Growth and characterization of all-inorganic lead halide perovskite semiconductor CsPbBr3 single crystals

Article abstract of DOI:10.1039/c7ce01709j

As a typical representative of all-inorganic lead halide perovskites, cesium lead bromide (CsPbBr₃) has attracted significant attention in the context of photovoltaics and other optoelectronic applications in recent years. In this paper, CsPbBr₃ single crystal growth was conducted by a creative electronic dynamic gradient (EDG) method. The crystal structure was systematically investigated using scientific instruments and equipment. X-ray diffraction techniques, including X-ray diffraction (XRD), temperature-dependent X-ray powder diffraction and the X-ray rocking curve, were used to identify the phase and to investigate phase transition rules. Electron diffraction techniques, including high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and electron backscatter diffraction (EBSD), were used to investigate the crystal micro-structure. The final results indicated that the grown CsPbBr₃ crystal was a perfect single crystal preferentially orienting in the (110) direction and met the basic demand of its applications.

Full text of DOI:10.1039/c7ce01709j

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The crystal structure transform from orthorhombic to tetragonal at 88 °C and then to cubic at 130 °C.

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The crystal structure transform from orthorhombic to tetragonal at 88 °C and then to cubic at 130 °C.
9x26mm (300 x 300 DPI)
3

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Growth and characterization of the all-inorganic lead halide
perovskite semiconductor CsPbBr single crystals
3
Received 00th January 20xx,
Accepted 00th January 20xx
a
*a
a, b
a
a
a
Mingzhi Zhang, Zhiping Zheng, Qiuyun Fu, Zheng Chen, Jianle He, Sen Zhang,
a
a
a
Liang Yan, Yunxiang Hu, and Wei Luo
DOI: 10.1039/x0xx00000x
As a typical representative of all-inorganic lead halide perovskites, cesium lead bromine (CsPbBr
3
) has attracted significant
www.rsc.org/
attention in the context of photovoltaics and other optoelectronic applications in recent years. In this paper, CsPbBr
3
single crystal growth was conducted by a creative electro dynamic gradient (EDG) method. The crystal structure was
systematic investigated by scientific instruments and equipment. X-ray diffraction techniques, including X-ray diffraction
(XRD), temperature-dependent X-ray powder diffraction and X-ray rocking curve were used to identify phase and to
investigate phase transition rules. Electron diffraction techniques, including high-resolution transmission electron
microscopy (HRTEM), selected area electron diffraction (SAED) and electron backscatter diffraction (EBSD) were used to
3
investigate crystal micro-structure. The final results indicated that the grown CsPbBr crystal was a perfect single crystal
preferentially orienting in the (110) direction and met the basic demand of applications.
inorganic lead halide perovskites show nearly the same power
conversion efficiency as the leading solar cell material, hybrid
1
. Introduction
23
3 3 3
organic-inorganic CH NH PbI .
Lead halide perovskite materials have attracted significant
In this study, we turn readers’ attention to one kind of all-
inorganic lead halide perovskites, cesium lead bromine
attention in the context of photovoltaics and other
optoelectronic applications in recent years. Demonstrated
optoelectronic applications of lead halide perovskites include
(
CsPbBr
nuclear radiation in view of its relatively high density (4.84
g/cm ) and high average atomic number (Cs: 55, Pb: 82 and Br:
5). Additionally, its large band gap (2.25 eV) offers the
possibility of low noise performance at room temperature.
1,12 What is more, CsPbBr has a same order of carrier mobility
3 3
). CsPbBr is an attractive detection medium for
1
,2
3,4
high-efficiency solar cells, lasers,
light-emitting diodes
5,6
7-10
3
(LED), and high-gain photodetectors.
However organic-
3
inorganic hybrid lead halide perovskite materials (the general
formula APbX are often criticized for their inherent
instability, such as high sensitivity to oxygen and moisture.
These instability originated from the A-site organic cations or
3
)
1
3
-
3
2
lifetime products for both electrons and holes (1.7×10 cm /V
7
-
and 1.3×10 cm /V for electrons and holes, respectively),
3
2
+
+
1-3,11,13
cationic clusters (MA , FA et. al).
more research efforts have been directed to all-inorganic lead
Recently, more and
implying that no special engineering methodologies are
required for patching mismatches between holes and
electrons. Thus, this ternary compound shows potential
characteristic in the optoelectronic performance, especially in
1
4-19
halide perovskite,
which has better mechanical and
moisture stability than organic–inorganic hybrid lead halide
ones. Benefiting from their promising properties such as
excellent optical performance, high charge carrier mobility and
a general tolerance to defects, all-inorganic lead halide
7,10
the high energy radiation detection.
However, the
overwhelming majority of perovskite devices are based upon
polycrystalline thin films, which suffer immensely from a high
density of traps and grain boundaries. Compared with the
perovskites MPbX
3
(M=K, Rb, and Cs, X = I, Br, and Cl) have
2
0-22
drawn much attention to them.
Furthermore, these all-
polycrystalline CsPbBr
3 3
thin films, CsPbBr single crystals
display exceptionally low trap densities (6 orders of magnitude
2
4
less compared to their polycrystalline films). However, the
available research on the structure and physical properties of
3
the CsPbBr single crystals is not very sufficient and many great
blanks need to be filled. Therefore, the potential application of
these polycrystalline devices is markedly limited. Although the
synthesis, crystallography, and photoconductivity of all-
inorganic lead halide perovskites have been first reported
more than 50 years ago, few researchers have focused on the
2
5
direct band-gap MPbX
3
single crystals until 2015. Therefore,
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the growing interest in perovskite single crystals motivated us transmission electron microscopy (HRTEM) were performed
to develop facile methods for the single crystal growth of using a Tecnai F30 G2 electron microscope with an incident
7
, 10,14, 26
CsPbBr
3
.
electron energy of 300 keV. The micro-structural
crystallographic characterization of the crystal was
investigated by EBSD patterns using accelerating voltage of 20
kV by a FEI Nova Sirion 200.
2
. Experimental
2
.4 Optical characterization
2
.1 Synthesis of CsPbBr
Synthesis of the CsPbBr
carried out by chemical co-precipitation method.
Commercial available lead (II) bromide (PbBr , 99.999%) and
cesium bromide (CsBr, 99.999%) were supplied by Alfa Aesar
Sain Louis, UK). Aqueous hydrobromic acid (HBr, 48 wt% in
O, 99.99% metals basis) was purchased from Aladdin
Shanghai, China). PbBr (20 mmol, 7.34g) and CsBr (20 mmol,
.26g) were respectively dissolved in the hydrobromic acid
3
48% HBr(aq)] in separate beakers to form PbBr and CsBr 3.1 Phase identification of CsPbBr powder
3
polycrystalline powders
The quality of the crystal was mainly characterized by the
3
polycrystalline powders was
2
7
optical performance. The optical transmittance was studied by
-
1
Bruker Vertex70 FT-IR (wavenumber range 1000-4000 cm )
and Perkin-Elmer Lambda 35 Ultraviolet spectrophotometer
2
(wavelength range 190-2600 nm) at room temperature.
(
H
2
(
2
3
. Result and discussion
4
[
2
solutions in advance. Then the solutions were simultaneously
dropwise added into 5 ml of 48% aqueous HBr with stirring
during the synthesis reaction. The precipitation reaction was
as following:
The powder XRD patterns of the synthesized
polycrystalline powders, together with the standard patterns
of cubic phase (ICSD 29073, Pm-3m(221), a=b=c=0.5874 nm)
30
and orthorhombic phase (ICSD 97851, Pbnm(62), a=0.8207 nm,
3
1
b=0.8255 nm, c=1.1759 nm) of CsPbBr
. The standard patterns of tetragonal phase (ICSD 109295,
3
were shown in Figure
PbBr + CsBr = CsPbBr
↓
(1)
3
2
1
32
P4/mbm(99), a=b=0.5859 nm, c=0.5895 nm) were shown in
Figure S4 It was illustrated that the first three strong peaks of
3
Bright orange precipitation of CsPbBr immediately formed in
.
the aqueous HBr solution. The precipitation was filtered,
copiously rinsed three times by absolute ethyl alcohol and
the synthesized polycrystalline powders, (110) at 15.198°, (112)
at 21.443° and (220) at 30.663°, matched up with the standard
orthorhombic perovskite structure well. Thus the synthesized
then dried under vacuum to obtain orange CsPbBr
polycrystalline powders.
3
powders can be identified as CsPbBr
clear splitting of (110) and (220) diffraction peaks further
powders indicated that the synthesized CsPbBr polycrystalline powders
3
powders. Meanwhile the
2
.2 A tube furnace and EDG crystal growth
The thermogravimetric analysis of the CsPbBr
3
3
3
was described in supporting information (Supporting may be of room-temperature orthorhombic phase (Pbnm),
Information 1.1 and Figure S1-S2). The melting point and but further study was needed to prove it.
solidifying point was 567 °C and 550 °C according to Figure S1.
The melting point has the same result as the reported in Ref 7,
but the solidifying point had a slight deviation. This deviation
maybe come from the different degree of supercooling under
diverse testing conditions (rate of temperature rise, protective
atmosphere etc.). The reported crystal structure transitions
from the orthorhombic (Pnma) to the tetragonal (P4/mbm)
symmetries and from tetragonal (P4/mbm) to cubic (Pm-3m)
were not observed in our analysis, possibly due to insufficient
7, 14,28
sensitivity of the measurement.
The single crystal growth
was conducted in a self-designed vertical two-zone tube
furnace by a simplified electronic dynamic gradient (EDG)
29
3
method. The detailed procedure of CsPbBr crystal growth
was described in supporting information (Supporting
Information 1.2 and Figure S3).
2.3 Structural characterization
The crystal structure was systematically investigated by
scientific instruments and equipments. A BRUKER AXS D8
ADVANCE X-ray diffractometer equipped with heating system
was used to characterize the phase identification of the
crystal. The rocking curve was tested in ω scan mode using
CuK1 source with a wavelength of 1.5406 Å, under a generator
voltage of 40 kV, and a generator current of 40 mA. Selected
area electron diffraction (SAED) and high-resolution
Figure 1 Powder X-ray diffraction patterns of the synthesized
powders and the split diffraction peaks
In order to further study the final phase of CsPbBr
a small portion of the grown CsPbBr ingot was ground into
fine powders. Then temperature-dependent powder X-ray
diffraction was used to study the phase transitions of CsPbBr
3
crystal,
3
3
,
2
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and the results were shown in Figure 2, with the standard phase and the quality of the crystal. The fabrication of wafers
patterns of cubic (ICSD 29073), tetragonal (ICSD 109295) and was described in supporting information (Supporting
orthorhombic (ICSD 97851) perovskite structure shown in the Information 1.4). Figure S6 presented a photograph of the
top, middle and bottom of the figure, respectively. Obviously, isometric part of the crystal ingot. Figure 3 showed
a
the crystal structure of CsPbBr changed with the temperature photograph of a typical wafer with 8 mm in diameter and 1.5
3
increasing from room temperature (300 K) to high mm in thickness. Obviously, the wafer had orange yellow
temperature (500 K). Splitting of the strong diffraction peaks color, a good transparency and a bright, shiny and mirror-like
disappeared gradually with the temperature increasing. And surface.
the weak diffraction peaks at 24.165°, 25.347°, 28.587° (the
featured peaks of low temperature phase) also disappeared
gradually with the temperature increasing. These phenomena
can be observed more clearly in the zoom-in image of the XRD
pattern, which shown in supporting information (Supporting
Information 1.3 and Figure S5). These phenomena indicated
that the phase transitions of CsPbBr
temperature rise and the phase transition temperatures were
around 360 K (87 °C) and 400 K (127 °C). According to Ref 7
CsPbBr had two successive phase transitions at 88 °C and 130
C, corresponding to the crystal structure transforming from
3
were occurred with
，
3
°
room temperature orthorhombic (Pbnm, equal to Pnma) to
tetragonal (P4/mbm) and then to cubic (Pm-3m), respectively.
The temperature-dependent XRD patterns of this work were
similar to that reported in Ref.7. The orthorhombic phase
(
Pbnm) had a typical characteristic of splitting diffraction peaks
3
at 15.198° and 30.663° relative to the cubic phase (Pm-3m).
3
Figure 3 Photograph of a CsPbBr wafer
3
.3 X-ray diffraction and rocking curve analysis
Figure 4 presented the XRD pattern of a CsPbBr
with the standard pattern of the orthorhombic structure (ICSD
7851) provided at the bottom. It can be seen that the
3
wafer,
9
intensity of the (110) peak was quite strong, indicating that the
crystal was a perfect single crystal preferentially orienting in
the (110) direction. The secondary diffraction peak of (220)
plane suggested crystalline perfection. The clear splitting of
(
3
110) and (220) peaks indicated that the grown CsPbBr crystal
3
was of the room-temperature orthorhombic phase.
Figure 2 Temperature-dependence X-ray powder diffraction
patterns of CsPbBr powders
3
3.2 General appearance of CsPbBr
3
single crystal
An as-grown CsPbBr crystal with 60 mm overall length
3
was obtained from EDG method. The conical part of the crystal
ingot was about 30 mm in length as shaped by the ampule,
and it was irregular with a gradually varied diameter. The
isometric part, with a diameter of 8 mm and an approximate
length of 30 mm, was sliced into wafers to investigate the
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Figure 4 XRD pattern and rocking curve of the (110) plane of the
crystal, inset: rocking curve
weak spots (111) and (222) (marked by blue circles), which
were unique for the orthorhombic (ICSD 97851) phase and
were missing in the cubic (ICSD 29073) and tetragonal (ICSD
1
09295) phases. The weak and unique spots help to distinguish
34,35
the orthorhombic from the cubic phase.
To further study the crystalline quality of the crystal, the
X-ray rocking curve of the (110) plane was measured, as
inserted in Figure 4. Evidently, the curve was a primarily
symmetric single peak without any split peaks, which meant
there was no twinning in the crystal. The full width at half-
maximum (FWHM) of the (110) peak of the rocking curve was
Therefore the HRTEM and SAED image analyses revealed
that the CsPbBr
3
single crystal had a structure matching with
an orthorhombic crystal phase (ICSD 97851, Pbnm (62), a =
8
.207 Å, b =8.255 Å, c = 11.759 Å), which was also reported by
0.16°. The relatively small FWHM of the crystal indicated a low
36
Zhang et al. for CsPbBr
37
31
nanowires , and by Abhishek
38
3
dislocation density and small residual stress in the crystal.
Swarnkar et al.
and Cottingham et al.
for CsPbBr
3
nanocuboids. The crystal was along the [110] zone axis and
the spots (002), (112), (111) and (110) were in the same plane
3.4 Electron diffraction analysis
(see Figure 6(a)). The vetorial angles among the diffraction
Considering the detection limit of XRD measurements spots (002), (112), (111) and (110) were 45.3°, 18.4° and 26.3°,
3
3
(
concentration > 5%), the purity of orthorhombic phase was still in respectively, as marked in Figure S7. Figure 6(b) showed the
doubt. Then high resolution TEM (HRTEM) technology was used to standard reciprocal lattice patterns of the orthorhombic (ICSD
analyze the micro-structure of the crystal. A typical HRTEM image of 97851) and the cubic (ICSD 29073) CsPbBr3 phases,
3
the CsPbBr single crystal observed at room temperature was respectively.
shown in Figure 5. A fast Fourier transform (FFT) image of the
HRTEM image was inset in Figure 5. The well-regulated arrayed
spots indicated the grown crystal had a perfect quality without
twinning, dislocation and stacking fault. The interplanar distances of
the orthogonal directions in HRTEM image were 0.582 nm and
Formatted: Font: 9 pt
Formatted: Font: 9 pt
Formatted: Font: 9 pt
0
.586 nm, respectively. Meanwhile, the interplanar distances of the
orthogonal directions in FFT image were calculated as 0.58 nm and
.595 nm, respectively. As the diffraction spots in FFT image were
0
of low resolution, it is hard to distinguish the cubic phase from the
orthorhombic one. Therefore more clear and detailed diffraction
spots were needed.
Figure 5 Typical HRTEM and FFT images of the CPB crystal,
inset: FFT image
A selected area electron diffraction (SAED) image of the
CsPbBr
lattice primitive vetors in the SAED image, with a length of 1.72
/nm (0.581 nm in direct lattice) and 1.70 1/nm (0.588 nm in
3
single crystal was shown in Figure 6. Two reciprocal
Figure 6 SAED pattern of the CsPbBr
3
crystal along the [110]
zone axis: (a) SAED pattern; (b) standard patterns for the
orthorhombic (ICSD 97851) and the cubic (ICSD 29073) phases
1
direct lattice), were rectangular. Other two reciprocal lattice
vetors, with a length of 1.92 1/nm (0.52 nm in direct lattice)
and 3.85 1/nm (0.26 nm in direct lattice) were measured from
In order to identify the crystallographic orientations and
domains of the crystal, the micro-structure crystallographic
4
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was further analyzed by electron backscatter diffraction (EBSD)
ARTICLE
crystallographic orientation map, and (d) Inverse pole figure
(IPF) map.
39,40
.
EBSD is a SEM based micro-structural crystallographic
characterization technique that is well established to
determine the crystallographic orientations, texture, defects, 3.5 Optical characterization
grain morphology and deformation of micro-structures. In this
The IR and UV-Vis-NIR transmittance spectra of the wafer were
shown in Figure 8(a) and (b), respectively. high IR
technique, the focused electron beam strikes the surface of
the crystal at a high angle (here, 70°). Backscatter diffraction
A
transmittance over 55% at the whole spectrum region was
observed. Since the IR average transmittance was mainly
affected by point defects, vacancies and impurities in the
electrons scattered from the surface form
a diffraction
pattern, called a Kikuchi pattern because of its prominent
Kikuchi bands. Before the EBSD measurement, wafer surfaces
were etched by argon ions for 30 min to smooth and clean the
wafer. Figure 7 showed the surface topography and micro-
crystal, the high IR average transmittance meant low defect
41,42
density in the crystal.
Two absorption peaks were found
-1
-1
clearly at about 1600 cm and 3500 cm in the transmittance
structural crystallographic orientation of a CsPbBr
wafer. As labelled in Figure 7(a), an area of 900 × 900 μm on
the CsPbBr wafer surface was selected for EBSD pattern
3
crystal
spectrum, and they were regarded as the infrared absorption
43,44
2
peaks of water vibrational modes in the atmosphere.
The
3
wafer also possessed a high transmittance in the UV-Vis-NIR
region, as shown in Figure 8(b). The good optical performance
indicated that the crystal had a high purity and a good crystal
quality. Furthermore, the absorption edge of the wafer was
measurement. The corresponding EBSD patterns (Kikuchi
patterns) were shown in Figure 7(b). Remarkably, these
patterns were similar, indicating the same crystallographic
orientation and no grain boundaries within the crystal. Figure
found to be at 550 nm in the UV-Vis-NIR transmittance
7, 10,45
7(c) showed the crystallographic orientation map with the
spectrum.
The band gap of the crystal was calculated to
standard colour orientation reference system inserted. The
crystallographic orientation map was formed by the numbers
of Kikuchi patterns through statistical analysis. A specific color
represented a specific orientation. Clearly, the map showed
nearly the same color, indicating the crystal had a single
orientation. And this single orientation was confirmed by the
inverse pole figure (IPF) map as shown in Figure 7(d). The
concentrated point in the inverse pole figure (IPF) indicated
the crystal was a perfect single oriented crystal. More
information about characterization of EBSD pattern on various
regions from the edge to center of the wafer was described in
supporting information (Figure S8-9).
be approximately 2.252 eV according to the equation:
h⋅c
E
=
,
g
λ
e
e
where the λ was the absorption edge wavelength. The result
was in line with the data reported in Ref 7.
Figure 8 (a) IR transmittance spectrum and (b) UV-Vis-NIR
3
transmittance spectrum of a CsPbBr wafer
4
. Conclusions
In this paper, CsPbBr
3
polycrystalline powders were
synthesized by a chemical co-precipitation method. CsPbBr
3
single crystal of 8 mm diameter and 60 mm overall length was
successfully grown by a facile melt-method (EDG method). The
phase transitions and micro-structure were systematic
investigated by scientific instruments and equipment. The
temperature-dependent powder XRD patterns indicated
3
CsPbBr had two successive phase transitions at around 88 °C
and 130 °C, corresponding to the crystal structure
transforming from room temperature orthorhombic (62, Pbnm,
equal to Pnma) to tetragonal (99, P4/mbm) and then to cubic
(221, Pm-3m), respectively. The XRD patterns showed that the
crystal was a single crystal preferentially orienting in the (110)
direction. The X-ray rocking curve of (110) plane showed a
sharp peak with a FWHM of 0.16°, indicating a low dislocation
Figure 7 Microstructure and crystallographic orientation map
3
of a CsPbBr crystal (a) SEM image, (b) Kikuchi patterns, (c)
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density and residual stress in the crystal. HRTEM image 14 Y. Rakita, N. Kedem, S. Gupta, A. Sadhanala, V. Kalchenko, M.
L. Böhm, M. Kulbak, R. H. Friend, D. Cahen and G. Hodes,
showed the high quality of the crystal without twinning,
Cryst. Growth Des, 2016, 16(10), 5717−5725.
5 G. P. Li, H. Wang, Z. F. Zhu, Y. J. Chang, T. Zhang, Z. H. Song
dislocation and stacking fault. FFT and SAED image indicated
the crystal had a pure room-temperature orthorhombic phase.
1
and Y. Jiang, Chem. Commun., 2016, 52(75), 11296-11299.
3
The results of EBSD confirmed that CsPbBr crystal was a 16 P. Ramasamy, D. H. Lim, B. Kim, S. H. Lee, M. S. Lee and J. S.
perfect single crystal along single orientation with no grain
boundaries. The crystal showed good transparency with a high
IR and UV-Vis-NIR transmittance. The above results proved
that the EDG method was a feasible and effective method to
Lee, Chem. Commun., 2016, 52(10), 2067-2070.
7 J. De Roo, M. Ibanez, P. Geiregat, G. Nedelcu, W. Walravens,
J. Maes, J. C. Martins, I. Van Driessche, M. V. Kovalenko and
Z. Hens, ACS Nano, 2016, 10(2), 2071-2081.
8 Y. Wang, X. Li, X. Zhao, L. Xiao, H. Zeng and H. Sun, Nano Lett.,
2016, 16(1), 448-453.
1
1
1
2
3
grow perfect CsPbBr single crystals.
9 S. Seth, N. Mondal, S. Patra and A. Samanta, J. Phys. Chem.
Lett., 2016, 7(2), 266-271.
0 Q. A. Akkerman, S. G. Motti, A. R. Srimath Kandada, E.
Mosconi, V. D'Innocenzo, G. Bertoni, S. Marras, B. A. Kamino,
L. De Miranda, F. Angelis, A. Petrozza, M. Prato and L.
Manna, J. Am. Chem. Soc., 2016, 138(3), 1010-1016.
1 I. Chung, B. Lee, J. He, R. P. Chang and M. G. Kanatzidis,
Nature, 2012, 485(7399), 486-489.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China under Grant Nos. 11575065 and
2
2
1
1275078. The authors acknowledge the assistance of the
Analytical and Testing Center (ATC) and State Key Laboratory
of Material Processing and Die Mold Technology of
2 L-y. Huang and W. R. L. Lambrecht, Phys. Rev. B., 2016,
93(19), 195211.
&
Huazhong University of Science and Technology (HUST). The 23 M. Kulbak, D. Cahen and G. Hodes, J. Phys. Chem. Lett., 2015,
6
(13), 2452-2456.
authors also wish to express their hearty thanks to School of
Physics and Technology of Wuhan University for X-ray rocking
curve testing.
2
4 M. I. Saidaminov, A. L. Abdelhady, G. Maculan and, O. M.
Bakr, Chem. Commun., 2015, 51(100), 17658-17661.
5 C. K. Møller, Nature, 1958, 182(4637),1436–1436.
6 J. X. Ding, S. j. Du, Z. Y. Zuo, Y. G. Zhao, H. Z. Cui and X. Y.
Zhan, J. Phys. Chem. C, 2017, 121(9), 4917–4923.
2
2
Notes and references
27 D. X. Zhou, L. Quan, X. Chen, S. Yu, Z. Z. Zheng and S. P. Gong,
J cryst. Growth, 2009, 311(8), 2524-2529.
1
2
3
4
5
C. Yi, J. Luo, S. Meloni, A. Boziki, N. Ashari-Astani, C. Grätzel,
S. M. Zakeeruddin, U. Röthlisberger and M. Grätzel, Energy
Environ. Sci., 2016, 9(2), 656–662.
M. Kulbak, S. Gupta, N. Kedem, I. Levine, T. Bendikov, G.
Hodes and D. Cahen, J. Phys. Chem. Lett., 2016, 7(1), 167-
172.
S. W. Eaton, M. Lai, N. A. Gibson, A. B. Wong, L. Dou, J. Ma, L.
W. Wang, S. R. Leone and P. Yang, PNAS, 2016, 113(8), 1993-
2
2
3
3
8 M. Rodová, J. Brožek, K. Knížek and K. Nitsch, J. Therm. Anal.
Calorim., 2003, 71(2), 667−673.
9 D. X. Zhou, L. Quan, X. Y. Chen, S. J. Yu, C. Wang, Z. Z. Zheng,
and S. P. Gong, Cryst. Growth Des., 2009, 9(10), 4296-4300.
0 H. Huang, M. Liu, J. Li, L. Luo, J. Zhao, Z. Luo, X. Wang, Z. Ye,
H. He and J. Zeng, Nanoscale. 2017, 9(1), 104-108.
1 M. Imran, F. Di Stasio, Z. Dang, C. Canale, A. H. Khan,J.
Shamsi, R. Brescia, M. Prato and L. Manna, Chem. Mater.,
1
Y. Xu, Q. Chen, C. Zhang, R. Wang, H. Wu, X. Zhang, G. Xing,
998.
2016, 28(18), 6450−6454.
2 J. Zhao, M. Liu, L. Fang, S. Jiang, J. Zhou, H. Ding, H. Huang, W.
Wen, Z. Luo, Q. Zhang, X. Wang and C. Gao, J Phys Chem Lett.
3
W. W. Yu, X. Wang, Y. Zhang and M. Xiao, J. Am. Chem. Soc.,
2
016, 138(11), 3761-3768.
2
017, 8(13), 3115-3121.
3 L. Luo, W. Jie, Y. Xu, Y. He, L. Xu and L. Fu, CrystEngComm,
014, 16(23), 5073-5079.
4 Z. Dang, R. Brescia, Q. Akkerman, J. Shamsi, M. Prato and L.
Manna, European Microscopy Congress 2016: Proceedings,
H. Cho, S. H. Jeong, M. H. Park, Y. H. Kim,C. Wolf, C. L. Lee, A.
Sadhanala, N. S. Myoung, S. Yoo, S. H. Im, R. H. Friend and T.
W. Lee, Science, 2015, 350(6265), 1222-1225.
3
3
2
6
7
X. Zhang, H. Lin, H. Huang, C. Reckmeier, Y. Zhang, W. C.
Choy and A. L.Rogach, Nano Lett., 2016, 16(2), 1415-1420.
C. C. Stoumpos, C. D. Malliakas, J. A. Peters, Z. Liu, M.
Sebastian, J. Im, T. C. Chasapis, A. C. Wibowo, D. Y. Chung, A.
J. Freeman, B. W. Wessels and M. G.Kanatzidis, Cryst.
Growth Des., 2013, 13(7), 2722-2727.
2
016, 530–531.
5 J. Shamsi, Z. Dang, P. Bianchini, C. Canale, F. D. Stasio, R.
3
Brescia, M. Prato and L. Manna, J. Am. Chem. Soc, 2016,
1
38(23), 7240
6 D. Zhang, S. W. Eaton, Y. Yu, L. Dou and P. Yang, J. Am. Chem.
Soc., 2015, 137(29), 9230 9233.
7 A. Swarnkar, R. Chulliyil, V. K. Ravi, M. Irfanullah, A.
Chowdhury and A. Nag, Angew. Chem., Int. Ed, 2015, 54(51)
5424-15428.
8 P. Cottingham and R. L. Brutchey, Chem. Commun, 2016,
2(30), 5246-5249.
9 P. Khoram, S. Brittman,W. I. Dzik, J. N. H. Reek and E. C.
Garnett, J. Phys. Chem. C., 2016, 120(12), 6475-6481.
0 S. K. Sundaram, C. H. Henager, D. J. Edwards, A. L. Schemer-
Kohrn, M. Bliss and B. R. Riley, Journal of Crystal
Growth, 2011, 329(1), 12-19.
−
7243.
3
3
8
9
L. Lv, Y. Xu, H. Fang, W. Luo, F. Xu, L. Liu, B. Wang, X. Zhang,
D. Yang, W. Hu and A. Dong, Nanoscale., 2016, 8(28), 13589-
13596.
L. Gao, K. Zeng, J. Guo, C. Ge, J. Du, Y. Zhao, C. Chen, H.
Deng, Y. He, H. Song, G. Niu and J. Tang, Nano Lett., 2016,
–
,
1
3
3
4
1
6(12), 7446-7454.
0 D. N. Dirin, I. Cherniukh, S. Yakunin, Y. Shynkarenko and M. V.
Kovalenko, Chem. Mater, 2016, 28(23), 8470 8474.
1 X. Zhang, B. Xu, W. Wang, S. Liu, Y. Zheng, S. Chen, K. Wang
and X. W. Sun, ACS Appl. Mater. Interfaces, 2017, 9(5), 4926-
5
1
1
−
4
931.
2 K. A. Bush, C. D. Bailie, Y. C. Andrea, R. Bowring, W. Wang, W.
Ma, T. Leijtens, F. Moghadam and M. D. Mcgehee, Adv.
1
1
4
4
1 J. Min, X. Liang, J. Chen, D. Wang, H. Li and J.
Zhang, Vacuum, 2012, 86(7), 1003-1006.
2 S. Yu, D. Zhou, S. Gong, Z. Zheng, Y. Hu, C. Wang and L. Quan,
Nuclear Instruments and Methods in Physics Research
Mater. 2016, 28(20), 3937
3 X. He, Y. Qiu and S. Yang, Advanced materials, 2017, 29(32)
700775.
−3943.
,
1
6
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Section A: Accelerators, Spectrometers, Detectors and
Associated Equipment, 2009, 602(2), 484-488.
3 K. Ataka, T. Yotsuyanagi and M. Osawa, J. Phys. Chem., 1996,
4
4
4
1
00(25), 10664-10672.
4 M. Osawa, M. Tsushima, H. Mogami, G. Samjeske and A.
Yamakata, J. Phys. Chem. C, 2008, 112(11), 4248-4256.
5 M. I. Saidaminov, M. A. Haque, J. Almutlaq, S. Sarmah, X. H.
Miao, R. Begum, A. A. Zhumekenov, I. Dursun, N. Cho, B.
Murali, O. F. Mohammed, T. Wu and O. M. Bakr, Adv. Opt.
Mater., 2017, 5(2), 1600704.
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