
which also inhibit monomer uptake during PNC growth to
typically result in smaller sizes and NCu formation.57,61 As a
result, longer-chain-length acids, such as OA and tetradecanoic
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Invited Feature Article
acid, have yielded higher PLQYs (>80%) than their shorter-
chained derivatives.58
Phosphorus-containing ligands have also been used in PNC
synthesis. Of these, trioctylphosphine (TOP) has been the most
common because it forms highly soluble complexes with PbX2.16
Its use in mixed-ligand reactions involving OA and OLA has
enabled the synthesis of high-quality CsPbI3 quantum dots, with
PLQYs approaching 100%.14 Importantly, nuclear magnetic
resonance (NMR) spectroscopy measurements have revealed its
absence from the synthesized PNC surfaces, with only OLA+
and OA− species being detected. A similar observation was
observed when CsPbI3 PNCs were synthesized with OA
substituted with branched bis(2,4,4-trimethylpentyl)phosphinic
acid (TMPPA) in the HI synthesis, only this time OLA+ was
observed as the sole ligand on the surface.45 Despite the
phosphinic acid not being an active surface binding species for
the final CsPbI3 PNC, the resulting OLA+ surface ligand shell
allowed for the successful metastabilization of the functional α-
phase under ambient conditions (Figure 3a−d). It remains
unclear as to whether the absence of the phosphorus-containing
ligands in the above NMR studies arises from weaker chemical
interactions at the PNC surface and/or from steric effects from
the branched ligand chains. The use of trioctylphosphine oxide
(TOPO) has similarly improved size uniformity and stability of
PNCs, although its presence on the surface confirms that it plays
a passivating role rather than merely acting as a sacrificial
additive or spectator ligand.69,71
Investigations into less common ligands have included
nonprimary amines (i.e., secondary to quaternary amine
substitutes),58,85 bidentate ammonium species,51,85 aniline
derivatives,86 and zwitterions.81 Generally, these have yielded
lower-quality PNCs compared to the more traditional ligand
combinations because of factors that include poorer steric
stabilization, modified precursor/monomer solubilities, and
more prominent Ostwald ripening.51 However, there are a few
exceptions, with the most notable being by Krieg et al.,81 who
used a long-chained sulfobetaine zwitterion as the sole ligand
(Figure 3e), which yielded improved chemical durability and
storage lifetimes compared to the standard OA and OLA ligand
pair. This was attributed to the sulfobetaine molecule being
unaffected by Bronsted acid−base equilibria and, because of a
kinetically stabilized chelation mechanism, had a PNC surface
binding energy similar to that of OLA+.
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Table 1. Summary of Major Classes of Injection and Noninjection Synthetic Methods for Perovskite Nanocrystals

Table 2. Summary of the Major Synthetic Procedures for Perovskite Nanocrystalsa

method composition shape size (nm) PLQY reaction conditions ref
NT MAPbX3 NP 6 17% ambient, 80 °C 4
NT CsPbBr3 NCu, NPL 8.5, 41 × 8 31−78% ambient, RT 52
LARP MAPbX3 QD ∼3.3 50−70% ambient/N2, RT 88
LARP MA3Bi2X9 QD ∼3 4−12% ambient/N2, RT 89
LARP CsPbX3 QD 11 70−95% ambient, 0−30 °C 63
LARP Cs3Sb2X9 QD ∼3 20−46% ambient, RT 92
HI CsPbX3 NCu 4−15 50−90% N2, 140−200 °C 16
HI Mn:CsPbCl3 NCu 11 <27% N2, 185 °C 40
HI Lanthanide: CsPbCl3 NCu 6.3−7.6 28% N2, 160 °C 41
HI CsSnX3 NCu ∼10 0.14% N2, 170 °C 38
HI Cs3Sb2X9 NR, NW 20 × ≤3400 4% N2, 170−200 °C 106
HI Cs3AgBiCl6 NCu ∼8 ∼0.3% N2, 140 °C 110
convection CsPbX3 NCu 4.0−15 87% N2, 50−170 °C 46
solvothermal CsPbX3 NCu, NW 8.2−12.5 80% ambient, 160 °C 55
microwave CsPbX3 NCu 10−13 11−92% ambient, 800 W 115
ultrasonication CsPbX3 NP, NPL 8−15 10−92% ambient, RT 70
a
QD, quantum dot; NP, nanoparticle; NCu−nanocube; NPL, nanoplatelet; NS, nanosheet; NR, nanorod; NW, nanowire; RT, room temperature
∼25 °C; PLQY, photoluminescence quantum yield; N2, nitrogen gas; W, watts

■ SYNTHETIC METHODS
In this section, we will discuss the advances across the various synthesis
approaches that have been developed within both injection and
noninjection approaches. A brief description and a summary of the
advantages and limitations of each of these is presented in Table 1.
Furthermore, in Table 2, we provide an overview of the major synthetic
procedures used across these methods. By far, the most investigated
synthetic approaches for PNCs are the injection methods. As such, here
we have divided these sections to reflect the key advances across both
lead-based and lead-free perovskite classes.
Anti-Solvent-Assisted Low-Temperature Injection. Lead-
Based Perovskites. The first reported low-temperature injection
synthesis of any PNC was by Schmidt et al., who prepared hybrid
MAPbBr3 nanoparticles.4 This synthesis was subsequently dubbed the
non-template (NT) method. In their synthesis, a DMF solution that
contained solubilized precursor salts (MABr, PbBr2) was mixed with a
ligand solution containing OA and octylammonium bromide in 1-

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octadecene (ODE) at 80 °C. This was followed by the addition of an

antisolvent (acetone) to reduce the solubility of the salts and precipitate
the PNCs. The synthesized MAPbBr3 nanoparticles were found to have
an average size of 6.2 nm, with a typical emission at ∼525 nm and a
PLQY of 17%. Fine tuning of the molar ratios between the ammonium
species and PbBr2 to 4:1 was shown to yield ∼5.5 nm PNCs, with a
comparable emission wavelength but a significantly enhanced PLQYs
of up to 83%.87 This enhancement in PLQY was considered to arise
from ammonium cations binding to undercoordinated bromide ions.
The NT method has also been applied to all-inorganic CsPbX3 PNCs
by incorporating a Cs-oleate precursor solution, analogous to that used
in HI syntheses.52 Driven by the search for a more scalable and robust
processing method, Akkerman et al. explored the use of low-boiling-
point ligands and solvents within the NT method.28 By employing
propionic acid and butylamine as ligands and IPA and n-hexane as
solvents, the authors were able to scale the synthesis of crude CsPbBr3
PNCs to volumes of as high as 900 mL. The sizes of NT-synthesized
QDs could be controlled between 2.6 and 7.2 nm by simply changing
the relative polar and nonpolar solvent volumes.32 The PLQYs were
found to range between 80 and 92%.
As an analogue of the NT method, Zhang et al. introduced the
ligand-assisted re-precipitation (LARP) approach to synthesize
MAPbX3 QDs at room temperature.88 In this synthesis, all precursor
materials (MABr and PbBr2) and ligands (OLA and OA) were
dissolved in a polar solvent (DMF or DMSO). This solution was added
to a toluene antisolvent to drive the precipitation of 3.3 nm MAPbBr3
PNCs, which exhibited PLQYs of up to 70%. Through reaction
temperature control between 0 and 60 °C, the sizes of the MAPbBr3
PNCs were found to be tunable in the range of 1.8 and 3.6 nm, with
lower temperatures yielding lower particle sizes.47 Quantum confine-
ment effects could be observed at the smaller particles sizes, with the
enhanced exciton binding energies permitting enhanced PLQYs of as
high as 93%.
The synthesis of all-inorganic CsPbX3 PNCs has also been explored Figure 4. (a) Photograph of CsPbX3 (X = Cl, Br, I) PNC solutions
using LARP through the substitution of the A-site organic halide salt under UV illumination and (b) their associated PL spectra. Reproduced
with a CsX salt analogue.32,58,63 Such studies have demonstrated PNCs with permission from ref 58. Copyright 2016 Royal Society of
with controllable NCu sizes from 9 to 20 nm that exhibited PLQYs of as Chemistry. (c) Different chain length acid−base ligand combinations
high as 95% and narrow PL fwhm’s of 12 to 38 nm.32,63 Tuning the influencing the CsPbX3 morphology. Reproduced from ref 17.
halide composition between CsPbCl3 and CsPbI3 has further allowed Copyright 2016 American Chemical Society.
for spectral control across the 405 to 680 nm visible region (Figure
4a,b).58,63 Notably, the synthesis of functional cubic CsPbI3 has been
challenging using CsX salts because of the relatively large synthesized tune the emission between 370 and 560 nm. These all-inorganic PNCs
particle sizes, resulting in phase instability. It has been shown that exhibited enhanced thermal and chemical stabilities compared to their
through the use of Cs-oleate precursors, smaller ∼5 nm CsPbI3 QDs hybrid counterparts.90,91
could be prepared, thus enabling the cubic phase to be metastabilized.17 In addition to Cs+-containing Pb-free all-inorganic perovskites, the
The same authors showed that CsPbX3 PNCs could be synthesized synthesis of Rb+-containing zero-dimensional Rb3Bi3Cl16 has also
with a range of morphologies (QD, NCu, NPL, and NR) through recently been reported.93 The authors dissolved RbCl and BiCl3 in γ-
control of the acid−amine ligand chain lengths (Figure 4c). butyrolactone with small amounts of OA and octylamine as ligands.
Lead-Free Perovskites. Leng et al. was the first to report MA3Bi2Br9 This precursor solution was held at 80 °C for an hour before being
QDs synthesized through a modified LARP approach.89 The authors injected into ethanol. The resultant Rb3Bi3Cl16 PNCs displayed a PL
dissolved MABr and BiBr3 in DMF and ethyl acetate, using n- peak centered at 437 nm with a fwhm of 93 nm and a PLQY of 28%.
octylamine as a ligand, and then injected this solution into octane Their small size of ∼1.85 nm was attributed to the smaller atomic radii
containing OA at 80 °C. This resulted in ∼3 nm PNCs, which possessed of Rb+ and Bi3+, as well as the lower solubility of RbCl compared to that
a modest PLQYs of up to 12%. Postsynthetic halide exchange was able of CsCl, which would result in a more supersaturated solution and
to access MA3Bi2X9 (X = Cl, Br, I) compositions and tune the PL peaks therefore more rapid nucleation. Importantly, for their prospective use
from 360 to 540 nm. in real-world applications, these particles were found to retain 70% of
All-inorganic Cs3Bi2X9 (X = Cl, Br, I) has been synthesized by their fluorescence after a month of ambient storage and had a thermal
injecting a DMSO solution containing CsX and BiX3 precursors into stability of up to 400 °C.
IPA. The nanocrystals showed an emission tunability range of 400 to Hot Injection. Lead-Based Perovskites. The first report outlining
560 nm (Figure 5a−c).90 Without any aliphatic reaction ligands the HI synthesis of inorganic CsPbX3 PNCs was by Protesescu et al.16
present, ∼6 nm trigonal Cs3Bi2Br9 QDs were formed under these The authors reacted Cs2CO3 with OA in ODE under an inert gas (N2)
synthetic conditions, albeit with a low PQLY of 0.2%. This was environment at 120 °C to make a Cs-oleate precursor (eq 3).
enhanced to 4.5% when OA was introduced into the reaction. By using Meanwhile, PbX2 was separately dissolved in ODE with the assistance
octylamine and OA in the reaction and ethanol as the nonsolvent, of OLA and OA (eq 4). The Cs-oleate was injected into the PbX2
reactions carried out at 80 °C yielded 3.9 nm Cs3Bi2Br9 QDs with an solution at a temperature of 140 to 200 °C to form colloidal CsPbX3
improved PLQY of up to 19.4%.91 Using very similar synthetic PNCs (eq 5). Mixed-halide PNCs could be readily achieved by
approaches, antimony-substituted Cs3Sb2Br9 QDs have also been combining different PbX2 salts. Generally, Cs/Pb ratios of 1:2 to 1:4
successfully demonstrated.92 The 3.1 nm trigonal Cs3Sb2Br9 exhibited have yielded the most monodisperse PNCs.18 To preserve the narrow
an emission peak at 410 nm and a very promising PLQY of 46% (Figure size distribution of the PNCs, the reaction was terminated after 5 s by
5d−f). Postsynthetic halide exchange could be further performed to quenching in an ice bath. The resulting NCu’s were 4 to 15 nm in size,

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Figure 5. (a) Photographs and (b) XRD and (c) UV−vis absorption and PL spectra of Cs3Bi2X9 (X = Cl, Cl0.5Br0.5, Br, Br0.5I0.5, I) PNCs. Reproduced
with permission from ref 90. Copyright 2016 John Wiley and Sons. (d) UV−vis absorption and PL spectra of Cs3Sb3Br9 with an inset of its colloidal
solution under UV light. (e) Diagram of its atomic structure and (f) HR-TEM of ∼3 nm Cs3Sb3Br9 QDs. Reproduced from ref 92. Copyright 2017
American Chemical Society.

Figure 6. Colloidal dispersions of all-inorganic CsPbX3 perovskite nanocrystals (a) under UV light (λ = 365 nm), (b) their photoluminescent emission
profiles, (c) and UV−vis absorption spectra. Reproduced from ref 16. Copyright 2015 American Chemical Society.

with lower temperatures yielding the smaller particle sizes. Through
temperature and halide composition engineering, the resulting CsPbX3
PNCs exhibited tunable absorption and PL across the entire visible
spectrum, with PLQYs of 50 to 90% and narrow PL fwhm of 12 to 42
nm (Figure 6).
Further investigations into the effects of reaction temperature on the
HI synthesis of CsPbX3 showed that lower reaction temperatures of 90
to 130 °C strongly favored asymmetric growth through oriented
attachment, resulting in 2D NPLs or NSs (Figure 7a).78,94 The PLQYs
of the NPLs ranged between 10 and 84%, with the thinner NPLs having
lower values likely due to enhanced surface trap contributions.
Lowering the reaction temperature to 70 °C resulted in a transparent
suspension of amorphous, micrometer-sized sheets composed of
unreacted precursors. Meanwhile, within the standard 150 to 200 °C
synthetic window, extended reaction times of more than 10 min were
shown to transform the NCu PNCs, initially into NWs through an
oriented attachment mechanism and then into coarsened micrometer-
sized crystals at prolonged reaction times of >180 min (Figure 7b).49
Beyond the reaction temperature and time, ligand and precursor
engineering are the other major handles used to modify the resulting
structural properties of PNCs. Pan et al. investigated a variety of
aliphatic carboxylate and amine ligand pairs, ranging from acetic to oleic
acid and hexyl- to oleylamine, respectively, generally observing an
increased NCu size for decreasing acid chain lengths across these.57
Meanwhile, using shorter amines than OLA resulted in PNCs adopting
NPL morphologies. The NPL thickness exhibited an amine chain-
length dependence, with the thinnest NPLs of 1.8 nm in thickness being
grown using hexylamine. Alternative metal precursors, including lead
oxide,95 lead acetate,68 cesium acetate,57 and cesium hydroxide,58 have
also been explored as a way to gain finer control of the reaction
conditions.56,83 In these syntheses, the use of ammonium halides or
benign metal halides as halide sources allowed for better stoichiometric
control over the reaction mixture.96 Typically, X/Pb ratios ranging from
2:1 to 4:1 have been shown to yield the highest-quality PNCs, with
improved PLQYs, narrower fwhm’s, and higher PL lifetimes.95 The
optoelectronic improvements under these halide-rich syntheses were
considered to arise from reduced surface halide vacancies on the PNCs,
which can act as traps.
Tuning the halide composition readily modifies the spectral nature of
PNCs: A- and B-site engineering can provide extended opportunities to
modify their structure−property relations. Protesescu has been one of a
few authors to demonstrate A-site modification using HI, incorporating
FA into CsPbI3 PNCs by simply injecting the FA-oleate precursor
together with Cs-oleate during synthesis.12 Using a molar ratio of 2:1
FA/Cs in the precursor solution, it was found that only 10% of the FA
was incorporated into the PNC structure. The synthesized
FA0.1Cs0.9PbI3 PNCs exhibited PL emission at 685 nm with a PLQY
of >70%, and their cubic phase was maintained for months under
ambient conditions (Figure 8a). The latter is consistent with CsPbI3
PNCs alloyed with a larger secondary A-site cation (e.g., FA+) being
more stable in a cubic phase because of their Goldschmidt tolerance
factor being closer to 1.97,98

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Figure 7. Conditions that can influence the morphology of HI-synthesized CsPbBr3 PNCs with inset photographs of solutions under UV light. (a)
Reaction temperature showing NPLs forming at lower temperatures as opposed to NCu at 150 °C, scale bar 50 nm. Reproduced from ref 78. Copyright
2015 American Chemical Society. (b) Reaction times of >180 min showing initial NCu transitioning into NWs and NSs with a scale bar of 100 nm.
Reproduced from ref 49. Copyright 2015 American Chemical Society.
Rubidium has also been shown to be an alternative to cesium for all-
inorganic PNCs. This was first demonstrated with the synthesis of
orthorhombic RbPbI3 NWs by following the standard HI procedure
and replacing Cs2CO3 with Rb2CO3.99 A reaction time of 30 min at 150
°C allowed the initially formed NRs to grow into NWs with a diameter
of ∼32 nm and lengths of <100 μm. More extensive studies have found
that the low tolerance factor of ∼0.8 for RbPbX3 (X = Br, Cl) is close to
the lower formability range of perovskites and is not readily
synthesized.100 This problem could be alleviated by using mixed A-
site RbxCs1−xPbX3 (X = Br, Cl) compositions, yielding PLQYs
comparable to CsPbX3 PNCs.
B-site cation doping has been shown to be more compatible with
current HI protocols. Mn2+ has emerged as one of the more successful
dopants because it has the same valence as the native Pb2+. Liu et al. first
reported that by simply dissolving MnX2 precursor simultaneously with
PbX2 within a typical PNC HI protocol, Mn/CsPbX3 PNCs could be
produced.40 At higher MnX2 precursor concentrations, the Mn2+
dopant amount in the PNCs would increase, achieving a saturated
substitution ratio of 46% at a Mn/Pb reaction ratio of 10:1 (Figure
8d,e).39 As a result of the doping process, these PNCs exhibited dual
emission properties, with a higher-energy intrinsic perovskite emission
competing with a lower-energy radiative recombination process
between the 4T1 and 6A1 states of Mn2+ at ∼580 nm.101 Mn2+ doping
has been shown to further improve the thermal and ambient
atmospheric stabilities of CsPbBr3 PNCs.102
Pan et al. has demonstrated that lanthanide ions (Ce3+, Sm3+, Eu3+,
Tb3+, Dy3+, Er3+, and Yb3+) can also be introduced into the CsPbCl3
PNCs by simply adding lanthanide chloride salts to the Pb precursor
solution during the HI process.41 Because of the 3+ valence of the
lanthanide ions and their significantly smaller ionic radius versus that of
lead, the doped CsPbCl3 exhibited a distorted perovskite structure with
a smaller lattice constant (e.g., 3.96 Å for undoped CsPbCl3 and 3.87 Å
for Yb/CsPbCl3, Figure 8b). In these systems, the perovskite acts as a
sensitizer for the dopant, which enables secondary emission from the
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specific lanthanide to be observed. By changing the lanthanide species,
tunable photoluminescence ranging from 500 nm to the near-infrared
has been observed under laser illumination, with the overall PLQY
being around 15 to 30% (Figure 8c). Importantly, Zhou et al. reported
that cerium and ytterbium codoped CsPbCl1.5Br1.5 PNCs possessed a
QY of 146% at 988 nm.103 This demonstration of quantum cutting
further highlights that lanthanide-doped PNCs provide a scope of
application as security and biological markers, high-efficiency photo-
voltaics, and optical sensors.
Lead-Free Perovskites. Efforts toward replacing Pb with Sn within
HI synthesis have shown that by simply substituting PbX2 with SnX2,
lead-free CsSnX3 PNCs with an ∼10 nm size can be readily produced.38
These RT orthorhombic (X = Br, I) or cubic (X = Cl) CsSnX3 NCu’s
exhibited a perovskite structure with a tunable band gap based on their
halide composition (Figure 9a−c). However, because of the distortion
of the halide sites and higher defect densities compared to those of their
lead analogues, they exhibited a maximum PLQY of only 0.14%.
Interestingly, by using SnI4 as a precursor within the same HI
procedure, more air-stable Cs2SnI6 PNCs resulted, although the exact
mechanism for this remains unclear.104 By extending the reaction time
from 1 min to 1 h, the initial Cs2SnI6 PNCs were observed to transition
to NRs and NWs before adopting NPL morphologies. Their highest
PLQY remained low at 0.48%, indicating a significant scope for further
structural refinement.
Bismuth substitution has been another common approach to
achieving lead-free PNCs. By using BiX3 as the precursor in the HI
protocol, ∼18 nm hexagonally shaped Cs3Bi2X9 PNCs were produced,
which also possessed a hexagonal crystalline phase (Figure 9e).105
Owing to this large size and different phase, the PLQY of these Cs3Bi2X9
PNCs was very low (0.017%) compared to that of those synthesized
using low-temperature methods. Notably, the hexagonal Cs3Bi2X9
PNCs possessed an interesting direct−indirect band structure, which
is composed of a direct exciton transition and also a phonon-assisted
indirect transition. Such a unique band structure endows the Cs3Bi2X9
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Figure 8. (a) Optical absorption and PL spectra of FA0.1Cs0.9PbI3 and FAPbI3 PNCs freshly synthesized and 6 months later. Insets show photographs
of their respective solutions under sunlight and λ = 365 nm UV light. Reproduced from ref 12. Copyright 2017 American Chemical Society. (b) XRD
and (c) PL characterization of lanthanide-alloyed CsPbCl3 PNCs. Reproduced from ref 41. Copyright 2017 American Chemical Society. (d) TEM
micrographs of CsPbxMn1−xCl3 NCu prepared at 170 °C with various Pb/Mn molar ratios in its reaction mixture and (e) the corresponding PL spectra
with emission peaks at ∼410 nm and ∼580 nm (higher Pb/Mn ratios result in higher Mn levels of doping determined via EDX). Reproduced from ref
39. Copyright 2017 American Chemical Society.

Figure 9. (a) XRD and (b) UV−vis absorption spectra of CsSnX3 (X = Cl, Cl0.5Br0.5, Br, Br0.5I0.5, I) PNCs. (c) TEM micrograph of CsSnI3 nanocrystals
(scale 100 nm) with the inset showing NCu ≈ 9.9 nm in size. Reproduced from ref 38. Copyright 2016 American Chemical Society. (d) UV−vis
absorption and PL spectra of Cs3Bi2I9 PNCs showing direct (580 nm) and indirect (605 nm) emission. (e) TEM micrographs showing particle sizes of
∼18 nm. Reproduced from ref 105. Copyright 2017 American Chemical Society.

PNCs with a dual peak emission, which is centered at 580 and 605 nm
for X = I (Figure 9f). This dual emission was not observed in LARP-
synthesized Cs3Bi2X9 PNCs, which may be due to their different
morphology and/or crystalline phase.
To a lesser extent, antimony-substituted perovskites have also been
investigated. By using antimony chloride (SbCl3) within HI protocols
comparable to those mentioned above, mostly trigonal Cs3Sb2Cl9 NRs
and NWs with diameters of 20 nm have been synthesized with tunable
lengths of up to 290 nm and 3.4 μm, respectively.106 This size tunability
was achieved through controlling the amount of the SbCl3 precursor
and OA/hexadecylammonium ligand ratios in their reactions. The
emission peak maximum of NW samples at 436 nm exhibited a PLQY
of 4%. Cs3Sb2I9 NPLs and NRs have been similarly synthesized using
reaction temperatures of 180 and 230 °C, respectively.107 The NPLs

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Figure 10. (a−d) TEM micrographs of convection-synthesized CsPbI3 PNCs with sizes of 3.3, 4.5, 6.5, and 10.4 nm. (e) PL spectra for different halide
compositions. (f) Photographs of CsPbBr3 and CsPbI3 PNC solutions. (g) Absorption and PL spectra of CsPbI3 PNCs grown at 50, 80, and 110 °C,
adapted with permission from ref 46. Copyright 2016 Springer Nature.

Figure 11. TEM micrographs of solvothermally synthesized PNCs with different morphologies. (a) CsPbBr3 NCu, inset: HR-TEM revealing 0.58 nm
lattice spacing; (b) CsPbBr3; (c) CsPb(Br/I)3; (d) CsPb(Cl/Br)3 NWs; and (e) their corresponding absorption and PL spectra. Reproduced with
permission from ref 55. Copyright 2017 John Wiley and Sons. (f) CsPbBr3 NPLs; (g) hexagonal Cs4PbBr6 nanocrystals; and (h) transformation of the
unit cell and optical properties between the two phases with Cs-oleate and PbBr2 additions. Reproduced from ref 113. Copyright 2018 American
Chemical Society.

had lateral lengths ∼14−27 nm with thicknesses of ∼1.5 nm and NRs
with diameters of ∼46 nm with lengths of ∼655 nm. These PNCs
exhibited low PLQYs of ∼5% due to deep defects originating from the
Sb 5p orbital splitting.
Beyond single B-site perovskites, double perovskites have also been
demonstrated using monovalent Ag+ and trivalent Bi3+ B-site ion pairs
to synthesize Cs2AgBiX6.108 Colloidal Cs2AgBiBr6 PNCs were
synthesized from a modified HI method in which BiBr3 and AgNO3
were first dissolved in ODE at 200 °C using OA, OLA, and
hydrobromic acid solubilizers. Then a solution of Cs-oleate in ODE
was injected into this reaction mixture to form 9.5 nm NCu of
Cs2AgBiBr6 after 5 s of reaction time.109 Alternative syntheses of
Cs2AgBiX6 (X = Cl, Br) have explored dissolving the acetate salts of Cs,
Ag, and Bi in ODE, OA, and OLA solutions and then injecting

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Figure 12. (a) TEM micrographs, (b) XRD patterns, and (c) absorption and PL spectra of different PNC halide compositions. Reproduced with
permission from ref 115. Copyright 2017 Royal Society of Chemistry.
trimethylsilyl halide at 140 °C into grown ∼8.1 nm NCu over 10 to 60
s.110 The decoupling of the metallic salts and the halide precursors in
this approach provided greater control over the stoichiometry. These
cubic double perovskites exhibited low PLQY (0.3%),110 albeit with
improved thermal, light, and moisture stability compared to that of
other Pb-free perovskites.109 Notably, detailed structural investigations
have indicated that the major degradation pathway in these materials
arises from silver diffusion and its chemical reduction and coalescence
to form Ag and trigonal-phase Cs3Bi2X9 and Cs3BiX6.110,111 Over-
coming these structural limitations remains one of the existing
challenges in effectively harnessing double perovskite structures.
Convection. Convection synthesis (often referred to generally as
“heat-up”) is among the simplest noninjection syntheses, relying on
controlled heating to induce nucleation and growth. It is also the least
explored, owing to the still nascent understanding of precursor
evolution for PNCs, resulting in challenges in controlling their
nucleation and growth dynamics. Nonetheless, Chen et al. has used
this approach to successfully synthesize CsPbX3 PNCs.46 Cs2CO3 and
PbX2 precursors were dissolved in ODE using OA and OLA ligands at
room temperature, and then the reaction mixture was heated to
temperatures ranging from between 50 and 170 °C for 10 min to
nucleate and grow 1 to 4 nm CsPb(Cl/Br)3 and 1.6 to 10.4 nm CsPbI3
QDs (Figure 10a−d). While the size tunability demonstrated in this
approach is superior to those for injection methods, it is evident that it
also yielded PNCs with higher polydispersity and irregular shapes.
Despite this, the control of size and composition enabled tunable PL
across the entire visible region with PLQYs of >80% (Figure 10e−g).
The scalability of the reaction was demonstrated at gram levels.
Tsiwah et al. further showed that by using reaction chemistries
similar to that above, bromide PNCs exhibited a rhombohedral
Cs4PbBr6 to orthorhombic CsPbBr3 phase transformation upon
increased reaction temperature or time.112 By replacing the OLA
with shorter-chained octylamine, NSs with a diameter of several
micrometers were produced. This indicated that the shorter amine
similarly induced anisotropic growth in both injection and convection
syntheses.
Solvothermal. The solvothermal route is a simple, scalable, and
versatile method for nanocrystal production. It is performed in an
isochoric environment, with the reaction being conducted in a
pressurized vessel at elevated temperature. Chen et al. was the first to
use the solvothermal method to prepare CsPbX3 PNCs.55 Cesium
acetate (CsAc), PbX2, OA, and OLA in ODE were placed inside an
autoclave, with TOP and TOPO being used to enhance the final
solubility of the different lead salts. Upon heating the reaction mixture
to 160 °C for 30 min in a rolling oven, high-quality perovskite NCu with
a size of 8 to 12 nm was produced (Figure 11a). By using different lead
halides or their mixtures, the emission properties of these PNCs could
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be tuned across the visible region while maintaining high PLQYs of up
to 80% and narrow fwhm’s of 12 to 36 nm. It was additionally shown
that if the precursors were predissolved prior to heating the reaction
mixture, then the modified reaction kinetics results in NWs with a
thickness of only ∼3.2 nm and lengths of several hundred nanometers
could be produced in almost 100% morphological yield (Figure 11b−
e).
The solvothermal synthesis of CsPbBr3 was further modified by
tuning the Cs/Pb precursor ratio and the reaction time.113 Using
predissolved precursors, at a Cs/Pb molar ratio of ∼1:10 and a reaction
time of at least 30 min at 100 °C, ∼4.2-nm-thick NPLs with lateral
lengths of ∼100 nm and widths of ∼15 nm formed (Figure 11f). As the
thickness of the NPLs remained unchanged in the quantum
confinement regime, the PL emission could be fine-tuned to between
452 to 465 nm by controlling the lateral NPL sizes to between 101 × 15
nm and 44 × 42 nm, respectively. At progressively longer reaction
times, the NPLs exhibited coarsening behavior, demonstrated by a
shortening of their lengths and an increase in their widths. Similar
trends in the shape evolution were observed as the Cs/Pb molar ratio
was increased, although at a nearly equimolar ratio rhombohedral-
phased Cs4PbBr6 PNCs with a hexagonal shape were observed (Figure
11g,h).
The synthesis of Pb-free perovskites using a solvothermal method
has also been demonstrated with CsSnX3 (X = Cl, Br, I) NRs.114 In this
approach, SnX2 was mixed with ODE, OA, and OLA. A secondary
mixture of Cs2CO3, ODE, OA, hydrochloric acid, TOPO, and
diethylenetriamine was then combined with the first mixture under
stirring at 80 °C for an hour. The combined mixture was further diluted
with diethylenetriamine and transferred to an autoclave at 180 °C for 6
h. This resulted in NRs of 5 nm diameter and 10 nm length, with
absorption onsets and photoluminescence emission peaks that could be
tuned via their halide composition from 588 to 688 nm and 625 to 709
nm, respectively.
Microwave. The use of a microwave as the heat source requires a
polar solvent and/or ligands within a reaction medium that can absorb
the microwave radiation to ensure rapid and uniform heating. Long et
al. were the first to report the microwave synthesis of inorganic PNCs
(Figure 12).115 The authors reacted Cs2CO3, PbX2, OA, and OLA in
ODE at a Cs/Pb molar ratio of 1:3 within a 800 W household
microwave oven for 4 min. Despite the rather rudimentary nature of the
synthesis, 10 to 13 nm NCu CsPbX3 PNCs were achieved. The
microwave irradiation time was correlated to the size of the PNCs, with
times of between 2 and 7 min yielding tunable sizes of between 5 and 14
nm. By decreasing the Cs/Pb precursor ratio to 1:6 in the above
synthesis, NWs with a length of >100 nm were preferentially
formed.115,116
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Figure 13. (a) Schematic illustration of ultrasonication PNC synthesis. (b) Photographs under visible and UV light for PNCs with different halide
compositions (c) and their respective absorption and PL spectra. Reproduced with permission from ref 70. Copyright 2016 John Wiley and Sons. (d)
TEM micrograph for a CsPbBr3 supercrystal. (e) PL comparison for normal and supercrystal CsPbBr3 films. Reproduced with permission from ref 119.
Copyright 2016 John Wiley and Sons.
Pan et al. further investigated the synthesis of CsPbBr3 NCs using a
microwave reactor, studying factors that included temperature, the
predissolution of precursors, and heating rates.71 It was found that a
synthesis temperature of ∼80 °C drove anisotropic growth, yielding
NPLs with a thickness of ∼3.3 nm and edge lengths of ∼23.4 nm.
Increasing the temperature to 140 °C produced homogeneous ∼10.2
nm NCu PNCs. A further temperature rise to 180 °C yielded
inhomogeneous PNC dispersions. Predissolving the precursors at 60
°C and then reacting them at 160 °C under otherwise identical
conditions resulted in the formation of NRs at morphological yields of
>90%, with lengths of >60 nm and diameters of only ∼2.7 nm. It was
noted that the presence of TOPO in the reaction mixture was critical to
obtaining high-quality NRs. The authors suggested that the TOPO
aided the dissolution of the precursors. Finally, a minimum heating rate
of 18 °C/min was found to be required to generate homogeneous
PNCs. A slower heating rate of 8 °C/min significantly broadened the
PNC size distribution and produced particles >150 nm in size. The
latter is consistent with the fundamental limitation of heat-up syntheses
in that slow heating rates prolong the nucleation event to yield
inhomogeneous dispersions.117
Ultrasonication. The formation of hybrid MAPbX3 (X = Br, I)
PNCs has been demonstrated using ultrasonication, albeit in an indirect
manner. Huang et al. dispersed PbX2 and MAX in a mixture of OA and
OLA that acted as a coordinating solvent.118 This mixture was
ultrasonicated to form bulk MAPbX3 within 5 min. After several further
hours of ultrasonication, these bulk perovskite crystals were trans-
formed into nanocrystals. It is not clear whether these were generated
through a dissolution−recrystallization process and/or progressive
fragmentation caused by the cavitation process. Nonetheless, an
analysis of the MAPbBr3 samples indicated that the PNCs were ∼4 nm
in size and possessed PLQYs of up 72%.
In a more direct synthesis, Tong et al. was the first to use
ultrasonication to synthesize CsPbX3 nanocrystals (Figure 13a).70
Cs2CO3, PbX2, OA, and OLA were mixed in ODE under ambient air,
and then a 30 W sonication tip was applied to the mixture for 10 min.
This induced the in situ formation of solubilized Cs+ and Pb2+ precursor
complexes, which concurrently reacted to produce CsPbX3 (X = Cl, Br,
I, Cl/Br, and Br/I) PNCs. The sizes of the CsPbBr3 and CsPbI3 PNCs
were determined to be 10 to 15 nm and 8 to 12 nm, respectively, which
are slightly higher than those obtained via HI. The produced PNCs
exhibited visibly tunable optical absorption and emission properties,
with the emission possessing QYs of up to 90% for the Br and I
derivatives and narrow fwhm’s of 12 to 40 nm (Figure 13b,c).
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Analogous to the solvothermal method, decreasing the Cs/Pb ratio
favored the formation of NPLs.
By increasing the concentration 10-fold (1 mmol Cs2CO3, 3 mmol
PbBr2) and extending the reaction time to 30 min, it has been shown
that the ultrasonication approach can produce CsPbBr3 supercrystals of
200 to 400 nm diameter that are composed of closely assembled 10
sized NCu (Figure 13d).119 Such supercrystals exhibit PLQYs
comparable to those of their isolated NC counterparts but are red-
shifted by ∼20 nm due to strong electronic coupling (Figure 13e).
■ POSTSYNTHETIC TREATMENTS
Purification. Postsynthetic purification of PNCs involves
the removal of residual solvent, ligand, and precursor impurities
through multiple precipitation and redispersion steps. Owing to
the highly ionic perovskite structure, antisolvents with larger
dipole moments of ∼4.0 D (DMF, DMSO) or protic solvents
(methanol, ethanol) in which the underlying perovskite lattice
exhibits a high solubility have been found not to preserve the
structural properties of the nanocrystals.79 As a result, modest-
polarity aprotic antisolvents have been favored. The inability of
such solvents to undergo proton-mediated X-type ligand
exchange further enables a better preservation of the surface
chemistry during purification.75
Because of the modest binding constants of the ligands at the
surface of PNCs, the required multiple purification cycles
decrease the ligand density at the PNC surface.120 To mitigate
ligand loss and the deterioration of PNC quality during this
process, it has been shown that small amounts of additional
organic acid and amine ligands are required to maintain the
acid−base equilibria required for colloidal stability and the
retention of PL properties.75,121 Despite this, under a large
excess of amine,80,122 the irreversible degradation of PNCs was
observed, as governed by eq 6. Excess acid was also found to
destabilize the PNCs.122
amine
4CsPbBr3 ⎯⎯⎯⎯⎯→ Cs4PbBr6 + 3PbBr2 (6)
123
Postsynthetic additives in the form of thiocyanate- and
tetrafluoroborate-based124 salts have also been successfully used
to improve PNCs, achieving PLQYs approaching unity. It is
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Figure 14. Postsynthesis anion exchange for mixed PNC halide compositions. (a) Schematic of possible halide exchanges, (b) XRD spectra, (c)
combined UV−vis absorption (solid lines) and PL emission spectra (dashed lines), and TEM micrograph of (d) CsPb(Br1.5Cl1.5) and (e)
CsPb(Br1.5I1.5). Reproduced from ref 129. Copyright 2015 American Chemical Society.

Figure 15. Postsynthesis cation exchange for mixed PNC B-site compositions. Colloidal CsPbBr3 PNCs under UV illumination with increasing
additions of (a) SnBr2, (b) CdBr2, and (c) ZnBr2. Combined UV−vis absorption (dashed lines) and PL emission (solid lines) spectra of CsPbBr3
dispersions with (d) Sn2+ and (e) Cd2+ and Zn2+ additions resulting in spectral blue shifts. Reproduced from ref 130. Copyright 2017 American
Chemical Society.

believed that these anions salts remove excess surface lead atoms
from the surface, thereby removing shallow traps that
detrimentally impact the optical properties. Similar effects
have been observed with the addition of ammonium salts to
enhance surface passivation and restrict PNC growth to improve
their overall colloidal and PL stability.125 Moreover, the use of
mixed treatment solutions, in the form of didodecyldimethyl-
ammonium bromide (DDAB) and PbBr2 in toluene has resulted
in PNCs with PLQYs of >90% that were amenable to multiple
11621
wash cycles.126 Further exploration of such additives during
purification processes will be necessary to achieve the optimized
structural and optoelectronic properties of PNCs.
Anion Exchange. The highly ionic nature of PNCs can
readily undergo postsynthetic anion exchange reactions to
enable tuning of their optical properties (Figure 14).16 The
relatively rigid cationic sublattice and the high diffusivity of
halide vacancies31 facilitate rapid Cl− ↔ Br− and Br− ↔ I− halide
exchange across all PNCs upon the addition of the introduced
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halide source (e.g., PbX2 solution or an ammonium halide
solution). The extent of anion exchange can be fully controlled
by the ratio between the original and introduced halides.127 The
exchange process retains monodisperse colloidal PNCs with
similar optical properties compared to directly synthesized
PNCs of the same composition.31,115 Furthermore, this process
is morphologically independent, as has been demonstrated on
NW- and NPL-shaped PNCs.52,128 However, the exchange
process is not universal across halide-based perovskites. Because
of the large difference in ionic radii of Cl− (1.81 Å) and I− (2.20
Å), attempts to perform a Cl− ↔ I− halide exchange process
have resulted in only the slow conversion to a full trihalide
perovskite material.31 To circumvent this limitation, it has been
shown that Cl− ↔ I− exchanges can be achieved through
intermediate exchange processes using Br− (1.96 Å). This
unique property of PNC systems to undergo anion exchange is
the key reason for its ability to easily tune its emission across the
visible spectrum. In comparison, traditional metal chalcogenide
nanocrystal systems undergo only cation exchanges and are
limited to tuning their emissions via the quantum confinement
effect through particle size control.3
Cation Exchange. Analogous to anionic exchange pro-
cesses, cation exchange at both the A and B sites can similarly
tune the optoelectronic properties of PNCs. Akkerman et al.
observed that for CsPbX3, the A-site Cs+ (1.67 Å) could be
exchanged for the larger MA+ (2.17 Å) cation.129 Similarly, Cs+
and FA+ (2.53 Å) cations could be interchanged to form
(FA,Cs)PbI3 PNCs.12
Partial exchange of the B-site Pb2+ cation in CsPbBr3 was first
demonstrated by van der Stam et al. by mixing a PNCs solution
and M2+ cation precursor solutions (MBr2, M = Sn2+, Zn2+, and
Cd 2+ ) in toluene. 130 The emission of the resultant
CsPb1−xMxBr3 PNCs exhibited a blue shift proportional to the
M2+ precursor concentration (Figure 15). The blue shift of the
emission was attributed to the contraction of the PbBr6
polyhedra, after partial substitution of Pb2+ cations by the
smaller M2+ cations, which caused a closer and stronger Pb−Br
orbital interaction that raised the conduction band minimum.
Despite M2+ being present in large excess, there was only partial
(≤10%) substitution of the M2+ cation into the PNC. It was
reasoned that the perovskite crystal structure is primarily
stabilized by the rigid cationic sublattice and that cation
substitution, especially at the B site, required higher activation
energies than for anion exchange.31 This is consistent with the
findings from studies on the solid state ion exchanges in single-
crystal perovskite NWs.131
To overcome this B-site stability, Mondal et al. showed that
ultrasonication facilitated enhanced alloying of CsPbCl3 PNCs
with Cd2+ using a saturated solution of CdCl2 in ethanol.132
Doping levels of up to 40% were claimed, with the PLQY
increasing from 3% to near unity. The significant PLQY increase
was attributed to the removal of nonradiative defect states
caused by chloride vacancies and a reduction in the PbCl6
polyhedral tilting through the incorporation of the smaller Cd2+
ions. This also gave Cd/CsPbCl3 PNCs improved photo-
stability, with PLQYs of up to 90% being retained after several
months.
Postsynthetic Mn2+ doping of PNCs has also been explored.
Huang et al. used a concurrent halide exchange approach
through the addition of MnCl2 in DMF to CsPbBr3 PNCs in
toluene to yield PNCs with characteristic emission peaks of the
sensitized Mn and CsPb(Cl,Br)3.133 In a more direct approach,
Nag’s group simply used MnBr2 dissolved in an acetone and
11622
Invited Feature Article
toluene mixture to directly dope CsPbBr3 NPLs and NCu.134 In
this case, sensitized emission from the Mn was observed only at
room temperature for the NPLs, with back energy transfer from
the Mn to the host PNCs causing quenching for the NCu.
Notably, the same authors showed that a similar cosolvent
approach, albeit using toluene and methyl acetate, could
successful dope CsPbX3 with Yb3+, as evidenced by its
characteristic 2F5/2 → 2F7/2 IR emission being observed at
∼990 nm. Importantly, the doping of both Mn and Yb into the
CsPbX3 nanocrystals narrowed their Urbach tail, indicating a
favorable reduction in their intrinsic defect states.
Attempts to substituting the A-site Cs+ cations with Rb+, Ag+,
Cu+, or Ba2+ or the B-site Pb2+ cations with Ge2+ or Bi3+ have
resulted in the decomposition of the original CsPbX3 PNCs.31
This incompatibility could stem from oxidative instabilities,
incompatible ion sizes, or competition with more thermody-
namically stable phases.10
■ SUMMARY
Here we have assessed the progress toward the synthesis of
colloidal metal halide perovskite nanocrystals. These materials
have leveraged advances from traditional semiconductor
colloids to achieve modest size and morphological control
across various hybrid and inorganic compositions within a span
of only 5 years. This structural and compositional control has
enabled the exceptional optoelectronic properties of perovskites
in their nanocrystalline forms to be showcased, with visibly
tunable absorption and photoluminescence properties, narrow
emission bands, and near-unity photoluminescence quantum
yields being demonstrated. These properties make perovskite
nanocrystals a remarkable candidate for many optoelectronic
applications, where high efficiency and low-temperature
processing are advantageous.
The hot-injection method has emerged as the most common
for synthesizing high-quality perovskite nanocrystals. Relying on
a high-temperature mixing process under aliphatic chemical
conditions, control of the rapid nucleation and growth stages
through ligand, precursor, solvent, and temperature profile
tuning has yielded reasonable size- and shape-controlled
perovskite nanocrystals. Lower-temperature injection syntheses
that mostly use aliphatic and polar solvent mixtures have been
concurrently developed. These have taken advantage of the
slower kinetics to scale the reactions from tens of mL up to >1 L.
A number of noninjection methods have also emerged as
suitable synthetic alternatives that are more suitable for scale up.
By adopting similar reaction mixtures to the injection methods,
perovskite nanocrystals of varying size and shape have been
synthesized through these, although with lesser structural
tunability and quality compared to those of the injection
approaches.
In reviewing all of the reported synthetic approaches to date, it
is apparent that a greater understanding of the nucleation and
growth processes, the precursor evolution, and the interactions
at the perovskite nanocrystal surface is still required for each
method. The fast dynamics in these systems have largely masked
the intricate details around the nucleation process and early
growth stages. Further uncertainties around specific solvent and
ligand interactions at the perovskite nanocrystal surface, which
include the role that stereochemistry, polarity, conjugation, and
chemical functionality play in mediating ligand−surface
interactions, provide an incomplete picture of what is occurring
at the surface and how the specific interactions can be tuned.
Progress in these areas will require the expansion of the currently
DOI: 10.1021/acs.langmuir.9b00855
Langmuir 2019, 35, 11609−11628
Langmuir Invited Feature Article

limited library of precursors and ligands as well as more detailed

theoretical studies to understand the synthetic evolution of the
reaction mixtures. These insights will concurrently assist in
further developing postsynthetic ligand and ion-exchange
processes to provide greater structural and optical versatility of
these materials.
In going forward, the overarching goal in the field of
perovskite nanocrystals is the development of stable and
nontoxic perovskite derivatives that maintain the lucrative
optoelectronic properties of existing lead-based derivatives.
Preliminary works on hybrid and inorganic systems, such as
MA3Bi2X9 and Cs3Sb2X9, respectively, have shown great promise
toward achieving this goal. However, the low-quantum yields,
high intrinsic defects, and structural instabilities that are
currently observed within such materials remain major hurdles. Chujie Wang received his BE (Honors) in materials science and
To overcome these, tremendous effort in tailored ligand and engineering from Monash University and Central South University in
precursor design and compositional engineering will be required 2015. During his bachelor’s degree, he worked on different projects in
to achieve the degree of synthetic and structural control several research groups: mass production of reduced graphene (Prof.
necessary to yield high-quality perovskite nanomaterials with the Dan Li) and tissue engineering of artificial skin (Prof. Neil Cameron
desirable optoelectronic properties. Through these continuing and Alfred Hospital). In 2016, he continued at Monash University with
advances, this exciting field of perovskite nanocrystals will reach a Ph.D. in the Department of Materials Science and Engineering under
a state of maturity, one that will deepen our understanding of the supervision of Assoc. Prof. Jacek Jasieniak. His current research
structure−property relations at the nanoscale and foster a interests are focused on the phase transformation and surface chemistry
paradigm shift in the application of nanocrystals across many of inorganic perovskite nanocrystals.
fields.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: jacek.jasieniak@monash.edu.
ORCID
Chun Kiu Ng: 0000-0001-5456-1020
Jacek J. Jasieniak: 0000-0002-1608-6860
Author Contributions
The manuscript was conceived by J.J. and written through the
contributions of all authors.
Notes
The authors declare no competing financial interest.
Biographies
Jacek Jasieniak completed a Bachelor of Science (First Class Honours)
from Flinders University (2003) and a Ph.D. from the University of
Melbourne (2008) under the supervision of Prof. Paul Mulvaney. He
then undertook postdoctoral work at the Commonwealth Scientific and
Industrial Research Organisation (CSIRO) with Dr. Scott Watkins and
Dr. Ezio Rizzardo (2008−2011), and was a Fulbrigh Scholar with Prof.
Alan Heeger at the University of CaliforniaSanta Barbara (2011 to
2012). In 2012, he returned to CSIRO, progressing to a senior research
scientist and then group leader. In 2015, he moved to Monash
University as an associate professor, where he was also appointed as the
director of the cross-disciplinary Monash Energy Materials and Systems
Institute. His research interests include the development of nanoma-
terials and their use in various next-generation energy technologies.

Chun Kiu received his BE(Hons)/BSc at Monash University in 2015.

During his bachelor’s degree, he worked on numerous projects under
■ ACKNOWLEDGMENTS
The authors thank the ARC Centre of Excellence in Exciton
Science (CE170100026) for financial support.

several academics: cobalt electrolytes for dye-sensitized solar cells
(Prof. Udo Bach), perovskite photovoltaic-driven water splitting (late
Prof. Leonne Spiccia), and organic photovoltaics (Prof. Chris McNeill).
In 2016, he continued at Monash University with a Ph.D. in the
Department of Materials Science and Engineering under the super-
vision of Assoc. Prof. Jacek Jasieniak in the area of perovskite
nanocrystal synthesis and its incorporation into solar cells.
11623
■
ABBREVIATIONS
°C, degrees Celsius; μm, micrometer; Ag, silver; Ba, barium; Bi,
bismuth; Br−, bromide; Cd, cadmium; CdBr2, cadmium
bromide; CdSe, cadmium selenide; Ce, cerium; Sm, samarium;
Cl−, chloride; cm, centimeter; Cs, cesium; Cs2CO3, cesium
DOI: 10.1021/acs.langmuir.9b00855
Langmuir 2019, 35, 11609−11628
Langmuir
carbonate; Cs4PbBr6, zero-dimensional cesium lead bromide;
CsAc, cesium acetate; CsBr, cesium bromide; CsOA, cesium
oleate; CsPbBr3, cesium lead bromide; CsPbCl3, cesium lead
chloride; CsPbI3, cesium lead iodide; CsPbX3, cesium lead
halide; CsX, cesium halide; Cu, copper; DDAB, didodecyldi-
methylammonium bromide; D, dipole moment in debye; DFT,
density functional theory; DMF, dimethylformamide; DMSO,
dimethyl sulfoxide; Dy, dysprosium; E0, standard reduction
potential; EDX, energy-dispersive X-ray; Er, erbium; EtOH,
ethanol; QDs, quantum dots; Eu, europium; eV, electronvolt;
FA+, formamidinium; FACsI3, formamidinium cesium iodide;
FAPbBr3, formamidinium lead bromide; FAPbI3, formamidi-
nium lead iodide; FTIR, Fourier transform infrared spectrosco-
py; fwhm, full width at half-maximum; min, minutes; g, gram;
GaAs, gallium arsenide; Ge, germanium; HI, hot injection; I−,
iodide; IPA, isopropanol; LARP, ligand-assisted reprecipitation;
LEDs, light-emitting diodes; M, moles per liter; MA+,
methylammonium; MABr, methylammonium bromide;
MAPbBr3, methylammonium lead bromide; MAPbCl3, methyl-
ammonium lead chloride; MAPbI3, methylammonium lead
iodide; MAPbX3, methylammonium lead halide; MASnCl3,
methylammonium tin chloride; MASnI3, methylammonium tin
iodide; MAX, methylammonium halide; mL, millimeters; mm,
millimeter; Mn, manganese; MnCl2, manganese chloride;
MnX2, manganese halide; N2, nitrogen gas; NCu, nanocubes;
NH3+, ammonium; NH4X, ammonium halide; nm, nanometer;
NMR, nuclear magnetic resonance; NPL, nanplatelet; NR,
nanorod; ns, nanoseconds; NS, nanosheet; NT, nontemplate;
NW, nanowire; OA−, oleate; OA, oleic acid; ODE, 1-
octadecene; OLA, oleylamine; OLA + , oleylammonium;
OLAX, oleylammonium halide; Pb, lead; PbBr2, lead bromide;
PbCl2, lead chloride; PbI2, lead iodide; PbO, lead oxide; PbOA2,
lead oleate; PbS, lead sulfide; PbSe, lead selenide; PbX2, lead
halide; PL, photoluminescence; PLQY, photoluminescence
quantum yield; PNC, perovskite nanocrystal; ref, reference;
Rb, rubidium; rpm, revolutions per minute; s, seconds; SAXS,
small-angle X-ray scattering; Sb, antimony; SbCl3, antimony
chloride; SEM, scanning electron microscopy; Sn, tin; SnBr2, tin
bromide; t, Goldschmidt tolerance factor; Tb, terbium; TEM,
transmission electron microscopy; TMPPA, bis(2,4,4-trimethyl-
pentyl)phosphinic acid; TOP, trioctylphosphine; TOPO, tri-
octylphosphine oxide; UV−vis, ultraviolet−visible; V, volt; W,
watts; mmol, millimole; X, halide; XPS, X-ray photoelectron;
XRD, X-ray diffraction; Yb, ytterbium; Zn, zinc; ZnBr2, zinc
bromide; ZnX2, zinc halide.
■
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11628 DOI: 10.1021/acs.langmuir.9b00855

Langmuir 2019, 35, 11609−11628