Letter

Cite This: ACS Energy Lett. 2018, 3, 329−334

Tuning the Size of CsPbBr3 Nanocrystals: All at

One Constant Temperature
Anirban Dutta,† Sumit Kumar Dutta,† Samrat Das Adhikari, and Narayan Pradhan*
Department of Materials Science, Indian Association for the Cultivation of Science, Kolkata 700032, India
*
S Supporting Information

ABSTRACT: For varying the size of perovskite nanocrystals,

See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via UNIV OF LOUISIANA AT LAFAYETTE on January 8, 2019 at 10:28:21 (UTC).

variation in the reaction temperature and tuning the ligand

chain lengths are established as the key parameters for high-
temperature solution-processed synthesis. These also require
sharp cooling for obtaining desired dimensions and optical
stability. In contrast, using preformed alkylammonium
bromide salt as the precise dimension-controlling reagent,
wide window size tunable CsPbBr3 nanocrystals were
reported without varying the reaction temperature or
changing the ligands. The size tunability even with ∼1 nm
step growth regimes was achieved as a function of only the
concentration of added alkylammonium bromide salt. Not
only the cube shape but also the width varied in the sheet
structures. Because these nanostructures lose their optical stability and crystal phase on prolonged annealing, stabilizing
these in high-temperature synthesis for all-inorganic lead halide perovskites is important and remains challenging. In this
aspect, this method proved to be more facile because it does not require sharp cooling, and the nanocrystals retained their
phase and optical properties even upon prolonged annealing.

L ead halide perovskites, which have emerged as a new

class of functional energy materials for both light-
emitting and photovoltaic applications, remain in the
forefront of current research.1−16 Enormous efforts have been
put forward in designing these nanocrystals and understanding
their formation chemistry.4,6,8,17−57 The high-temperature
synthesis of tunable monodisperse lead halide perovskite
nanocrystals is typically achieved by modifying the surface
ligands, ligands ratio, reaction temperature, precursors ratio,
etc.,24,27,37,48,52,57 but not in a unique reaction setup with
similar reagents and in a concise preprogrammable manner.
Moreover, all such approaches required instant cooling for
protecting the emission intensity, phase, and the dimensions of
these nanocrystals. This indicates that these synthesis methods
are indeed sensitive and demand more flexible processes for
obtaining phase-stable, highly emissive nanocrystals.
One of the most widely studied all-inorganic perovskite
system is CsPbBr3 nanocrystals which have a room-temperature
air stable highly emissive crystal phase. A close examination of
the literature reports on high-temperature synthesis of lead
halide perovskite nanocrystals reveals that their surfaces are
coordinated or bonded with alkylamines (or ammonium ions)
and acids (or carboxylate ions).24,27,58,59 A recent study also
suggested that ammonium ions replaced surface Cs ions to
passivate and stabilize the perovskite nanocrystals.60 Inspired by
this concept, herein, alkylammonium bromide salt was
introduced as a size-controlling additive reagent which
successfully controlled the size of cubes from the quantum
confinement regime to bulk size just as a function of the
amount of added salt without varying the reaction temperature
or any other reaction parameters. The synthetic control
remained robust, which could predict precisely the size of the
nanocubes even in 1 nm step growth regimes. This approach
does not require any sharp cooling strategy and retained the
stable optical emission even upon prolonged annealing. Not
only cube shapes but also the widths of sheets are tuned by
varying the concentration of added salts.
For the synthesis of CsPbBr3 nanocrystals, a stock solution of
oleylamine−HBr (OLA−HBr) was first prepared (see exper-
imental methods in the Supporting Information), and for
controlling the size or shape, the required amount of this salt
was introduced into the reaction system. Cs−oleate solution
was injected at the desired reaction temperature for triggering
the reactions following the procedure reported by Protesescu et
al.4 When the reactions were optimized at different reaction
temperatures, 140−180 °C was observed to be the ideal
temperature window for obtaining wide size-tunable nanocryst-
als. Figure 1a−h (and Figures S1−S8) presents the TEM
images of eight different sizes of CsPbBr3 nanocubes with
introduction of different amounts of OLA−HBr at 160 °C. The
Received: December 6, 2017
Accepted: January 2, 2018
Published: January 2, 2018

© 2018 American Chemical Society 329 DOI: 10.1021/acsenergylett.7b01226

ACS Energy Lett. 2018, 3, 329−334
ACS Energy Letters Letter

Figure 1. (a−h) TEM images of CsPbBr3 nanocubes obtained from the reaction with varying amount of OLA−HBr stock solution. The size of
these cubes varied from ∼3.5 to ∼17 nm with introduction of 0.52, 0.44, 0.35, 0.26, 0.17, 0.09, 0.04, and 0.0 mmol of the salts. Scale bar in all
cases is 100 nm. (i) Size distribution histograms of the set of nanocrystals (from a to h and Figures S1−S8). These are calculated considering
200 nanocrystals.

average size of ∼17 nm in the standard case obtained without

salt addition was reduced to ∼3.5 nm with increasing the
amount of OLA−HBr from 0 to 0.6 mL (0 to 0.52 mmol). The
size tuning window of these nanocubes is further represented in
their size distribution histograms shown in Figure 1i, which
clearly suggested the effect of the concentration of OLA−HBr
on the particles size. A representative high-resolution TEM
image for ∼9 nm nanocubes is shown in Figure S9. Similarly,
nanocrystals obtained in 180 °C reactions also showed that
with changing the amount of added salt, the size was tuned.
TEM images and corresponding size distribution histograms of
these nanocrystals are presented in Figure S10.
Interestingly, with an increase in the OLA−HBr amount,
monodispersity of the nanocubes was also enhanced. Smaller
nanocubes that were obtained with higher amounts of salt were
highly monodisperse, and this result was reflected in their two-
dimensional self-assemblies on the TEM grid (Figures 1a−d
and S1−S4). To correlate further the size of nanocubes as a
function of added ammonium salts, a plot of size versus the
amount of introduced salt for both 160 °C and 180 °C are
presented in Figure 2. These size variations were also highly
reproducible with ∼6−10% error range.
Figure 3a shows the powder X-ray diffraction (XRD)
patterns of four different sizes of nanocubes obtained from
four different concentrations of the salt. The peak positions
resembled the orthorhombic phases of CsPbBr3. However,
several studies showed that the orthorhombic phase is the
stable phase, and we have also found the same phase (COD:
4510745).54,61−65 Figure 3b presents the absorption spectra of
all eight samples where the tunability is clearly observed from
below the quantum confinement regime to bulk size.
Corresponding photoluminescence (PL) spectra of all these
samples are shown in Figure 3c where the emissions were
observed to be tunable from 465 to 510 nm. The quantum yield
of these nanocrystals (varied from 70 to 80%) remained similar
to its best reports, and the excited-state decay lifetime was also
observed in nanoseconds (4.9−5.24 ns; see Figure S11).24
The interesting observation noticed here is the PL stability of
these nanocrystals (Figure 3d). For the standard reaction
without the salt carried out at 160 °C, the PL intensity is
significantly reduced, and it is completely quenched for 180 °C
330
Figure 2. Plot of amount of added OLA−HBr vs obtained size of
nanocubes carried out at 160 °C (black squares) and 180 °C (red
triangles). Reaction conditions for all cases remain identical in both
temperatures. The error bars remain ∼6−10%.
reaction while annealing. However, in the presence of salt, the
intensity remained unchanged. The comparison PL spectra are
shown in Figure 3d, and corresponding ultraviolet−visible
(UV−vis) spectra are presented in Figure S12. The decrease in
the optical property might be due to the possible phase change
as reported in the literature.66 This suggests that this approach
not only results in a precise, tunable size but also remained
thermally stable.
However, we also observed a limiting stage for the density of
OLA−HBr for retaining the cube shape at 160 °C reaction.
Introducing excess salt changed the shape to square platelets.
UV−vis spectra, PL spectra, powdered XRD pattern, and TEM
images of these platelets are shown in Figure S13. Hence, our
entire study was limited within the permitted amount of OLA−
HBr for retaining the cube shape.
It is widely established that the surface is bound with both
ammonium and carboxylate ions. Though, carboxylate binds
strongly to the nanocrystal surface, the ammonium ion is more
effective in tuning the growth of anisotropic platelet
structure.24,48,62 While oleylamine leads to exclusively nano-
DOI: 10.1021/acsenergylett.7b01226
ACS Energy Lett. 2018, 3, 329−334
ACS Energy Letters Letter

Figure 3. (a) XRD patterns of CsPbBr3 nanocrystals with variation of amount of OLA−HBr. (b) Absorption and (c) corresponding PL spectra
of CsPbBr3 nanocrystals with variations of OLA−HBr salts. (d) Annealing time-dependent successive PL spectra of nanocrystals obtained at
160 and 180 °C reactions in presence and absence of the salt. In each case the amount of salt is written alongside each spectrum. Excitation
wavelength is 350 nm.

Figure 4. (a) Absorption spectra, (b) PL spectra, and (c) powder XRD patterns of CsPbBr3 nanosheets obtained with introduction of 0.44
mmol and without OCTA−HBr salt. TEM images of nanosheets in different resolutions obtained in (d, e) absence and (f, g) presence of
OCTA−HBr, respectively.

cubes, octylamine (OCTA) forms nanosheets under identical
reaction conditions.4,48 It is interesting to note that when these
nanosheet formations are carried out in the presence of
octylamine−HBr (OCTA−HBr), the thickness of the sheets
was observed to decrease. Figure 4 presents the optical spectra,
XRD patterns, and TEM images obtained with and without
OCTA−HBr. The appearance of a new absorption peak (∼440
nm) (Figure 4a) suggested that the length of one of the
confinement directions (thickness) of the sheets was reduced.
PL spectra (Figure 4b) further supported with dual emissions,
where one was controlled by quantum confinement regime and
another by the bulk. These are typically observed for sheetlike
structures for their dual modes of confinement.48 Powder XRD
patterns confirmed the same orthorhombic phase of these
nanosheets. Figures 4d,e and 4f,g present TEM images
obtained without and with OCTA−HBr (0.5 mL) respectively.
The contrast differences clearly indicate sheets obtained with
OCTA−HBr were thinner.
From atomic force microscopy (AFM) images, the widths of
sheets obtained with and without OCTA−HBr were observed
331
to be ∼5 and ∼15 nm, respectively (also visible from the TEM
image of marked area in Figure 4e) (Figure S14). This
confirmed that alkylamine−HBr not only reduced the size of
the nanocubes of CsPbBr3 but also reduced the thickness of
sheets obtained in different amine media.
All the above results either for the size of the cubes or width
of sheets suggested that the preformed ammonium bromide salt
played an important role for such dimension variations. From
NMR and Fourier transform infrared spectroscopic data
analysis, it is observed that ammonium ions are present on
the surfaces (Figures S15 and S16). The results also overlapped
with previous reports in oleylamine and oleic acid mixed
systems.24,60 These ions typically replace surface Cs+ ions and
act as integrated bonded ions on the surface of perovskite
crystals.60 Accordingly, with increase of their density or
concentration on the reaction mixture, the dimension of the
nanocrystals became smaller because of instant capping.
Schematic presentations for the surface bonding with
ammonium ions in replacement of Cs+ ions are shown in
Figure S17, which is the most plausible condition expected
DOI: 10.1021/acsenergylett.7b01226
ACS Energy Lett. 2018, 3, 329−334
ACS Energy Letters
here. Furthermore, it is also observed that PbBr2, which is
widely known as bromide source, does not control the
dimensions. While reactions were carried out using PbO for
the synthesis of CsPbBr3, similar results were obtained (Figures
S18 and S19 and Supporting Information). The bromide source
of this reaction was also the ammonium bromide. In a typical
case under these reaction conditions, more precursor should
result in larger particle size, but the case remained the opposite.
Hence, the sole reason for the size restrictions with more alkyl
ammonium bromide assumed here is the strong interface
binding, which restricts the size.
This alkyl ammonium halide approach was extended to the
chloride system at 160 °C; a mixture of differently shaped
particles was formed, probably because of less solubility of
PbCl2 at this temperature. However, a wide size tunable
window was observed for CsPbCl3 at 180 °C, ranging from 25
to 6 nm. The TEM images of the nanocubes obtained on
varying the amount of salt and the corresponding size
histogram are presented in Figure S20. The method also did
not function for iodides, possibly because of the phase
instability of the nanocrystals.
In conclusion, a fixed reaction temperature synthetic
approach for wide window size tunable CsPbBr3 perovskite
nanocrystals is reported. This has been achieved by introducing
alkylammonium bromide salts, and with the increase of its
concentration, the size of the cubes and width of sheets were
reduced. The size window tunability also varied while the
reaction temperature varied. Importantly, this approach
requires no instant cooling, and the stable emission, size,
shape, and phase of the nanocrystals remained intact even on
prolonged annealing, which were typically not observed in
standard synthetic routes. Although this approach may lead to
more widespread synthesis of these materials, the chemistry of
controlling the dimensions of ionic perovskites is still not
clearly understood, and such an understanding is necessary for
better control of the synthesis of these nanostructures.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsenergy-
lett.7b01226.
Experimental methods and supporting figures (lifetime
decay plots, additional TEM images, AFM images, etc.)
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: camnp@iacs.res.in.
ORCID
Anirban Dutta: 0000-0001-9915-6985
Narayan Pradhan: 0000-0003-4646-8488
Author Contributions
†
Authors A.D. and S.K.D. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A.D., S.K.D., and S.D.A. acknowledge CSIR for fellowships.
DST (SR/NM/NS-1383/2014(G)) of India is acknowledged
for Funding.
332
Letter
■ REFERENCES
(1) Manser, J. S.; Christians, J. A.; Kamat, P. V. Intriguing
Optoelectronic Properties of Metal Halide Perovskites. Chem. Rev.
2016, 116, 12956−13008.
(2) Swarnkar, A.; Ravi, V. K.; Nag, A. Beyond Colloidal Cesium Lead
Halide Perovskite Nanocrystals: Analogous Metal Halides and Doping.
ACS Energy Lett. 2017, 2, 1089−1098.
(3) Lin, H.; Zhou, C.; Tian, Y.; Siegrist, T.; Ma, B. Low-Dimensional
Organometal Halide Perovskites. ACS Energy Lett. 2018, 3, 54−62.
(4) Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Krieg, F.; Caputo,
R.; Hendon, C. H.; Yang, R. X.; Walsh, A.; Kovalenko, M. V.
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br,
and I): Novel Optoelectronic Materials Showing Bright Emission with
Wide Color Gamut. Nano Lett. 2015, 15, 3692−3696.
(5) Hörantner, M. T.; Leijtens, T.; Ziffer, M. E.; Eperon, G. E.;
Christoforo, M. G.; McGehee, M. D.; Snaith, H. J. The Potential of
Multijunction Perovskite Solar Cells. ACS Energy Lett. 2017, 2, 2506−
2513.
(6) He, X.; Qiu, Y.; Yang, S. Fully-Inorganic Trihalide Perovskite
Nanocrystals: A New Research Frontier of Optoelectronic Materials.
Adv. Mater. 2017, 29, 1700775−1700801.
(7) Guria, A. K.; Dutta, S. K.; Adhikari, S. D.; Pradhan, N. Doping
Mn2+ in Lead Halide Perovskite Nanocrystals: Successes and
Challenges. ACS Energy Lett. 2017, 2, 1014−1021.
(8) Weidman, M. C.; Goodman, A. J.; Tisdale, W. A. Colloidal Halide
Perovskite Nanoplatelets: An Exciting New Class of Semiconductor
Nanomaterials. Chem. Mater. 2017, 29, 5019−5030.
(9) Niezgoda, J. S.; Foley, B. J.; Chen, A. Z.; Choi, J. J. Improved
Charge Collection in Highly Efficient CsPbBrI2 Solar Cells with Light-
Induced Dealloying. ACS Energy Lett. 2017, 2, 1043−1049.
(10) Saidaminov, M. I.; Almutlaq, J.; Sarmah, S.; Dursun, I.;
Zhumekenov, A. A.; Begum, R.; Pan, J.; Cho, N.; Mohammed, O. F.;
Bakr, O. M. Pure Cs4PbBr6: Highly Luminescent Zero-Dimensional
Perovskite Solids. ACS Energy Lett. 2016, 1, 840−845.
(11) Zhumekenov, A. A.; Saidaminov, M. I.; Haque, M. A.; Alarousu,
E.; Sarmah, S. P.; Murali, B.; Dursun, I.; Miao, X.-H.; Abdelhady, A. L.;
Wu, T.; et al. Formamidinium Lead Halide Perovskite Crystals with
Unprecedented Long Carrier Dynamics and Diffusion Length. ACS
Energy Lett. 2016, 1, 32−37.
(12) Peng, W.; Miao, X.; Adinolfi, V.; Alarousu, E.; El Tall, O.;
Emwas, A.-H.; Zhao, C.; Walters, G.; Liu, J.; Ouellette, O.; et al.
Engineering of CH3NH3PbI3 Perovskite Crystals by Alloying Large
Organic Cations for Enhanced Thermal Stability and Transport
Properties. Angew. Chem., Int. Ed. 2016, 55, 10686−10690.
(13) De Bastiani, M.; Dursun, I.; Zhang, Y.; Alshankiti, B. A.; Miao,
X.-H.; Yin, J.; Yengel, E.; Alarousu, E.; Turedi, B.; Almutlaq, J. M.;
et al. Inside Perovskites: Quantum Luminescence from Bulk Cs4PbBr6
Single Crystals. Chem. Mater. 2017, 29, 7108−7113.
(14) Maculan, G.; Sheikh, A. D.; Abdelhady, A. L.; Saidaminov, M. I.;
Haque, M. A.; Murali, B.; Alarousu, E.; Mohammed, O. F.; Wu, T.;
Bakr, O. M. CH3NH3PbCl3 Single Crystals: Inverse Temperature
Crystallization and Visible-Blind UV-Photodetector. J. Phys. Chem.
Lett. 2015, 6, 3781−3786.
(15) Braly, I. L.; Stoddard, R. J.; Rajagopal, A.; Uhl, A. R.; Katahara, J.
K.; Jen, A. K.; Hillhouse, H. W. Current Induced Phase Segregation in
Mixed Halide Hybrid Perovskites and its Impact on Two-Terminal
Tandem Solar Cell Design. ACS Energy Lett. 2017, 2, 1841−1847.
(16) Isarov, M.; Tan, L. Z.; Bodnarchuk, M. I.; Kovalenko, M. V.;
Rappe, A. M.; Lifshitz, E. Rashba Effect in a Single Colloidal CsPbBr3
Perovskite Nanocrystal Detected by Magneto-Optical Measurements.
Nano Lett. 2017, 17, 5020−5026.
(17) Jana, A.; Mittal, M.; Singla, A.; Sapra, S. Solvent-Free,
Mechanochemical Syntheses of Bulk Trihalide Perovskites and their
Nanoparticles. Chem. Commun. 2017, 53, 3046−3049.
(18) Mittal, M.; Jana, A.; Sarkar, S.; Mahadevan, P.; Sapra, S. Size of
the Organic Cation Tunes the Band Gap of Colloidal Organolead
Bromide Perovskite Nanocrystals. J. Phys. Chem. Lett. 2016, 7, 3270−
3277.
DOI: 10.1021/acsenergylett.7b01226
ACS Energy Lett. 2018, 3, 329−334
ACS Energy Letters
(19) Eperon, G. E.; Ginger, D. S. B-Site Metal Cation Exchange in
Halide Perovskites. ACS Energy Lett. 2017, 2, 1190−1196.
(20) Manser, J. S.; Saidaminov, M. I.; Christians, J. A.; Bakr, O. M.;
Kamat, P. V. Making and Breaking of Lead Halide Perovskites. Acc.
Chem. Res. 2016, 49, 330−338.
(21) Balakrishnan, S. K.; Kamat, P. V. Au-CsPbBr3 Hybrid
Architecture: Anchoring Gold Nanoparticles on Cubic Perovskite
Nanocrystals. ACS Energy Lett. 2017, 2, 88−93.
(22) Draguta, S.; Yoon, S. J.; Brennan, M. C.; Morozov, Y. V.; Kamat,
P. V.; Schneider, W. F.; Kuno, M.; Sharia, O.; Manser, J. M.
Rationalizing the Light-Induced Phase Separation of Mixed Halide
Organic-Inorganic Perovskites. Nat. Commun. 2017, 8, 200.
(23) Huang, W.; Manser, J. S.; Sadhu, S.; Kamat, P. V.; Ptasinska, S.
Direct Observation of Reversible Transformation of CH3NH3PbI3 and
NH4PbI3 Induced by Polar Gaseous Molecules. J. Phys. Chem. Lett.
2016, 7, 5068−5073.
(24) Pan, A.; He, B.; Fan, X.; Liu, Z.; Urban, J. J.; Alivisatos, A. P.;
He, L.; Liu, Y. Insight into the Ligand-Mediated Synthesis of Colloidal
CsPbBr3 Perovskite Nanocrystals: The Role of Organic Acid, Base, and
Cesium Precursors. ACS Nano 2016, 10, 7943−7954.
(25) Koscher, B. A.; Bronstein, N. D.; Olshansky, J. H.; Bekenstein,
Y.; Alivisatos, A. P. Surface- vs. Diffusion-Limited Mechanisms of
Anion Exchange in CsPbBr3 Nanocrystal Cubes Revealed through
Kinetic Studies. J. Am. Chem. Soc. 2016, 138, 12065−12068.
(26) Akkerman, Q. A.; Park, S.; Brescia, R.; Rastogi, P.; Prato, M.;
Manna, L.; Radicchi, E.; Nunzi, F.; Mosconi, E.; De Angelis, F. Nearly
Monodisperse Insulator Cs4PbX6 (X = Cl, Br, I) Nanocrystals, Their
Mixed Halide Compositions, and Their Transformation into CsPbX3
Nanocrystals. Nano Lett. 2017, 17, 1924−1930.
(27) Akkerman, Q. A.; Motti, S. G.; Srimath Kandada, A. R.;
Mosconi, E.; D’Innocenzo, V.; Bertoni, G.; Marras, S.; Kamino, B. A.;
Miranda, L.; De Angelis, F.; et al. Solution Synthesis Approach to
Colloidal Cesium Lead Halide Perovskite Nanoplatelets with
Monolayer-Level Thickness Control. J. Am. Chem. Soc. 2016, 138,
1010−1016.
(28) Palazon, F.; Almeida, G.; Akkerman, Q. A.; De Trizio, L.; Dang,
Z.; Prato, M.; Manna, L. Changing the Dimensionality of Cesium Lead
Bromide Nanocrystals by Reversible Postsynthesis Transformations
with Amines. Chem. Mater. 2017, 29, 4167−4171.
(29) Dang, Z.; Shamsi, J.; Palazon, F.; Imran, M.; Akkerman, Q. A.;
Park, S.; Bertoni, G.; Prato, M.; Brescia, R.; Manna, L. In Situ
Transmission Electron Microscopy Study of Electron Beam-Induced
Transformations in Colloidal Cesium Lead Halide Perovskite
Nanocrystals. ACS Nano 2017, 11, 2124−2132.
(30) Yang, S.; Niu, W.; Wang, A.-L.; Fan, Z.; Chen, B.; Tan, C.; Lu,
Q.; Zhang, H. Ultrathin Two-Dimensional Organic-Inorganic Hybrid
Perovskite Nanosheets with Bright, Tunable Photoluminescence and
High Stability. Angew. Chem., Int. Ed. 2017, 56, 4252−4255.
(31) Kamat, P. V. Semiconductor Nanostructures for Energy
Conversion. ACS Energy Lett. 2017, 2, 1128−1129.
(32) Akkerman, Q. A.; Gandini, M.; Di Stasio, F.; Rastogi, P.;
Palazon, F.; Bertoni, G.; Ball, J. M.; Prato, M.; Petrozza, A.; Manna, L.
Strongly Emissive Perovskite Nanocrystal Inks for High-Voltage Solar
Cells. Nat. Energy 2017, 2, 16194−16200.
(33) Das Adhikari, S.; Dutta, S. K.; Dutta, A.; Guria, A. K.; Pradhan,
N. Chemically Tailoring the Dopant Emission in Manganese-Doped
CsPbCl3 Perovskite Nanocrystals. Angew. Chem., Int. Ed. 2017, 56,
8746−8750.
(34) Huang, H.; Xue, Q.; Chen, B.; Xiong, Y.; Schneider, J.; Zhi, C.;
Zhong, H.; Rogach, A. L. Top-Down Fabrication of Stable
Methylammonium Lead Halide Perovskite Nanocrystals by Employing
a Mixture of Ligands as Coordinating Solvents. Angew. Chem., Int. Ed.
2017, 56, 9571−9576.
(35) Liu, L.; Huang, S.; Pan, L.; Shi, L.-J.; Zou, B.; Deng, L.; Zhong,
H. Colloidal Synthesis of CH3NH3PbBr3 Nanoplatelets with Polarized
Emission through Self-Organization. Angew. Chem., Int. Ed. 2017, 56,
1780−1783.
(36) Zhang, F.; Huang, S.; Wang, P.; Chen, X.; Zhao, S.; Dong, Y.;
Zhong, H. Colloidal Synthesis of Air-Stable CH3NH3PbI3 Quantum
333
Letter
Dots by Gaining Chemical Insight into the Solvent Effects. Chem.
Mater. 2017, 29, 3793−3799.
(37) Zhang, F.; Chen, C.; Kershaw, S. V.; Xiao, C.; Han, J.; Zou, B.;
Wu, X.; Chang, S.; Dong, Y.; Rogach, A. L.; et al. Ligand-Controlled
Formation and Photoluminescence Properties of CH3NH3PbBr3
Nanocubes and Nanowires. ChemNanoMat 2017, 3, 303−310.
(38) Huang, H.; Zhao, F.; Liu, L.; Zhang, F.; Wu, X.-g.; Shi, L.; Zou,
B.; Pei, Q.; Zhong, H. Emulsion Synthesis of Size-Tunable
CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient
Light-Emitting Diodes. ACS Appl. Mater. Interfaces 2015, 7, 28128−
28133.
(39) Zhang, F.; Zhong, H.; Chen, C.; Wu, X.-g.; Hu, X.; Huang, H.;
Han, J.; Zou, B.; Dong, Y. Brightly Luminescent and Color-Tunable
Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential
Alternatives for Display Technology. ACS Nano 2015, 9, 4533−4542.
(40) ten Brinck, S.; Infante, I. Surface Termination, Morphology, and
Bright Photoluminescence of Cesium Lead Halide Perovskite
Nanocrystals. ACS Energy Lett. 2016, 1, 1266−1272.
(41) Rosales, B. A.; Hanrahan, M. P.; Boote, B. W.; Rossini, A. J.;
Smith, E. A.; Vela, J. Lead Halide Perovskites: Challenges and
Opportunities in Advanced Synthesis and Spectroscopy. ACS Energy
Lett. 2017, 2, 906−914.
(42) Peng, L.; Geng, J.; Ai, L.; Zhang, Y.; Xie, R.; Yang, W. Room
Temperature Synthesis of Ultra-Small, Near-Unity Single-Sized Lead
Halide Perovskite Quantum Dots with Wide Color Emission
Tunability, High Color Purity and High Brightness. Nanotechnology
2016, 27, 335604−335611.
(43) Huang, H.; Bodnarchuk, M. I.; Kershaw, S. V.; Kovalenko, M.
V.; Rogach, A. L. Lead Halide Perovskite Nanocrystals in the Research
Spotlight: Stability and Defect Tolerance. ACS Energy Lett. 2017, 2,
2071−2083.
(44) Samu, G. F.; Janáky, C.; Kamat, P. V. A Victim of Halide Ion
Segregation. How Light Soaking Affects Solar Cell Performance of
Mixed Halide Lead Perovskites. ACS Energy Lett. 2017, 2, 1860−1861.
(45) Ahmadi, M.; Wu, T.; Hu, B. A Review on Organic-Inorganic
Halide Perovskite Photodetectors: Device Engineering and Funda-
mental Physics. Adv. Mater. 2017, 29, 1605242−1605265.
(46) Yassitepe, E.; Yang, Z.; Voznyy, O.; Kim, Y.; Walters, G.;
Castaneda, J. A.; Kanjanaboos, P.; Yuan, M.; Gong, X.; Fan, F.; et al.
Amine-Free Synthesis of Cesium Lead Halide Perovskite Quantum
Dots for Efficient Light-Emitting Diodes. Adv. Funct. Mater. 2016, 26,
8757−8763.
(47) Lignos, I.; Stavrakis, S.; Nedelcu, G.; Protesescu, L.; de Mello, A.
J.; Kovalenko, M. V. Synthesis of Cesium Lead Halide Perovskite
Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Para-
metric Space Mapping. Nano Lett. 2016, 16, 1869−1877.
(48) Shamsi, J.; Dang, Z.; Bianchini, P.; Canale, C.; Di Stasio, F.;
Brescia, R.; Prato, M.; Manna, L. Colloidal Synthesis of Quantum
Confined Single Crystal CsPbBr3 Nanosheets with Lateral Size
Control up to the Micrometer Range. J. Am. Chem. Soc. 2016, 138,
7240−7243.
(49) Nedelcu, G.; Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.;
Grotevent, M. J.; Kovalenko, M. V. Fast Anion-Exchange in Highly
Luminescent Nanocrystals of Cesium Lead Halide Perovskites
(CsPbX3, X = Cl, Br, I). Nano Lett. 2015, 15, 5635−5640.
(50) Mir, W. J.; Jagadeeswararao, M.; Das, S.; Nag, A. Colloidal Mn-
Doped Cesium Lead Halide Perovskite Nanoplatelets. ACS Energy
Lett. 2017, 2, 537−543.
(51) Hassan, Y.; Song, Y.; Pensack, R. D.; Abdelrahman, A. I.;
Kobayashi, Y.; Winnik, M. A.; Scholes, G. D. Structure-Tuned Lead
Halide Perovskite Nanocrystals. Adv. Mater. 2016, 28, 566−573.
(52) Teunis, M. B.; Johnson, M. A.; Muhoberac, B. B.; Seifert, S.;
Sardar, R. Programmable Colloidal Approach to Hierarchical
Structures of Methylammonium Lead Bromide Perovskite Nanocryst-
als with Bright Photoluminescent Properties. Chem. Mater. 2017, 29,
3526−3537.
(53) Tong, Y.; Bladt, E.; Aygueler, M. F.; Manzi, A.; Milowska, K. Z.;
Hintermayr, V. A.; Docampo, P.; Bals, S.; Urban, A. S.; Polavarapu.;
et al. Highly Luminescent Cesium Lead Halide Perovskite Nanocryst-
DOI: 10.1021/acsenergylett.7b01226
ACS Energy Lett. 2018, 3, 329−334
ACS Energy Letters Letter

als with Tunable Composition and Thickness by Ultrasonication.

Angew. Chem., Int. Ed. 2016, 55, 13887−13892.
(54) Zhao, J.; Liu, M.; Fang, L.; Jiang, S.; Zhou, J.; Ding, H.; Huang,
H.; Wen, W.; Luo, Z.; Zhang, Q.; et al. Great Disparity in
Photoluminesence Quantum Yields of Colloidal CsPbBr3 Nanocrystals
with Varied Shape: The Effect of Crystal Lattice Strain. J. Phys. Chem.
Lett. 2017, 8, 3115−3121.
(55) Zhumekenov, A. A.; Burlakov, V. M.; Saidaminov, M. I.; Alofi,
A.; Haque, M. A.; Turedi, B.; Davaasuren, B.; Dursun, I.; Cho, N.; El-
Zohry.; et al. The Role of Surface Tension in the Crystallization of
Metal Halide Perovskites. ACS Energy Lett. 2017, 2, 1782−1788.
(56) Ahmed, G. H.; Yin, J.; Bose, R.; Sinatra, L.; Alarousu, E.; Yengel,
E.; AlYami, N. M.; Saidaminov, M. I.; Zhang, Y.; Hedhili, M. N.; et al.
Pyridine-Induced Dimensionality Change in Hybrid Perovskite
Nanocrystals. Chem. Mater. 2017, 29, 4393−4400.
(57) Brennan, M. C.; Herr, J. E.; Nguyen-Beck, T. S.; Zinna, J.;
Draguta, S.; Rouvimov, S.; Parkhill, J.; Kuno, M. Origin of the Size-
Dependent Stokes Shift in CsPbBr3 Perovskite Nanocrystals. J. Am.
Chem. Soc. 2017, 139, 12201−12208.
(58) Teunis, M. B.; Jana, A.; Dutta, P.; Johnson, M. A.; Mandal, M.;
Muhoberac, B. B.; Sardar, R. Mesoscale Growth and Assembly of
Bright Luminescent Organolead Halide Perovskite Quantum Wires.
Chem. Mater. 2016, 28, 5043−5054.
(59) De Roo, J.; Ibanez, M.; Geiregat, P.; Nedelcu, G.; Walravens,
W.; Maes, J.; Martins, J. C.; Van Driessche, I.; Kovalenko, M. V.; Hens,
Z. Highly Dynamic Ligand Binding and Light Absorption Coefficient
of Cesium Lead Bromide Perovskite Nanocrystals. ACS Nano 2016,
10, 2071−2081.
(60) Ravi, V. K.; Santra, P. K.; Joshi, N.; Chugh, J.; Singh, S. K.;
Rensmo, H.; Ghosh, P.; Nag, A. Origin of the Substitution Mechanism
for the Binding of Organic Ligands on the Surface of CsPbBr3
Perovskite Nanocubes. J. Phys. Chem. Lett. 2017, 8, 4988−4994.
(61) Zhang, D.; Eaton, S. W.; Yu, Y.; Dou, L.; Yang, P. Solution-
Phase Synthesis of Cesium Lead Halide Perovskite Nanowires. J. Am.
Chem. Soc. 2015, 137, 9230−9233.
(62) Liang, Z.; Zhao, S.; Xu, Z.; Qiao, B.; Song, P.; Gao, D.; Xu, X.
Shape-Controlled Synthesis of All-Inorganic CsPbBr3 Perovskite
Nanocrystals with Bright Blue Emission. ACS Appl. Mater. Interfaces
2016, 8, 28824−28830.
(63) Swarnkar, A.; Chulliyil, R.; Ravi, V. K.; Irfanullah, M.;
Chowdhury, A.; Nag, A. Colloidal CsPbBr3 Perovskite Nanocrystals:
Luminescence beyond Traditional Quantum Dots. Angew. Chem., Int.
Ed. 2015, 54, 15424−15428.
(64) Kovalenko, M. V.; Protesescu, L.; Bodnarchuk, M. I. Properties
and Potential Optoelectronic Applications of Lead Halide Perovskite
Nanocrystals. Science 2017, 358, 745−750.
(65) Cottingham, P.; Brutchey, R. L. On the Crystal Structure of
Colloidally Prepared CsPbBr3 Quantum Dots. Chem. Commun. 2016,
52, 5246−5249.
(66) Li, G.; Wang, H.; Zhu, Z.; Chang, Y.; Zhang, T.; Song, Z.; Jiang,
Y. Shape and Phase Evolution from CsPbBr3 Perovskite Nanocubes to
Tetragonal CsPb2Br5 Nanosheets with an Indirect Bandgap. Chem.
Commun. 2016, 52, 11296−11299.

334 DOI: 10.1021/acsenergylett.7b01226

ACS Energy Lett. 2018, 3, 329−334