j m a t e r r e s t e c h n o l .

2 0 2 0;9(4):7149–7157

Available online at www.sciencedirect.com

www.jmrt.com.br

Original Article

The impact of Cs3 Bi2 Cl9 single crystal growth

modality on its symmetry and morphology

Naveen Kumar Tailor, Soumitra Satapathi ∗

Department of Physics, Indian Institute of Technology Roorkee, Roorkee, Haridwar, Uttarakhand, 247667, India

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

Article history: Perovskite single crystals have the potential to design a new path in optoelectronics. Due to
Received 15 February 2020 the toxicity and stability issue of lead halide perovskites, the substitution of lead is a chal-
Accepted 29 April 2020 lenge. Here, we have demonstrated two different single crystal growth mechanisms namely
Available online 8 June 2020 slow cooling and anti-solvent vapor diffusion method for lead-free Cs3 Bi2 Cl9 perovskite
single crystal and exhibited how these different growth methods affect the symmetry
Keywords: parameters and morphology evolution of single crystal structure. The synthesis, crystal
Perovskite single crystal growth, and detailed structural and thermal characterization have been carried out by
Glide plane optical and electron microscopy, elemental mapping, single crystal X-ray diffraction, and
Screw axes thermogravimetric analysis. Our study shows that contrary to the conventional expectation
Space group the crystal symmetry, Patterson vector, and Sheldrick’s criterion is different for the same
Reciprocal lattice. single crystal stoichiometry with two different crystal growth methods. The calculated met-
ric tensor in real and reciprocal space is different for two different growth mechanisms. Our
study opens up a personalized design strategy for choosing a suitable single crystal fabrica-
tion route among various available strategies for specific non-linear optical or optoelectronic
applications.
© 2020 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

nonlinear optical properties, they are the best candidate

1. Introduction for applications in multiphoton spectroscopy, infrared pho-
todetector, optical frequency converters optoelectronic and
The hybrid inorganic-organic perovskites are in limelight
non-linear optical applications such as light-emitting diodes,
due to its superior photophysical properties like direct
lasers, photo-detectors also as in X-ray and gamma-ray (␥-ray)
bandgap, large absorption coefficient, strong photolumines-
detectors [3–6]. The perovskite devices based on polycrys-
cence quantum yield, and higher charge-carrier mobility [1,2].
talline materials have low performance due to the existence
Since organic-inorganic halide perovskites are cost-effective,
of many voids, grains boundaries, and surface defect states
solution-processable, abundant in nature and have unique
inside the active perovskites layer. Consequently, single crys-
tals perovskites have been developed largely because of the
low trap density and no grain boundaries in them [7,8]. Y.
∗
Corresponding author. Liu et al. reported growth and optical properties of two-
E-mail: ssphf.fph@iitr.ac.in (S. Satapathi). inch sized perovskites single crystals of CH3 NH3 PbX3 (X = Cl,
https://doi.org/10.1016/j.jmrt.2020.04.097
2238-7854/© 2020 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).
7150 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157
Br, I) [4]. Therefore, large-sized perovskites single-crystalline
materials have the potential to fabricate viable large-scale
optoelectronic devices and might replace the single crystalline
silicon-based device.
Despite lead halide perovskites have proved to be excel-
lent material in the optoelectronics community, yet several
optimizations are still required before successful commercial-
ization of this technology because lead perovskites contain
the toxic lead, and they easily decompose into constituents’
materials in the presence of humidity, heat, and light [9,10].
That’s why the substitution of Pb2+ by isoelectronic ions
Ge and Sn (same group IV metals as that of lead) with
the comparable 6s2 6p0 electronic configuration of Pb2+ is
considered as a viable approach but many short-comings
like chemical instability, poor performance, etc. limit the
further device potential of these divalent metal cations
[9,11–15]. Transition metals (e.g., Mn) with compelling ultravi-
olet photo-responses are likewise examined as an alternative
to lead perovskites architectures. However, in the case of Mn-
based perovskites, spectral response lies in a narrow band
region (330–360 nm) and devices response speed is extremely
slow (>100 ms) [16]. These limits hinder the development of
Mn-based perovskite for successful commercial uses. There-
fore, the substitution of Pb2+ into perovskites phases with
non-lead metal cation is often a complex and needs opti-
mization of various parameters for varied optoelectronic
applications [9,10,17,18].
In such a manner, although the VA group components par-
ticularly nontoxic bismuth (Bi3+ ) has turned into a fascinating
candidate to interchange Pb2+ , it has a distinctive valence state
from Pb2+ due to the similarities in properties to that of Pb2+
[17,19–22]. Bi3+ has 6s2 lone pair same as Pb2+ and effective
ionic radius and electro-negativity of Bi3+ are close to Pb2+ ions.
Therefore, Bi3+ based mostly hybrid perovskites are expected
to exhibit semiconducting behaviors comparable with those
of lead-based hybrid perovskites [11,17,21–29]. On an extra
note, the possible theme of work nontoxic components in
lead-based perovskites with Bi3+ has opened up new potential
outcomes to grow eco-friendly optoelectronic devices. Zhuge
et al. reported lead free bismuth-based perovskites for X-ray
detection [27]. B. W. Park et al. demonstrated bismuth-based
perovskites for solar cell applications [17]. It has been also
reported by H. Wu et al. that new structures analogous to
perovskite such as K3 B6 O10 Cl can have high performances in
non-linear optical response [30].
In our present study, we have reported the fabrication of
cesium bismuth chloride lead-free perovskite single crystal
by two different methods in ambient conditions and stud-
ied their growth mechanism, kinetics, structural and thermal
properties. It was observed that the growth mechanism affects
the crystal structure and symmetry parameters due to their
different thermodynamic conditions [31,32]. The synthesis,
growth of the crystal, and detailed structural characterization
have been carried out by optical microscopy, field scanning
electron microscope (FESEM), energy dispersive X-ray analy-
sis (EDXA), elemental mapping, single crystal X-ray diffraction
(SCXRD). Transmission microscope and FESEM images have
shown clearly the single crystalline morphology and EDXA
has shown the stoichiometry matching by means of elemental
analysis of the crystal. The synthesized single crystal structure
and reciprocal lattice structure have been investigated. More-
over, symmetry operators in the crystal, hkl values, and linear
absorption coefficient of the synthesized single crystals have
been investigated in detail.
2. Experimental
2.1. Materials
Cesium chloride 99% (CsCl) and bismuth chloride 98% (BiCl3 )
were purchased from Avra Synthesis Pvt. Ltd. Hyderabad, India
and used without any further purification. Deionized water
(DI water) and hydrochloric acid (HCl) was used as a solvent.
Methanol was used as an antisolvent.
2.2. Synthesis of Cs3 Bi2 Cl9
Cesium chloride solution was prepared in DI water. 3 mol of
cesium chloride is dissolved in 10 ml of DI water under contin-
uous magnetic stirring at 120 ◦ C until no powder is observed.
2 mol of bismuth chloride is dissolved in 8 ml DI water and
2 ml HCl solution is prepared under continuous magnetic stir-
ring at 120 ◦ C until a homogeneous solution is formed. For the
synthesis of Cs3 Bi2 Cl9 crystals, cesium chloride and bismuth
chloride solution were mixed in a well-cleaned glass vial and
stirred at 120 ◦ C. The reaction in the synthesis of Cs3 Bi2 Cl9 can
be written using the following Eq. (1).
3CsCl + 2BiCl3 → Cs3 Bi2 Cl9 (1)
2.3. Growth of single crystal
Thermal fluctuations in the supersaturated solution give rise
to the formation of small clusters of molecules known as
‘embryos’ [33]. These embryos grow into stable nuclei due to
the change in free energy. Once nucleation has been achieved,
crystal growth dominates and is the process, which leads to
the evolution of crystal form of defined size and shape. Crys-
tallization starts with nucleation and control of nucleation
is crucial for the control of the crystal size and perfection.
Due to its crucial place at the start of the crystallization pro-
cess, the nucleation of crystals determines many properties of
the emerging crystalline phase. If fast nucleation takes place
then many small size crystals form simultaneously and if slow
nucleation takes place then fewer crystals nucleate at a time,
supersaturation in the solution drops slowly and large size
crystals grow [34]. Fig. 1 shows the schematic diagram of the
relation between nucleation and crystal size. The growth of
single crystal depends on solution concentration also. When
concentration is very close to the critical point of nucleation
then a single crystal can be grown. At this particular con-
centration, the molecule starts aggregating, which keeps on
forming and falling apart within the solution, begin to accom-
plish the critical size and convert into nuclei for the growth of
crystals. If the concentration is higher than the critical point of
nucleation then a huge number of nuclei will be generated and
consequently a crystalline powder will be formed. But if the
concentration is very low than the critical point of nucleation,
then no such nuclei will be generated.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157 7151

Fig. 1 – Schematic diagram of the relation between nucleation rate and crystal size.

Strategies used to grow single crystals are classified by seed placed in solution so homogeneous nucleation occurs
growth environment and include solid growth, liquid growth, and single crystals grew in this process. The nucleation rate
and vapor growth. To date, all reported perovskite crystals and the crystal growth process depend on controlling the
have been prepared with the liquid growth method [26,35–39]. temperature-cooling rate [34]. After reaching the room tem-
As discussed, the driving force for crystallization, supersatu- perature, the solution was left in the ambient condition for a
ration is generated by cooling of the solution and by adding few days.
antisolvent [40]. Crystal properties can be determined by con-
trol of supersaturation. Therefore to grow the perovskite single
2.3.2. Antisolvent vapor diffusion (AVD) method
crystals, we have used two strategies to modulate solubil-
In a different methodology, the supersaturation can be created
ity: slow cooling (SC), and antisolvent vapor diffusion (AVD)
by adding an antisolvent, that is, a solvent with significantly
method.
lower solubility. In this approach, the solubility of the required
product will be drastically decreased and precipitation will
2.3.1. Slow cooling (SC) method
occur (Fig. 2b) [42]. The efficacy of the approach relies upon
If the concentration of a compound surpasses its solubility
several parameters, for example, which type of antisolvent
then precipitation in a solution occurs rapidly, e.g., from a
being utilized, the volume ratio between solvent and anti-
supersaturated solution. Cooling crystallization is employed
solvent, the specific time of the diffusion of the antisolvent,
if the solubility changes significantly with temperature [40].
the diffusion rate, and so on. The cesium bismuth chloride
Generally, when more heat is added to a system then sol-
solution was taken in a well-cleaned glass vial. Antisolvent
ubility increases but this is not the general case for all
was taken in a beaker and glass vial with a precursor solu-
perovskites-in-solvent systems. If the solution-cooling rate is
tion is taken in this anti-solvent bath [43]. We produced a
faster than the rate of precipitation then the solution will
vapor of anti-solvent by heating the solution and the beaker
become supersaturated until the solute precipitates to the
was covered tightly. Vapor diffuses slowly into the perovskite
temperature-determined saturation point. The solubility of
precursor solution. We put this beaker in ambient conditions.
perovskites materials in an HX-based solvent use of HCl, HBr,
Solubility decreases with increasing the quantity of antisol-
and HI as the solvent will decrease with the cooling of solution
vent. At the critical point of concentration, nucleation starts
temperature. According to this principle, the cooling of the
and crystal produces.
perovskite precursor solution can produce single-crystalline
perovskites. Crystal size depends on the solution-cooling rate.
If the cooling rate is faster then fast nucleation takes place
and supersaturation drops rapidly and small size crystals pro- 3. Characterizations
duce and if the cooling rate is slower then slow nucleation
takes place and large size crystal grows (Fig. 1). Poglitsch and 3.1. Microscopy
Weber have reported this technique the first time more than
22 years ago [41]. We used this slow cooling method for grow- A transmission microscope EVOS FLc was used for the surface
ing Cs3 Bi2 Cl9 perovskite single crystal (Fig. 2a). In this method, image of the crystals. FESEM images taken by FESEM QUANTA
the precursor solution was cooled from 120 ◦ C to room tem- 200 FEG under electron excitation energy of 20 keV using elec-
perature with a cooling rate of 1 ◦ C per hour. There was no tron transmission detector at working distance 9.5 mm.
7152 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157
Fig. 2 – Schematic diagram of (a) SC method and (b) AVD method.
3.2. Single crystal X-ray diffraction measurement
SCXRD data-sets of cesium bismuth chloride single crystal
were collected using a Bruker Kappa APEX-II diffractometer
equipped with a charge-coupled device detector using Mo-K␣
radiation ( = 0.7107 Å). Data acquisition and processing were
performed using the APEX2 software. The structure was ana-
lyzed by and refined using the WinGX software package and
Mercury software.
3.3. Thermal analysis
Differential thermal analysis (DTA) and thermogravimetric
(TG) analysis were performed using an instrument EXSTAR
TG/DTA 6300. Sample (10.51 mg) was placed with refer-
ence alumina powder (10.5 mg) under nitrogen gas flow
(200 ml/min). The sample was heated at a rate of 10 ◦ C/min
in the temperature range from 34 ◦ C to 900 ◦ C.
4. Results and discussion
4.1. Crystal growth mechanism and morphology
Single crystals of cesium bismuth chloride Cs3 Bi2 Cl9 were
grown by the above described SC and AVD method. In the
SC method, cesium chloride and bismuth chloride are first
dissolved in DI water and HCl solution at 120 ◦ C and then grad-
ually cooled to room temperature with a cooling rate of 1 ◦ C per
hour. In the AVD method, the solution is placed in the presence
of antisolvent vapor. Antisolvent vapor diffuses slowly in pre-
cursor solution and crystals growth takes place. The formation
of a perovskite single crystal is a first-order phase transition
[34]. The change in free energy is written as:
G = H − TS,
where H is changed in enthalpy between perovskite solu-
tion and crystal phase, T is temperature and S is entropy
difference of solution and crystal phase. In the equilibrium
condition, change in free energy is zero, which results in S =
H/Te . Entropy change in slow cooling method is due to the
cooling of the solution because the temperature is changing
during this process. The rate of change in entropy and crystal
growth process depends on the temperature cooling rate. In
the AVD method, the entropy change is due to the diffusion of
antisolvent vapor in the precursor solution. The driving force
of crystallization is the change in chemical potential between
standing and equilibrium states of expressed as:
c c c
 = ln = −1= = S − 1 = , (3)
c∗ c∗ c∗
where  is the change in chemical potential, c is the
standing concentration of perovskite solution and c* the equi-
librium saturation concentration of perovskite solution, S is
the supersaturation ratio and  is the relative or absolute
supersaturation [44]. As we discussed above that solubility for
perovskite materials changes with the temperature so the con-
centration of the solution also changes with the temperature.
In the SC method, chemical potential changes due to change
in temperature that drives for the crystallization. The crystal
growth starts around 70 ◦ C and the solution further cools to the
room temperature and the size of crystal increases. Further,
solubility reduces with the antisolvent diffusion also. Hence
the concentration of solution also changes with antisolvent. In
the AVD method, chemical potential changes with the antisol-
vent diffusion that drives for crystallization. For this lead-free
material, we have calculated the Goldschmidt tolerance factor
and its value were found 0.86, which belongs to the perovskite
structure.
FESEM image of Cs3 Bi2 Cl9 perovskite single crystal is
shown in Fig. 3. Images show the single crystalline structure
of crystals. Fig. 3a shows the crystal structure of a perovskite
(2) single crystal grown by the SC method. This image of the
crystal is the same as an orthorhombic structure that is
calculated by SCXRD data. Fig. 3b shows the crystal structure
of a perovskite single crystal grown by AVD method and
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157
Fig. 3 – (a) FESEM image of Cs3 Bi2 Cl9 single crystal produced by the slow cooling method; and (b) FESEM image of Cs3 Bi2 Cl9
perovskite single crystal produced by antisolvent vapor diffusion method.
crystal forms trigonal structure. The difference in structure
may be a result of the different thermodynamic conditions.
The FESEM image shows that the well-isolated single crystals.
The corresponding microscope image depicts the shape and
surface of the crystal (Appendix BSupplementary information
Figs. S1 and S2). The EDXA spectrum shows the elemental
mapping in the crystal (Supplementary information Figs. S3
and S4). The atomic and the weight proportion of elements
are tabulated in (Supplementary information Table S1 and S2).
4.2. Single crystal X-ray diffraction
X-ray diffraction is a powerful technique to characterize the
quality of crystalline materials. Fig. 4 shows a single crystal
X-ray diffraction of small Cs3 Bi2 Cl9 single crystal produced by
the SC method (Fig. 4a) and AVD method (Fig. 4b). XRD pat-
tern shows that all of the synthesized samples have in fact a
crystalline nature with a characteristic structure.
Single crystal X-ray diffraction data analysis was done
by open-source Mercury and WinGx software and the cal-
culated parameters are shown in Table 1 [8,45]. The very
sharp and well defined XRD peaks suggest that the crystals
are highly oriented with the planes parallel to the substrate.
XRD crystallographic analysis reveals that the crystal struc-
ture of Cs3 Bi2 Cl9 lead-free perovskite crystal belongs to the
orthorhombic system for SC crystal and trigonal system for
AVD method at room temperature. For SC crystals, XRD shows
main diffraction peaks at 8.2, 14.283, 16.502 and 23.40◦ corre-
sponding to the (101), (300), (202) and (401) of lattice planes of
the orthorhombic structure with space group Pnma at room
temperature. For AVD crystal, XRD shows main diffraction
peaks at 8.3, 11.659, 14.283 and 23.46◦ corresponding to the
(101), (2−10), (201) and (4−20) of lattice planes of the trigonal
structure with space group P−31c at room temperature. Some
more parameters related to the structure of crystal such as
reciprocal lattice parameter, structure factor, resolution, and
hkl value was calculated and tabulated in Table 1.
We have observed different crystal structures by both
methods. Crystal produced by an SC method belongs to the
orthorhombic crystal system with the space group Pnma at
room temperature [46]. Here “P” indicates to the primitive
7153
cell, “n” indicates to n-glide plane (reflection + translation)
perpendicular to the x-axis, “m” indicates to a mirror plane
perpendicular to the y-axis and “a” indicates to an a-glide
plane perpendicular to the z-axis. This orthorhombic space
group possesses three mutually perpendicular two-one screw
axis (rotation + translation). Crystal produced by the AVD
method belongs to the trigonal crystal system with the space
group P−31c at room temperature. The density of crystal and
linear absorption coefficient are the approximate same for
both types of crystals.
It was observed from E-statistics that cesium bismuth chlo-
ride perovskite single crystal produced by SC method and AVD
method is centrosymmetric. Sheldrick’s [E2 -1] criterion was
calculated for both SC and AVD crystals and it was found 0.950
and 1.018 respectively. The ideal value for centrosymmetric is
0.968. The E-statistics strongly indicate that both structures
are centrosymmetric with 85.7% and 83.0% probability. The
experimental data curve matches well with the theoretical
data curve for the centric curve (Supplementary information
Fig. S5). There is no unique axis and no polarity observed in
the crystal. For SC crystal, a total of 25,706 reflections read, of
which 1042 rejected and 2971 unique reflections read, of which
2360 observed. It was observed 2374 reflections with nega-
tive/zero intensity. Here 1503 reflections were observed with
sin(␪)/␭ < 0.2. For AVD crystal total 18,314 reflections read, of
which 1170 rejected and 2915 unique reflections read, of which
1844 observed. It was observed 3540 reflections with nega-
tive/zero intensity. Here 826 reflections were observed with
sin(␪)/␭ < 0.2. The value of Rint is 0.0528 for SC crystal and 0.1387
for AVD crystal. The value of Rint is a measure of the closeness
of agreement in intensities for supposedly equivalent reflec-
tions. Rint values for merging under all Laue symmetries is
calculated with the formula:
 
|F2 (obs) − F2 (mean)|
R(int ) =  . (4)
[F2 (obs)]
In the SC crystal, the highest diffraction symmetry with a
reasonable value of Rint (i.e. <0.1) is mmm which corresponds
to the Laue group while in AVD crystal it is −3(hex) and the
7154 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157

Fig. 4 – The single crystal X-ray diffraction pattern (SCXRD) pattern of Cs3 Bi2 Cl9 single crystal grown by (a) slow cooling
method (SC) and (b) antisolvent vapor diffusion method (AVD).

Table 1 – Structure parameters for Cs3 Bi2 Cl9 single crystal produced by the SC method and AVD method.
Parameters SC crystal AVD crystal

Crystal system Orthorhombic Trigonal

Space group Pnma P−31c
a/Å 18.5894 15.1873
b/Å 7.6364 15.1873
c/Å 13.2033 18.015
˛/◦ 90 90
ˇ/◦ 90 90
/◦ 90 120
Volume/Å3 1874.29 3718.45
a* 0.0537941 0.0760307
b* 0.1309517 0.0760307
c* 0.0757386 0.0537193
˛* 90 90.00
ˇ* 90 90.00
* 90 120.00
Reciprocal cell volume 0.0005335 0.0002689
Density/g cm−3 6.02 6.018
Linear abs. coeff. (mm−1 ) 51.34 51.76
Lattice type P-primitive P-primitive
F000 2788.98 5580.0
Patterson vector 37.5 18.7
F2̂ −2.4 ≤ F2̂ ≤ 1000 −10.3 ≤ F2̂ ≤ 1000
F 0 ≤ F ≤ 31.62 0 ≤ F ≤ 31.62
Sin()/ 0.027 ≤ (sin()/) ≤0.723 0.027 ≤ (sin()/) ≤ 0.672
Theta (◦ ) 1.10 ≤  ≤ 30.96 1.09 ≤  ≤ 28.53
Resolution (A) 18.59 ≤ R ≤ 0.69 18.62 ≤ R ≤ 0.74
H index −25 ≤ H ≤ 26 −20 ≤ H ≤ 19
K index −10 ≤ K ≤ 8 −20 ≤ K ≤ 17
L index −19 ≤ L ≤ 16 −24 ≤ L ≤ 24

highest diffraction symmetry is compatible with the cell met-
rics.
4.3. Reciprocal lattice pattern
Fig. 5 shows the single crystal diffraction pattern of our syn-
thesized cesium bismuth chloride perovskite single crystal in
reciprocal lattice space. Here we constructed a diffraction pat-
tern for hkl reciprocal lattice planes of SC crystal (Fig. 5a) and
AVD crystal (Fig. 5b) [46]. Friedel pairs are also shown in the
reciprocal pattern. These controlled and large spatial arrange-
ments of the spots show the high quality of our fabricated
single crystal. There is no overlapped mapping of spots in
diffraction pattern which indicates the single crystal quality of
these lead-free perovskite crystals. Here, the spots in different
colors show the intensity of particular hk0 planes. For exam-
ple, the large spots in white color show the preferential growth
of particular hkl planes in the crystal where the small spots
in different colors show less growth of planes in the crystal.
In the reciprocal lattice for hkl values, no reflection condition
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157 7155

Fig. 5 – Single crystal X-ray diffraction patterns of cesium bismuth chloride: (a) hk0 reciprocal lattice plane reconstructed
from raw single-crystal diffraction data at room temperature for SC crystal and (b) hk0 reciprocal lattice plane reconstructed
from raw single-crystal diffraction data at room temperature for AVD crystal.

Table 2 – Real and reciprocal space metric tensor.

SC AVD

Real Metric tensor 345.566 0.0000 0.0000 230.654 −115.327 0.0000

0.0000 58.315 0.0000 −115.327 230.654 0.0000
0.0000 0.0000 174.327 0.0000 0.0000 346.529

Reciprocal Metric 0.002894 0.0000 0.0000 0.005781 0.002890 0.0000

tensor 0.0000 0.017148 0.0000 0.002890 0.005781 0.0000
0.0000 0.0000 0.005736 0.0000 0.0000 0.002886

is obeyed that corresponds to a primitive cell lattice. SC crys-
tal has space group Pnma which has eight different types of
symmetry in which three two-fold screw axis, two glide planes
perpendicular to x and z-axis, one mirror plane perpendicular
to y-axis and one inversion center and one identity element.
AVD crystal has space group P−31c that have twelve differ-
ent types of symmetry in which two three-fold rotation axis,
three two-fold rotation axis, three glide planes, two three-fold
rotoinversion axis and one inversion center (Details are given
in Supplementary Information). We observed that symmetry
parameters are different for both crystals grown by both meth-
ods. The diffraction pattern in the reciprocal space of crystals
shows the symmetry in the hk0 plane.
4.4. Metric Tensor
The crystals’ symmetry and their anisotropic physical prop-
erties are firmly related to crystal lattices. A lattice can be
carried into itself by suitable translations of the basic periods
of the crystal lattice [47]. The metrical properties of a 3D lat-
tice with an arbitrary primitive basis a, b, and c are comprised
in the metric tensor G represented by the symmetric positive-
definite 3 × 3 matrix [48]. The real and reciprocal space metric
tensor matrixes are of fundamental importance in crystallo-
graphic computations and transformations of basis vectors
and coordinates from direct to reciprocal space and vice versa.
Here we constructed a second-order tensor G, which reflects
the basic symmetry relations of the considered crystal class.
Real and reciprocal metric tensor was calculated and values
are tabulated in Table 2. We observed that metric tensor values
are different for single crystals grown by both methods.
4.5. Thermal Stability Analysis
The Thermal Gravetic Analysis (TGA) and differential tem-
perature analysis (DTA) were performed to investigate the
thermal stability of the perovskite single crystals grown by the
above-described methods and shown in Fig. 6. The TGA curve
shows that Cs3 Bi2 Cl9 perovskite crystals are thermally stable
up to 200 ◦ C when it then starts losing weight.
The perovskite crystals produced by the AVD method are
more thermally stable in temperature range 200 to 650 ◦ C.
From 200 ◦ C to 800 ◦ C, the compound continues to lose weight
until about 10% is left. The degradation behavior in perovskite
crystals produced by the above described both methods is
almost the same. Beyond the temperature of 670 ◦ C, perovskite
materials have been degraded rapidly. For comparison, TG
measurements of the precursor materials CsCl (Supple-
mentary information Fig. S6) and BiCl3 (Supplementary
information Fig. (S7) are also presented. The component BiCl3
undergo 80% weight loss in a single step, with the onset tem-
perature at 200 ◦ C and component CsCl undergo 100% weight
loss in a single step, with the onset temperature at 640 ◦ C,
suggesting clear sublimation without complex decomposition
7156 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):7149–7157
Fig. 6 – (a) TGA and (b) DTA curve of the lead-free Cs3 Bi2 Cl9 perovskite single crystals.
for this lead-free perovskite. Here it was observed that the
material first undergoes 60% mass loss of BiCl3 component,
followed by more loss of CsCl. It should be noted that this
decomposition behavior of CsCl and BiCl3 is in a single step
but in Cs3 Bi2 Cl9 it is in multiple steps showing that this
decomposition behavior occurs only when these species are
incorporated into the perovskite structure. Both precursors
CsCl and BiCl3 are sublimed in a single mass-loss step at a
well-defined temperature. One more observation is that CsCl
undergoes weight loss with onset temperature at 640 ◦ C while
in organic species like CH3 NH3 X (X = Cl, Br, I) undergo weight
loss with the onset temperature at 171 ◦ C, 202 ◦ C, and 202 ◦ C
respectively [49], suggesting that Cs-based material are more
references
thermally stable. DTA curve shows a phase transition at 551 ◦ C.
5. Conclusions
In conclusion, crystal growth kinetics is explained for the slow
cooling and antisolvent vapor diffusion method. In our best of
knowledge, first-time single crystal growth of Cs3 Bi2 Cl9 lead-
free perovskite is reported by both slow cooling method and
antisolvent vapor diffusion method in ambient conditions.
Structural and crystalline properties of Cs3 Bi2 Cl9 single crys-
tal have been investigated by single crystal x-ray diffraction
technique. E-statistics confirms that single crystals grown by
both methods are centrosymmetric, which means crystals are
not suitable for second-order non-linearity but it is suitable for
third-order nonlinearity. The diffraction pattern in the recip-
rocal space shows the growth of planes and symmetry in the
crystal. It was concluded that the growth methods environ-
ment and thermodynamic conditions affect the structure of
crystals. More study for other properties of the cesium bis-
muth chloride single crystal is ongoing.
Conflicts of interest
The authors declare no conflicts of interest.
Acknowledgments
SS like to acknowledge DST Solar Energy Research Grant (DST-
SER-47).
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.jmrt.2020.04.097.
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