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Ultrasonics Sonochemistry 32 (2016) 54–59

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Sonochemical synthesis of CH3NH3PbI3 perovskite ultrafine nanocrystal


sensitizers for solar energy applications
Vijay Bhooshan Kumar a, Laxman Gouda a, Ze’ev Porat b,c, Aharon Gedanken a,d,⇑
a
Bar-Ilan Institute for Nanotechnology and Advanced Materials, Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
b
Division of Chemistry, Nuclear Research Center-Negev, P.O. Box 9001, Be’er-Sheva 84190, Israel
c
Institutes of Applied Research, Ben-Gurion University of the Negev, Be’er-Sheva 841051, Israel
d
National Cheng Kung University, Department of Materials Science & Engineering, Tainan 70101, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: The organic–inorganic hybrid perovskite CH3NH3PbI3 is becoming an interesting material in the field of
Received 29 October 2015 energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is
Received in revised form 7 February 2016 available in ample amounts. However, most of the previous research work was done on thin film of this
Accepted 7 February 2016
material. In the present work we describe the preparation of a powder containing nanoparticles of
Available online 17 February 2016
CH3NH3PbI3 using a sonochemical method. Characterization of the product was done by various methods,
such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crys-
Keywords:
tal structure), polygonal in shape and having diameters of 10–40 nm.
Sonochemical
Perovskite
Ó 2016 Elsevier B.V. All rights reserved.
CH3NH3PbI3
Solar cell

1. Introduction whereas the iodine atom shares a bond between two Pb ions and
the methyl amine ion, present at the center of the cage, acts as a
Silicon cells are today’s most popular commercialized solar rotating dipole. Solar cells made of this material work effectively
cells, ruling all the photovoltaic industry with highest 24.7% effi- in both mesoscopic and thin film configurations. The highest
ciency for single-crystal silicon solar cells [1]. However, silicon reported efficiency of this material, according to Seok, was 20.4%
solar cells are expensive for large scale production. It is known that [10]. CH3NH3PbI3 exhibits a very high charge carrier diffusion
the organic solar cells are much cheaper than the inorganic ones length of about 1 micron which is extremely good for photovoltaic
because of the low cost of the components and the ease of fabrica- cells [10]. A thin film of perovskite shows very high polarizability,
tion. In the past decade the perovskite-type compounds methy- ferroelectric property and ionic movement in the system. Current
lammonium lead trihalides CH3NH3PbX3 (X = Cl, Br, I) gained researches are focusing on finding an efficient fabrication method
more interest in solar-energy application (‘‘perovkite solar sells”). of the perovskite material to make the solar cells and light emitting
The rapid advances and breakthroughs in the organic–inorganic diode (LED) devices cheaper and easier to produce [8].
hybrid photovoltaic materials make the field attractive and Quantum dots (QD) of perovskite are also one of the targets of
promising for the solar cell industry [2–7]. Recently, improvement current research as an additional means for increasing the effi-
in the efficiency of the perovskite solar cell has been reported [7,8]. ciency of the solar devices. Easy exciton formation and charge-
The fabrication costs of the perovskite solar cells are much lower separation are remarkably efficient in QD. These nanocrystals are
than those of any other photovoltaic device [6]. CH3NH3PbI3 has mainly used in the areas of fluorescent labeling, probing, LED and
a very high absorption coefficient in the visible region and a band solar points [11]. The fabrication of stable quantum dot of per-
gap of about 1.4–1.5 eV [9]. This material is of the crystal structure ovskites was previously reported [11–13] by several groups but
of perovskite ABX3 with distortion in the octahedral center, break- commercial application of perovskite-QD is still under investiga-
ing the inversion center and resulting in an octahedral tilt of the tion. Few reports described the synthesis of CH3NH3PbI3 by one-
system [3]. The Pb atom is located in the corner of the cage step deep coating and/or other methods without using any catalyst
[14–18]. Perovskite nanoparticles (NPs) have attracted attention
⇑ Corresponding author at: Bar-Ilan Institute for Nanotechnology and Advanced due to their easy synthesis for highly luminescent colloidal quan-
Materials, Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel. tum dot materials which are highly demanding in the field of
E-mail address: gedanken@mail.biu.ac.il (A. Gedanken). LED devices and solar cell fabrication.

http://dx.doi.org/10.1016/j.ultsonch.2016.02.012
1350-4177/Ó 2016 Elsevier B.V. All rights reserved.
V. Bhooshan Kumar et al. / Ultrasonics Sonochemistry 32 (2016) 54–59 55

Recently an ultrasound-assisted approach for the synthesis of PW1050 X-ray diffractometer using Cu Ka radiation operating at
the perovskite in the bulk form was reported [19]. However, a syn- 40 kV/30 mA with a 0.0019 step size and a 1.0 s step.
thetic route of perovskite NPs in the nanometric scale is still
required with good homogeneity, which is an essential parameter
required for the fabrication of LED and solar cell devices. In the pre-
sent work we report on a new sonochemical technique for the for-
mation of CH3NH3PbI3 NPs in the size-range of 10–40 nm. The
method involves ultrasonic irradiation of two materials, CH3NH3I
and PbI2, dissolved in isopropanol, without any catalyst. In addi-
tion, this study presents a detailed investigation of the effect of
the sonication parameters on the physical and chemical properties
of CH3NH3PbI3 NPs.

2. Experimental

2.1. Chemicals

Lead iodide (PbI2) and isopropanol were purchased from Sigma-


Aldrich and used as received. Methyl ammonium iodide (MAI) was
prepared according to a procedure published elsewhere [4,19,20].

2.2. Preparation procedure

The CH3NH3PbI3 ultrafine nanoparticles were prepared by son-


icating together solutions of the two components, CH3NH3I and
PbI2, in isopropanol. First, 8 mL of a 0.25 M solution of CH3NH3I
were transferred into a glass test tube and sonicated for 30 s. Then
6 mL of 0.25 M solution of PbI2 were added dropwise while sonica-
tion was continued for another 10, 20 or 30 min. A Change in the
color from yellow to dark brown was observed right after mixing
the two precursors, indicating the occurrence of a chemical reac-
tion. The sonication cell was immersed in a water bath and the
temperature inside was constantly monitored by a thermocouple
to be 40–44 °C.
To examine the effect of sonication, control experiments were
performed in which the solutions of the two components were
mixed by magnetic stirring at 40 °C, using either a regular labora-
tory stirrer (Fried Co. Israel) at 1000 rpm and or a high-speed stir-
rer (6000 rpm) Ultraturrax device (Leroy Somer, Digidrive SK,
make ESCO-LABOR).

2.3. Equipment Fig. 1. XRD patterns of CH3NH3PbI3 perovskite ultrafine nanoparticles. (A) After
sonication in isopropanol for 10, 20, and 30 min. The peak assigned to unreacted
PbI2 is marked. (B) After 20 min sonication in water.
The ultrasonic transducer (Sonics and Materials Inc., USA,
model VCX 750, frequency 20 kHz, volt 230V AC) was operated at
an amplitude of 60%.

2.4. Analytical techniques

Inspection of the products was done with a JEOL 2100 high-


resolution transmission electron microscope (HRTEM), operated
at an accelerating voltage of 200 kV. The samples for TEM were
prepared by suspending some CH3NH3PbI3 powder in isopropanol,
using an ultrasonic cleaning bath. A few droplets of the suspension
were applied on a carbon-coated TEM grid and dried in a vacuum
chamber. Elemental analysis and elemental mapping were per-
formed using the TEM Energy Dispersive X-ray Spectroscopy
(EDS) unit. Scanning electron microscopy (SEM) was performed
using an Inspect FEI microscope. Zeta potential and DLS measure-
ments of the particles were performed on ZetaSizer Nano-ZS
(Malvern Instruments Ltd., Worcestershire, UK). The photolumi-
nescence of the CH3NH3PbI3 was measured using a fluorescence
spectrophotometer (Varian Cary Eclipse). X-ray diffraction (XRD) Fig. 2. SEM image of CH3NH3PbI3 particles obtained by reaction of CH3NH3I and
was performed with a Bruker D8 Advance or with Philips PbI2 solutions under vigorous stirring (6000 RPM).
56 V. Bhooshan Kumar et al. / Ultrasonics Sonochemistry 32 (2016) 54–59

3. Results and discussion the diffraction planes (1 1 0), (1 1 2), (2 1 1), (2 0 2), (2 2 0), (3 1 0),
(3 1 2), (2 2 4), and (3 1 4), respectively [21]. A small peak can be
As stated above, the sonication of the CH3NH3I and PbI2 was observed at 2h = 13° (marked by an arrow), which is attributed to
conducted in isopropanol solution. A color change from yellow to unreacted PbI2. This peak was diminishing with the sonication
dark brown was observed right after mixing the two precursors, time, indicating the completion of the reaction. Measurements of
indicating the formation of CH3NH3PbI3 perovskite. The formation the particles size-distribution showed similar results after 20 and
of the perovskite was monitored by X-ray diffraction (XRD) and by 30 min. Therefore, it was decided that the optimum sonication
optical excitation and emission spectroscopy. The wide-angle XRD time is 20 min. The stability of the CH3NH3PbI3 perovskite ultrafine
patterns obtained from the products after 10, 20 and 30 min. are nanoparticles under ambient atmosphere was examined by occa-
presented in Fig. 1A, all showing similar phases at 2h = 14.2, 20.2, sional XRD measurements. Neither peaks of unreacted precursors
23.6, 24.6, 28.1, 28.7, 31.6, 34.8, and 41.6° that were assigned to nor peaks of PbO2 were detected in the XRD pattern for the 20-
min sonication product. It was found that after several weeks no
changes in the peak intensities and peak positions could be
observed.
Several control reactions were conducted in order to prove that
the sonochemical reaction was responsible for the formation of
CH3NH3PbI3 nanoparticles. When the same reagents, dissolved in
isopropanol, were stirred vigorously without the application of
ultrasonic irradiation, the same product was obtained but the size
of particles was in the micrometric range. When water was used as
the liquid medium for sonication instead of isopropanol, PbO and
unreacted PbI2 were detected by XRD analysis (Fig. 1B). Similar
results were obtained by other groups who have carried out the
same reaction using stirring or bath sonication and obtained larger
CH3NH3PbI3 particles in the micrometric scale [3,19,20,22]. The
experiment conducted under vigorous stirring using the Ultratur-
rax device yielded micron-size particles of CH3NH3PbI3, which
are presented in Fig. 2, together with some unreacted PbI2. Thus
it seems that intense ultrasonic irradiation is required to get parti-
cles in the nanometre scale. We assume that the experiment
reported in Ref. [19] was carried out in a sonication bath. To check
this claim a control experiment was conducted in a sonication bath
(MRS Ultrasonic Cleaner, Power 120 W, frequency 40 kHz) for
20 min, which yielded only micron-size particles of CH3NH3PbI3.
TEM images of the CH3NH3PbI3 nanoparticles that were
obtained by 10 min. sonication display non-uniform shapes
Fig. 3. TEM images of the CH3NH3PbI3 nanoparticles formed within 10 min. (A) and
(Fig. 3A). However, when the reaction time was increased to 20
20 min. (B) of ultrasonic irradiation. (C) Higher magnification image of the particles or 30 min. facetted crystallites were observed, mainly in the shapes
shown in 2B. Inset: SAED. (D) A higher magnification image of several CH3NH3PbI3 of hexagonal and triangles (Fig. 3B and C). The increase in the par-
particles. Inset: lattice fringes of a single particle. ticle size with sonication time can be explained as follows: it is

Fig. 4. Elemental analysis of the CH3NH3PbI3 nanoparticles obtained within 20 min. sonication.
V. Bhooshan Kumar et al. / Ultrasonics Sonochemistry 32 (2016) 54–59 57

Determination of the composition of the product was done by


energy dispersive X-ray spectroscopy (EDS) and by elemental map-
ping. EDS analysis of a sample of the 20-min. product shows the
presence of only three elements (C, Pb, and I). Fig. 4 shows the
nearly even distribution of these elements in the particles. More-
over, these images appear to be complementary to each other
Transmitance

and sites which are depleted with one element seem to be enriched
with another element. It seems that in each point all the three ele-
ments are present.
The chemical structure of CH3NH3PbI3 particles was character-
ized by FTIR (Fig. 5). The spectrum shows main characteristic broad
peaks at 1500 and 956 cm 1 which are assigned to the stretching
CH3NH3I modes of N–Pb–I and Pb–I–NH bending, respectively. The wide
PbI2 band around 3066 cm 1 is attributed to the CH–NH stretching
CH3NH3PbI3 20 minutes vibration. The FTIR spectra of pure PbI2 powder and of MAI are also
presented in Fig. 5. Comparing the three spectra shows that no
500 1000 1500 2000 2500 3000 3500 4000 traces of PbI2 and MAI can be found in the product obtained after
Wavenumber (cm-1) 20 min of sonication.
The size distributions of the particles formed in isopropanol
Fig. 5. FTIR spectra of CH3NH3PbI3 perovskite ultrafine nanoparticles in comparison
to the spectra of its precursors. were measured by Dynamic Light Scattering (DLS). As before, a
small portion of the dried particles was suspended in isopropanol
using sonication bath prior to the measurement. Three consecutive
known that in the presence of solid materials, further collapse of measurements (Fig. 6A) showed that the particles were in the size
the acoustic bubbles results in the formation of microjets moving range of 10–60 nm, which is in reasonable agreement with that
at very high speeds in the direction of the solid particles. Fig. 3B determined by the TEM measurements (10–40 nm)
shows particles of various polygonal shapes in the sizes range of The zeta potential of the particles, which may account for their
10–40 nm. Both the XRD pattern and the facetted-shaped particles stability, was also measured in the isopropanol suspension of the
indicate that they are crystalline, which implies that crystallization particles. Three consecutive measurements were performed, all
must occur during the sonication. The inset in Fig. 3C shows the showing good repeatability (Fig. 6B). The negative zeta potential
selected area electron diffraction (SAED) having a ring pattern, cor- ( 19 mV) indicates that negative ions reside on the surface, which
responding to the (1 1 0), (1 1 2), (2 1 1), (2 0 2), (2 2 0) and (3 1 0) is beneficial for the deposition of CH3NH3PbI3 on cathode for solar
planes of a perovskite structure (space group Pm3 m) [21]. The cell cell application.
parameter for the tetragonal CH3NH3PbI3 are a = b = 8.8 Ǻ and Further characterization included fluorescence measurements.
c = 12.64 Ǻ [23]. A high resolution image (Fig. 3D) show fringes The excitation spectrum showed a peak at 447 nm (Fig. 7A) while
with d spacing of 0.31 nm, corresponding to the CH3NH3PbI3 emission was recorded at 513 nm. When the CH3NH3PbI3 particles
tetragonal plane. were excited at 447 nm, a maximum emission peak was found at

Fig. 6. Plots of three consecutive measurements of DLS (A) and Zeta Potential (B) performed in isopropanol suspensions of the CH3NH3PbI3 perovskite particles, obtained
within 20 min. sonication.
58 V. Bhooshan Kumar et al. / Ultrasonics Sonochemistry 32 (2016) 54–59

250
300
A B
250 200

Ext. Intensity (a.u.)

PL Intensity (a.u.)
513 nm
200 447 nm 150
150
100
100
50
50

0 0
350 400 450 500 450 500 550 600 650 700 750
Wavelength (nm) Wavelength (nm)

Fig. 7. (A) Excitation spectrum (B) Emission spectrum and (C) UV–Visible–NIR spectrum of CH3NH3PbI3 nanoparticles, suspended in isopropanol.

513 nm (Fig. 7B). CH3NH3PbI3 exhibits excitation-dependent emis- indicate that negative ions reside on the surface. This may enable
sion behavior only when the excitation wavelength is longer than the deposition of CH3NH3PbI3 on cathode for use in solar cells.
430 nm. Indeed, the emission wavelength remained unchanged at The sonochemical reaction leads to the formation of nanoparticles
513 nm when the excitation wavelength varied from 440 nm to in a mechanism involving small seeding particles formed upon the
470 nm. Although the mechanism of the origin of luminescence collapse of the acoustic bubble that keep growing in the solution.
from CH3NH3PbI3 remains controversial, it is generally accepted
that different surface states caused by different functional groups
are responsible for these photoluminescence properties. The broad
PL signal might be due to the non-uniform particle distribution. References
The absorption band of the hybrid perovskite has normally an
[1] M.A. Green, The path to 25% silicon solar cell efficiency: history of silicon cell
edge at the wavelength of 850 nm (Fig. 7C), but the experimental
evolution, Prog. Photovoltaics Res. Appl. 17 (2009) 183–189, http://dx.doi.org/
absorbance spectra of our material shows absorption onset at 10.1002/pip.892.
around 550 nm. This shows that the band gap of the material [2] E. Edri, S. Kirmayer, S. Mukhopadhyay, K. Gartsman, G. Hodes, D. Cahen,
shifted from standard 1.15 eV (bulk) to 2.25 eV. This blue shift in Elucidating the charge carrier separation and working mechanism of
CH3NH3PbI3 xClx perovskite solar cells, Nat. Commun. 5 (2014) 1–8, http://
band gap indicates that our material possesses properties of quan- dx.doi.org/10.1038/ncomms4461.
tum dot. [3] Z. Chen, H. Li, Y. Tang, X. Huang, D. Ho, C.-S. Lee, Shape-controlled synthesis of
The mechanism of formation of these particles is as follows: organolead halide perovskite nanocrystals and their tunable optical
absorption, Mater. Res. Express. 1 (2014) 015034, http://dx.doi.org/10.1088/
upon the collapse of the acoustic bubbles many very small seeds 2053-1591/1/1/015034.
are formed. They come out from the bubble region and continue [4] R. Gottesman, E. Haltzi, L. Gouda, S. Tirosh, Y. Bouhadana, A. Zaban, et al.,
to grow. It was shown that the reaction can continue under stir- Extremely slow photoconductivity response of CH3NH3PbI3 perovskites
suggesting structural changes under working conditions, J. Phys. Chem. Lett.
ring, and stirring is continued as long as the ultrasonic waves are 5 (2014) 2662–2669, http://dx.doi.org/10.1021/jz501373f.
operated. The growth is continuing until all the amount of the reac- [5] Z. Zhu, J. Ma, Z. Wang, C. Mu, Z. Fan, L. Du, et al., Efficiency enhancement of
tant is exhausted. Since very many seeds were formed at the begin- perovskite solar cells through fast electron extraction: the role of graphene
quantum dots, J. Am. Chem. Soc. 136 (2014) 3760–3763, http://dx.doi.org/
ning of the growth only nanoparticles are obtained.
10.1021/ja4132246.
[6] L.C. Schmidt, A. Pertega, S. Gonzalez-Carrero, O. Malinkiewicz, S. Agouram, G.
M. Espallargas, et al., Nontemplate synthesis of CH3NH3PbBr 3 perovskite
4. Conclusion nanoparticles, J. Am. Chem. Soc. 136 (2014) 850–853.
[7] J.-H. Im, I.-H. Jang, N. Pellet, M. Grätzel, N.-G. Park, Growth of CH3NH3PbI3
CH3NH3PbI3 nanocrystals were synthesized by sonication of a cuboids with controlled size for high-efficiency perovskite solar cells, Nat.
Nanotechnol. 9 (2014) 927–932, http://dx.doi.org/10.1038/nnano.2014.181.
mixture of isopropanol solutions of methyl ammonium iodide
[8] D.M. Jang, K. Park, D.H. Kim, J. Park, F. Shojaei, H.S. Kang, et al., Reversible
and lead iodide. The product was obtained in the form of fine par- halide exchange reaction of organometal trihalide perovskite colloidal
ticles of polygonal shapes, in the size-range of 10–40 nm in 20 min nanocrystals for full-range band gap tuning, Nano Lett. (2015), http://dx.doi.
of sonication. The particles were crystalline and exhibited clear org/10.1021/acs.nanolett.5b01430. 150714104303009.
[9] V.D. Innocenzo, A. Ram, S. Kandada, M. De Bastiani, M. Gandini, A. Petrozza,
X-ray and electron diffraction patterns. Zeta potential ( 19 mV) Tuning the light emission properties by band gap engineering in hybrid lead
measurements of the particles gave negative values, which halide perovskite, J. Am. Chem. Soc. 136 (2014) 17730–17733.
V. Bhooshan Kumar et al. / Ultrasonics Sonochemistry 32 (2016) 54–59 59

[10] N.J. Jeon, J.H. Noh, Y.C. Kim, W.S. Yang, S. Ryu, S. Il Seok, Solvent engineering for novel optoelectronic materials showing bright emission with wide color
high-performance inorganic–organic hybrid perovskite solar cells, Nat. Mater. gamut, Nano Lett. 15 (2015) 3692–3696, http://dx.doi.org/10.1021/nl5048779.
(2014) 1–7, http://dx.doi.org/10.1038/nmat4014. [18] C. Wehrenfennig, M. Liu, H.J. Snaith, M.B. Johnston, L.M. Herz, Homogeneous
[11] S. Rühle, M. Shalom, A. Zaban, Quantum-dot-sensitized solar cells, emission line broadening in the organo lead halide perovskite CH3NH3PbI3–
ChemPhysChem 11 (2010) 2290–2304, http://dx.doi.org/10.1002/cphc. xClx, J. Phys. Chem. Lett. 5 (2014) 1300–1306.
201000069. [19] Y. Kesari, A. Athawale, Ultrasound assisted bulk synthesis of CH3NH3PbI3
[12] K. Zheng, Q. Zhu, M. Abdellah, M.E. Messing, W. Zhang, A.V. Generalov, et al., perovskite at room temperature, Mater. Lett. 159 (2015) 87–89, http://dx.doi.
Exciton binding energy and the nature of emissive states in organometal org/10.1016/j.matlet.2015.05.176.
halide perovskites, J. Phys. Chem. Lett. (2015) 2969–2975, http://dx.doi.org/ [20] H.-L. Hsu, C.-P. Chen, J.-Y. Chang, Y.-Y. Yu, Y.-K. Shen, Two-step thermal
10.1021/acs.jpclett.5b01252. annealing improves the morphology of spin-coated films for highly efficient
[13] X. Wang, L. Cao, S.-T. Yang, F. Lu, M.J. Meziani, L. Tian, et al., Bandgap-like perovskite hybrid photovoltaics, Nanoscale 6 (2014), http://dx.doi.org/
strong fluorescence in functionalized carbon nanoparticles, Angew. Chem. Int. 10.1039/C4NR02751E. Ahead of Print.
Ed. Engl. 49 (2010) 5310–5314, http://dx.doi.org/10.1002/anie.201000982. [21] T. Baikie, Y. Fang, J.M. Kadro, M. Schreyer, F. Wei, S.G. Mhaisalkar, et al.,
[14] J. Navas, A. Sánchez-coronilla, J. Gallardo, N.C. Hernández, C. Piñero, R. Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for
Alcántara, et al., New insights into organic–inorganic hybrid, Nanoscale 7 solid-state sensitised solar cell applications, J. Mater. Chem. A. 1 (2013) 5628,
(2015) 6216–6229, http://dx.doi.org/10.1039/c5nr00041f. http://dx.doi.org/10.1039/c3ta10518k.
[15] H. Kim, C. Lee, J. Im, K. Lee, T. Moehl, A. Marchioro, et al., All-Solid-State [22] G.E. Eperon, V.M. Burlakov, P. Docampo, A. Goriely, H.J. Snaith, Morphological
Submicron Thin Film, Sci. Rep. 591 (2012) 1–7, http://dx.doi.org/10.1038/ control for high performance, solution-processed planar heterojunction
srep00591. perovskite solar cells, Adv. Funct. Mater. 24 (2014) 151–157, http://dx.doi.
[16] T. Baikie, Y. Fang, J.M. Kadro, M. Screyer, F. Wei, S.G. Mhaisakar, M. Graetzel, T. org/10.1002/adfm.201302090.
J. White, J. Mater. Chem. A 1 (2013) 5628–5641, http://dx.doi.org/10.1039/ [23] J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M.K. Nazeeruddin,
c3ta10518k. et al., Sequential deposition as a route to high-performance perovskite-
[17] L. Protesescu, S. Yakunin, M.I. Bodnarchuk, F. Krieg, R. Caputo, C.H. Hendon, sensitized solar cells, Nature 499 (2013) 316–319, http://dx.doi.org/
et al., Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): 10.1038/nature12340.