Size Tunable Cesium Antimony Chloride Perovskite Nanowires and Nanorods

Article abstract of DOI:10.1021/acs.chemmater.8b00427

All-inorganic perovskite nanocrystals are emergent alternative of organolead halide perovskites. Cesium antimony halide (Cs₃Sb₂X₉, X = Cl, Br, I) all-inorganic perovskites nanocrystals possessing analogous electronic configuration to the organolead halide perovskites are promising materials for optoelectronic applications. We report on a colloidal route to synthesis uniform Cs₃Sb₂Cl₉ perovskite nanowires with lengths up to several microns. We have synthesized aspect ratio controlled nanorods with the same ～20 nm diameter of nanowires by tuning the precursors and ligands in the reaction. The crystallinity of the nanocrystals is significantly altered from the pristine bulk trigonal and orthorhombic phases owing to the one-dimensional shape of the nanocrystals. Rietveld refinement carefully separates out orthorhombic phase from the trigonal phase revealing a coexistence of both the phases in a minor and major ratio in the nanocrystals. The functionality in the form of fast photodetector demonstrates Cs₃Sb₂Cl₉ nanocrystals as promising materials for optoelectronic applications.

Full text of DOI:10.1021/acs.chemmater.8b00427

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Article
Size Tunable Cesium Antimony Chloride Perovskite Nanowires and Nanorods
Bapi Pradhan, Gundam Sandeep Kumar, Sumanta Sain, Amit Dalui,
Uttam Kumar Ghorai, Swapan Kumar Pradhan, and Somobrata Acharya
Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.8b00427 • Publication Date (Web): 26 Feb 2018
Downloaded from http://pubs.acs.org on February 26, 2018
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Chemistry of Materials
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Size Tunable Cesium Antimony Chloride Perovskite Nanowires and
Nanorods
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†
†
‡
†,§
¶
Bapi Pradhan , Gundam Sandeep Kumar , Sumanta Sain , Amit Dalui , Uttam Kumar Ghorai ,
#
,†
Swapan Kumar Pradhan and Somobrata Acharya*
†Centre for Advanced Materials, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India
‡Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, In-
dia
§Department of Chemistry, Jogamaya Devi College, Kolkata 700026, India
¶Department of Industrial & Applied Chemistry, Swami Vivekananda Research Center, Ramakrishna Mission
Vidyamandira, Belur Math, Howrah 711202, India
#Department of Physics, University of Burdwan, Burdwan 713104, West Bengal, India
ABSTRACT: All-inorganic perovskite nanocrystals are emergent alternative of organolead halide perovskites. Cesium an-
timony halide (Cs
tion to the organolead halide perovskites are promising materials for optoelectronic applications. We report on a colloidal
route to synthesis uniform Cs Sb Cl perovskite nanowires with lengths up to several microns. We have synthesized as-
3
2
Sb X
9
, X = Cl, Br, I) all-inorganic perovskites nanocrystals possessing analogous electronic configura-
3
2
9
pect ratio controlled nanorods with the same ~ 20 nm diameter of nanowires by tuning the precursors and ligands in the
reaction. The crystallinity of the nanocrystals is significantly altered from the pristine bulk trigonal and orthorhombic
phases owing to the one-dimensional shape of the nanocrystals. Rietveld refinement carefully separates out orthorhombic
phase from the trigonal phase revealing a coexistence of both the phases in a minor and major ratio in the nanocrystals.
The functionality in the form of fast photodetector demonstrates Cs
lectronic applications.
3
Sb
2
Cl nanocrystals as promising materials for optoe-
9
organic23 and all-inorganic perovskite NCs using colloidal
INTRODUCTION
1
5,24–30
route have been reported recently.
Antimony-
Organolead halide perovskites nanocrystals (NCs) possesses
remarkable properties leading to a variety of optoelectronic
containing thin films and anti-solvent vapor-assisted bulk
crystals of (CH
ovskites were developed using non-colloidal routes.
cently, solution phase synthesis of Cs Sb
quantum dots have been reported. Advantageously,
3
NH
3
)
3
Sb
2
I
9
, (NH
)
4 3
Sb
2
I
x
Br9-x and Cs
3
Sb
2
I
9
per-
1–4
applications. However, the stability of the organolead hal-
13,14,31
Re-
5
–8
ide perovskites NCs remains a major technical hurdle ow-
ing to the sensitivity towards oxygen and moisture, which
often disassociates under environmental stress. Hence,
there has been a swift surge of alternate all-inorganic perov-
skite NCs negating volatile organic component. In recent
years, a variety of inorganic perovskite materials have been
3
2 9
X (X = Cl, Br, I)
32
9
Cs
3
Sb
2
X
9
perovskite structure is favourable by Goldschmidt
33–35
tolerance factor suggesting an enhanced stability.
tionally, the similarity of electronic configuration of Cs
Addi-
2 9
Sb X
3
with the organolead halide perovskites NCs implies im-
portant advantages of this class of all-inorganic materials.
Although trigonal and orthorhombic phases of bulk
10–14
reported with promising optoelectronic properties.
How-
13
ever, most of these materials are developed in the form of
thin films. In comparison, the investigation on one-
dimensional (1D) perovskite nanowires (NWs) and nanorods
Cs
ago,
3
Sb
2
Cl
9
(CSC) have been reported more than 40 years
36,37
the NCs of this specific elemental composition has
2,15–20
(NRs) is rather limited.
The dimension dependent prop-
never been explored. Here we report on the microns long
ambient stable all-inorganic CSC perovskite NWs using col-
loidal synthesis route. Monodispersed NRs have been synthe-
sized by changing the ligands using the same reaction condi-
tions of NWs. Fine kinetic control over the aspect ratio of
NRs have been achieved by adjusting reactant precursor con-
centrations. Rietveld refinement reveals coherent existence
erties of 1D NCs is expected to show improved carrier migra-
tion, significant light trapping and enhanced mechanical
properties, in comparison to the 3D structures adding ad-
vantages in the functions of optoelectronics devices.
However, colloidal synthesis of 1D perovskite NWs or NRs
has remain challenging, although both hybrid inorganic-
21,22
1
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of major trigonal and minor orthorhombic phases in the
creased to 120°C (ramp 5°C/min) and annealing was carried
out for 30 min under N gas. Color of the solution changes
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NWs and NRs. We demonstrated fabrication of photodetec-
tor using the perovskite NWs with excellent sensitivity, fast
time response and repeatability.
2
from turbid to light transparent indicating Sb-OLAc-HDA
complex formation with annealing time. After 30 min, tem-
perature of the reaction was set to 160°C (ramp 5°C/min).
When reaction temperature was reached to 160°C, preheated
solution (at 100°C) of 0.65 mL of Cs-OLAc-ODE was swiftly
injected into the reaction mixture and reaction was annealed
for different time. To check the morphology of the formed
NCs, aliquots were collected for different time interval. The
reaction was quenched immediately by cooling on ice water
bath.
EXPERIMENTAL SECTION
Materials
Antimony Chloride (SbCl
3
, 98%, Sigma), Oleic acid (OLAc,
90%, Aldrich), 1-Octadecene (ODE, 90%, Aldrich), Hexadec-
ylamine (HDA, 70%, Aldrich), Oleylamine (OLAm, 70%,
Aldrich), Hydrochloric acid (HCl, 37%, Merck), Cesium car-
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0
bonate (Cs
2
CO
3
, 98%, Merck) acetone, toluene, t-butanol
t
(
BuOH) were used without further purification. All reactions
gas flow using Schlenk techniques
3 2 9
Isolation and purification of Cs Sb Cl NRs and NWs
were carried out under N
2
The crude NCs formed in the reaction flask were collected in
a centrifuge tube followed by the addition of equal volume of
unless otherwise stated. Gold patterned electrodes used for
photoconductivity measurements were purchased form
Qudos Technology LTD.
Methods
Cesium oleate preparation
t
BuOH. The mixture was centrifuged at 8500 rpm for 2 min.
After centrifugation, the supernatant part was discarded and
the precipitate NCs were re-dispersed in a small amount of
t
toluene. Excess BuOH was added to the NCs toluene disper-
Cesium-oleate (Cs-OLAc) was prepared by dissolving 0.8 gm
sion and re-centrifuged at 8500 rpm for 2 min. The proce-
dure was repeated for three times to remove unreacted pre-
cursors and ligands. After final wash, the precipitate was re-
dispersed in toluene to form stable colloidal suspension of
NCs and stored under 4°C refrigeration for further character-
ization, device fabrication.
Characterization
Absorption spectra were measured in a Varian Carry 5000
UV-Vis-NIR spectrophotometer. The photoluminescence
of Cs
mosphere until all Cs
was cooled to 100°C and stored under N
further use. Cesium-oleate-octadecene (Cs-OLAc-ODE) was
prepared by dissolving 0.4 g Cs CO in 1.75 ml OLAc and 15
2
CO
3
in 8 mL of OLAc at 150°C for 30 min under N
CO is dissolved. Then, the reaction
atmosphere for
2
at-
2
3
2
2
3
ml ODE by heating the mixture under vacuum at 120°C for 30
min followed by heating up to 150°C until clear solution was
obtained. Then the solution was cooled to room temperature
1
0,38,39
2
and stored under N .
(
PL) spectra were collected by using a Nanolog spectrofluo-
HDA.HCl preparation
rometer from HORIBA Jobin Yvon. The photoluminescence
quantum yield (QY) was recorded in calibrated integrated
sphere attached with the Edinburgh FLS 980 spectrofluo-
rometer. The FTIR spectra were taken in solid state KBr pel-
let form in a Perkin Elmer 100 FTIR spectrometer. X-ray-
electron-diffraction (XRD) measurements were performed on
a drop casted thin film of CSC NCs in a Bruker D8 advance
Hexadecylamine hydrochloride (HDA.HCl) was prepared by
the reacting of HDA with HCl. A total of 4.83 g (20 mmol) of
HDA was dissolved in 150 mL of acetone, and 2.46 mL (30
mmol) of HCl (37% in water) was added dropwise to the so-
lution. White precipitate was stirred overnight to complete
the reaction. White precipitate of HDA·HCl was filtered and
washed with Milli-Q water and dried under vacuum desicca-
tor.
α
powder diffractometer, using Cu K (λ=1.54 Å) as the incident
radiation. Scanning rate of 0.02°/sec was employed in 2θ
range of 10° to 70°. Transmission electron microscopy was
carried out using JEOL JEM-2010 electron microscopy operat-
ing at 200 kV electron source. A dilute CSC NCs toluene dis-
persion were drop casted on a carbon-coated copper grid
followed by vacuum drying before imaging. For chemical
Cs
In a three neck round bottom flask, 60 mg SbCl
OLAc, 440 mg HDA.HCl and 4 mL ODE was loaded and N
3 2 9
Sb Cl NWs synthesis
3
salt, 0.5 mL
2
gas was purged at 120°C (ramp 5°C/min) for 30 min. Color of
the solution changes from turbid to transparent yellow indi-
cating Sb-OLAc-HDA complex formation with annealing
time. After 30 min, the temperature of the reaction solution
was set to 170°C (ramp 5°C/min). When the reaction temper-
ature was reached to 170°C, 0.65 mL of Cs-OLAc was swiftly
injected into the reaction mixture and reaction was annealed
for 20 min. The reaction was quenched immediately by cool-
2
mapping of CSC NCs, a FEI, Tecnai G F30, S-Twin
microscope operating at 300 kV equipped with a GATAN
Orius B CCD camera was used. High-angle annular dark-field
scanning transmission electron microscopy (STEM-HAADF)
is employed in the same microscope which is equipped with
a scanning unit and a HAADF detector from Fischione
(model 3000). X-ray photoelectron spectroscopy (XPS) was
performed using PerkinElmer Phi 5500 ESCA spectrometer
3 2 9
ing on ice water bath. Pure trigonal phase Cs Sb Cl NCs was
obtained by using a similar methodology by injecting 0.15 ml
Cs-OLAc at 155°C keeping all other parameter unchanged.
with an Al K
α
X-ray source generating X-ray photons of
3 2 9
Pure orthorhombic phase Cs Sb Cl NCs was obtained using
1
486.7 eV in energy in an ultrahigh-vacuum chamber with
similar methodology by injecting 0.65 ml Cs-OLAc at 200°C
and annealing for 5 min keeping all other parameter un-
changed.
–9
base pressure of 10 Torr. The spectra were obtained with an
–
analyzer pass-energy of 23.5 eV and a scan speed of 0.05 eV s
1
.
For XPS measurements, a thin film of the NCs were pre-
Cs
3 2 9
Sb Cl NRs synthesis
pared on a silicon wafer substrate, followed by heating at
5°C for 80 min under N atmosphere. The film was then
Synthesis of CSC NRs was carried out by modifying previous-
8
2
1
0,38,39
ly reported methods
was loaded with 45 mg SbCl
and 4 mL ODE. The reaction mixture temperature was in-
. A three neck round bottom flask
cooled to 25°C and stored under vacuum before measure-
ment. Raman spectra were collected on a drop casted thin
film of NCs on silicon wafer substrate in a J-Y HORIBA
3
salt, 0.5 mL OLAc, 500 mg HDA
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Chemistry of Materials
T64000 triple Raman spectrophotometer. Thermogravimet-
ylammonium chloride (HDA.HCl) at 170°C under N
2
atmos-
+
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2
3
4
5
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7
8
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ric (TGA) experiment was carried out in a Q600, TA Instru-
ments. Atomic force microscopy (AFM) imaging of NCs on a
mica substrate were performed with an Asylum Research
MFP-3D AFM in tapping mode using AC160TS silicon probes,
with nominal tip radii ˂10 nm. Thin phosphorous doped sili-
con cantilever with resistance 1-10 Ωcm has been used for
scanning.
phere (see experimental section). We added Cs-OLAc as Cs
source in a solution of SbCl
3
in high boiling solvent 1-
Octadecene (ODE) containing a mixture of OLAc and
HDA.HCl ligands in a molar ratio of 3:2. In this reaction,
3
+
−
SbCl
3
serves as the source of both Sb and Cl ions and
−
HDA.HCl supplies additional Cl ions required for the charge
balance of the resultant NWs. Low resolution transmission
electron microscope (TEM) image shows microns long
(3.4±0.6 µm) CSC NWs with a diameter of ~20±6 nm (Figure
1a, Figure S1a,b, SI). AFM topographic image shows the uni-
form diameter of 20±2 nm (Figure 1b,c) along the length of a
NW with a thickness of ∼3±0.5 nm (Figure 1d). High resolu-
tion TEM (HRTEM) image of NWs reveals well-resolved lat-
tice planes implying crystalline nature of the NWs (Figure
1e). An interplanar spacing of ~0.29±0.05 nm corresponding
XRD analyses
Rietveld’s whole profile fitting method
4
0,41
is regarded as one
of the best methods to obtain different structure and micro-
structure parameters like lattice parameters, phase volume
fractions, coherently diffracting domain (crystallite) size,
r.m.s. lattice strain, etc. In the present study, we have adopt-
ed this method to evaluate different structure and micro-
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42
structure parameters using the software MAUD which al-
lows to refine different structure and microstructure parame-
ters simultaneously. Detail of this method has been dis-
to the
planes of trigonal crystal structure (ICSD 22075) is
observed. However, selected area electron diffraction (SAED)
pattern shows the existence of orthorhombic phase in addi-
tion to the trigonal phase (Figure 1f). Energy dispersive X-ray
(EDX) in TEM shows the atomic ratio of Cs:Sb:Cl3:2:8,
which matches closely with Cs Sb Cl chemical composition
4
3,44
cussed elaborately elsewhere.
Photoconductivity measurements
The device was fabricated by simple drop casting method.
For the preparation of film, Cs Sb Cl NWs and NRs solution
3 2 9
was prepared in toluene (20 mg/ml) and few microliters of
that solution was drop casted on the pre-patterned gold elec-
trodes on silicon wafer. The device was annealed at 80°C for
3
2
9
(Figure S1c, SI). UV-vis absorption spectrum of NWs reveals
an optical band gap of 3.4 eV (Figure S2a, SI). Reported band
47
gap of bulk Cs Sb Cl is ~3 eV. An increase in the band gap
3
2
9
10 mins in N
2
atmosphere to dry the film. The photoconduc-
of the NWs in comparison to the bulk is attributed to the
quantum confinement effect. In addition to the reduced size
effect, the 1D shape of the NWs also contributes to the quan-
tum confinement effect since the charge carriers are confined
along the diameter and allowed to move along the length of
tivity I-V measurements (dark and light) were carried out by
illuminating the fabricated photodetector device with New-
port white light source (mercury lamp-one sun–100
2
mW/cm ; model 69911) connected to a Keithley 4200 semi-
conductor characterization system. The photoswitching
measurements were done by using a slab, which is used to
illuminate or block the incoming light manually on the de-
vice. The monochromatic light (~ 70 µW power) of wave-
length ~ 410 nm is generated by using a monochromator
(
Newport, model 74125). The figure of merits of the photode-
tector like responsivity (R), detectivity (D) and external
quantum efficiency (EQE) are calculated by measuring the
d p
dark current (I ) and photocurrent (I ) at ~ 410 nm illumina-
tion. The following formulas are used for the calculation of
responsivity, detectivity, and EQE of photodetector device:
Responsivity (R)
p d p d
R = ΔI/A*P = I -I /A*P; where I , I represent the current at an
applied bias voltage in the dark and under illumination of
light respectively, A is the effective active area of the photo-
detector device and P is input power per unit area.
Detectivity (D)
D = R/√2qJ
tron and J is dark current density.
External Quantum Efficiency (EQE)
EQE = hcR /qλ; where h is planks constant, c is velocity of
light, R is responsivity measured at a specific wavelength of
d
; where R is Responsivity, q is charge of an elec-
d
λ
λ
monochromatic light source, q is charge of an electron and λ
is wavelength of monochromatic light source.
Figure 1. (a) TEM images of CSC NWs. Inset shows NWs
width distribution histogram. (b) Tapping mode AFM image
of a single NW. (c) Cross section profile along the black line
in Figure b. (d) Reconstruction of the AFM image showing
the thickness of the NW. (e) HRTEM image of CSC NWs
showing interplanar lattice spacing’s. (f) SAED pattern of
NWs showing coexistence of trigonal and orthorhombic
phases.
RESULT AND DISCUSSION
Synthesis of CSC NWs was carried out through ionic me-
1
0,15,45,46
tathesis process
3
using antimony chloride (SbCl ) and
cesium oleate (Cs-OLAc) in presence of mixture of long
chain capping ligands oleic acid (OLAc) and hexadec-
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the NWs.48 Photoluminescence (PL) spectrum shows a peak
as observed for Cs
and HDA.HCl ligands. C-O stretching frequency of carbox-
3 2 9
Sb Cl NWs overlaps with the free HDA
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maximum at 436 nm with quantum yield of 4% (Figure S2b-
d, SI). Raman spectrum (Figure S3, SI) shows major peaks at
-
1
ylate group observed at 1450-1470 cm for unbound OLAc
ligand. Presence of C-O stretching frequency peaks in NWs
-
1
-1
253 cm and 308 cm corresponding to B1g mode of SbCl
3
and
4
9,50
-1
-1
A
1g, E2g, T2g modes of CsCl respectively.
We have carried
(1471 cm and 1495 cm ) indicate binding of OLAc in oleate
form on the surface of NWs. TGA analysis shows that CSC
NWs are stable up to 600°C (Figure S6, SI), though the first
weight loss occurs at ~ 69°C due to the decomposition of
out XPS measurements to perceive the chemical states of the
elements in the NWs (Figure S4, SI). XPS confirms Cs (+1), Sb
(
+3) and Cl (-1) oxidation states within the CSC NWs. Details
5
3
analysis of XPS spectra shows relative ratio of
a
organic ligands.
Cs:Sb:Cl3:2:8 which matches closely with the EDX meas-
urements. Fourier transform infrared (FTIR) spectroscopy
shows the presence of OLAc, HDA and HDA.HCl on the sur-
Powder X-ray diffraction (XRD, Figure 2a) pattern of CSC
NWs shows reflections primarily corresponding to trigonal
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phase (ICSD 22075; space group:
; a=7.61Å, c=9.32Å).
30,51,52
face of CSC NWs (Figure S5, SI).
Presence of C-H
A careful observation using Rietveld analysis identifies low
intensity peaks at 11.9°, 19.9° and 30.9° corresponding to
(012), (020) and (043) planes of orthorhombic phase (space
group: Pmcn; a=7.63Å, b=13.079Å, c=18.663Å, ICSD 2066)
respectively (Figure 2b). Additional isolated reflection from
the orthorhombic phase is not observed, instead, several
overlapped reflections with the trigonal phase is evidenced
(Figure 2b). Notably, Rietveld analysis using solely trigonal
-
1
stretching frequencies (2914 and 2847 cm ) in Cs
3
2 9
Sb Cl NWs
are similar to free HDA and HDA.HCl since nonpolar C-H
bonds do not interact with the surface of the NCs. N-H bend-
-
1
ing vibrations appear at 1587 cm for NWs which is shifted
-
1
from free HDA, HDA.HCl ligands N-H vibration (1567 cm ).
N-H stretching vibration for free HDA and HDA.HCl appears
-
1
in the range of 3000-3500 cm . The N-H stretching vibrations
Figure 2. (a) XRD pattern of CSC NWs showing trigonal phase. (b) Rietveld analysis confirming the presence of orthorhombic
phase along with trigonal phase. Red curve represents the observed intensity (I ) and black curve represents calculated intensity
) and blue curve represents the residue (I −I ) of the fitted pattern. (c) Refined output pattern using only trigonal phase (red
O
(
I
C
O
C
curve) showing absence of orthorhombic phase (black curve). Enlarged sections are shown in the insets. (d) Individual contribu-
tion of trigonal and orthorhombic phases obtained from Rietveld refinement. (e) Atomic arrangements, unit cell (top-inset) and
SbCl
top-inset) and polyhedron (bottom-inset) of orthorhombic phase. Black spheres correspond to Sb, red spheres represent Cs and
white spheres correspond to Cl.
6
octahedra (bottom-inset) of trigonal phase. (f) Atomic arrangements, irregular triangular planar geometry of Sb and Cl
(
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phase shows a clear mismatch in the intensity pattern at the
cell consists of a Sb atom surrounded by six Cl atoms forming
SbCl octahedron (Figure 2e, top-inset). The bond lengths of
elements in the trigonal unit cell are calculated to be ~5.38Å
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peak positions of the minor orthorhombic phase (Figure 2c).
This observation implies the simultaneous presence of trigo-
nal and orthorhombic phases within the NWs. We have
quantified the crystal phases of the NWs using Rietveld’s
6
(Cs−Cs), ~4.66Å (Cs−Sb), ~3.81Å (Cs−Cl) and ~2.69Å (Sb−Cl)
respectively.
A change in bond angles of the SbCl
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structure refinement method.
Relative volume fractions
octahedron from their ideal value of 90° is observed (Figure
2e, bottom-inset). The orthorhombic CSC unit cell consists
of a Sb atom bonded with three nearest Cl atoms in an
irregular triangular planar geometry (Figure 2f). Different
Sb−Cl bond lengths and Cl−Sb−Cl bond angles of such
arrangement is observed (top-inset, Figure 2f). Each Cs atom
in the unit cell constitutes an irregular twelve coordination
numbered convex polyhedron with nearest twelve Cl atoms
(bottom-inset, Figure 2f). The Cs atom remains at the center
while Cl atoms occupy the corner positions of the
polyhedron. Out of twelve Cl atoms, six Cl atoms remain in
an equatorial plane within the polyhedron forming a
of crystalline phases are extracted from scale factors of the
respective calculated intensities (Figure 2d). Rietveld analysis
quantifies the volume fractions of major trigonal and minor
orthorhombic phases to be ~79% and ~21% respectively. This
observation implies that the size of the coherently diffracting
domains of trigonal phase is greater than the orthorhombic
phase in the NWs. Based on the experimental observation,
we have modelled the atomic arrangements of trigonal and
orthorhombic phases within the NWs. Both trigonal and
orthorhombic CSC shows a close-packed arrangement of Cs
and Cl atoms with Sb atoms (Figure 2e,f). The trigonal unit
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Figure 3. (a) TEM image, (b) HRTEM image, (c) SAED pattern of CSC NRs with 30 min of annealing time. (d-g) STEM-HAADF-
EDX elemental mapping of NRs showing homogeneous distribution of Cs, Sb and Cl. (h-k) TEM images of NRs with different
annealing time. (l) TEM image of elongated CSC NRs with SbCl amount variation for 30 min of annealing time. The bottom
3
panels represent respective width and length distribution histograms for (h-l).
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hexagon and the remaining six Cl atoms remain equally
above and below this equatorial plane. Different Cs−Cl bond
lengths suggest a distorted hexagon within the polyhedron
of 165±12 nm and diameter of 20±5 nm (Figure 3h). A system-
atic increase in the reaction annealing time reveals that the
size of the NRs remains the same (Figure 3h-k) suggesting
fast formation of NRs within 1 min annealing after injection
(
Figure S7, SI). Pristine trigonal and orthorhombic crystal
3
6,37
phases of bulk CSC have been reported earlier.
We have
of Cs-OLAc-ODE to the SbCl
3
precursor. Notably, the growth
3
NCs showed the formation of
synthesized phase pure trigonal CSC NCs using the same
reaction procedure at lower reaction temperature than NWs
synthesis (Figure S8a-c, SI). TEM images show irregular ag-
glomerated morphology of pure trigonal NCs (Figure S8b,c,
SI). Phase pure orthorhombic CSC NCs have been synthe-
sized at an elevated reaction temperature retaining the same
reaction procedure of NWs synthesis (Figure S9a-e, SI). TEM
images reveal NWs-like morphology of the NCs (Figure S9b-
e, SI). Notably, shape controlled NWs are obtained at an
intermediate reaction temperature when both trigonal and
orthorhombic phases coexist in the NCs. Simultaneous
presence of trigonal and orthorhombic phases in the NWs
appears to originate from the fact that the lattice parameter
mechanism of Sb , Sb Se
S
2 3
2
5
7,58
NRs and NWs with a slower reaction kinetics.
Hence,
CSC NRs follow a different reaction mechanism from the
reported antimony-chalcogenides, exhibiting a faster reac-
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tion kinetics.
Size tunability of the NRs is further
from 0.2 mmol
achieved by decreasing the amount of SbCl
3
to 0.12 mmol retaining other reaction parameters unchanged.
TEM image shows NRs with lengths of 290±12 nm and widths
of 20±5 nm suggesting an increased aspect ratio with de-
3
creased SbCl amount (Figure 3l). UV-vis absorption spectra
of CSC NRs show the same peak positions with annealing
time variation (Figure S12, SI). FTIR spectroscopy shows the
presence of OLAc, HDA and HDA.HCl on the surface of CSC
NRs (Figure S5). XRD patterns remain identical with the an-
nealing time (Figure S13a). Rietveld’s analysis of XRD shows
the simultaneous presence of trigonal and orthorhombic
phases in the NRs (Figure S13b,c, SI). Raman spectrum of
NRs replicates the peaks positions of NWs (Figure S14, SI).
‘
a’ of the trigonal phase remains in close proximity with that
of the orthorhombic phase which enables the coherent
growth of the two phases (Figure 2e,f). The lattice parameter
‘a’ of the trigonal phase increases and ‘c’ decreases marginally
from their bulk counterpart (ICSD 22075) (Table S1, SI). For
trigonal phase, the lattice volume of the unit cell marginally
One unique feature of NWs based photodetector is that
NWs can be deposited from the solution phase. CSC NWs
based photodetectors are fabricated on pre-patterned gold
electrodes with a channel length of ~ 100 nm. A schematic
representation of the device structure is shown in Figure 4a.
The current–voltage (I-V) characteristics show semiconduct-
ing behaviour both in the dark and under the illumination
(Figure 4b). A significant enhancement in the current is ob-
served upon illumination (Figure 4b). Further, to check the
3
3
increases from 467.43 Å to 468.55 Å with respect to its bulk
counterpart. In case of orthorhombic phase, all three lattice
parameters decrease in comparison to their bulk counterpart
(
ICSD 2066) which reduces the lattice volume from 1862.43
3
3
Å to 1839.83 Å (Table S1, SI). This observation implies that
the trigonal phase remains in a more compact form
compared to the orthorohmbic phase within the NWs. Such
distortion in the unit cells presumably occurs to incorporate
the 1D NWs shape instead of phase pure bulk CSC. A suitable
theoretical calculation of a NW containing Cs
3 2 9
Sb Cl ortho-
rhombic and trigonal phases may establish this observation
5
4,55
to a greater extent.
Perovskite CSC NWs are stable at
ambient conditions since the crystal structure remains un-
changed for more than two months as indicated by the XRD
analyses (Figure S10, SI).
Our attempt to synthesize CSC NCs following the syn-
3 3
thetic route of all-inorganic CsPbX NCs by dissolving SbCl
in OLAc, oleylamine (OLAm) and ODE followed by the in-
jection of cesium-oleate-octadecene (Cs-OLAc-ODE) result-
10
ed in uncontrolled morphologies of NCs (Figure S11, SI).
Hydrolysis of SbCl
OLAm yields Sb
causing uncontrolled morphologies. However, the use of
HDA instead of OLAm results in NRs with the average length
of 165±12 nm and diameter of 20±5 nm (Figure 3a). HRTEM
image of the NRs (Figure 3b) reveals well-resolved lattice
planes with interplanar spacing of 0.29±0.05 nm correspond-
3
salt in presence of mixture of OLAc and
Cl before addition of Cs-OLAc-ODE
4
O
5
2
5
6
Figure 4. (a) Schematic representation of photodetector
device. (b) Current versus voltage characteristics of CSC
NWs in dark and under illumination. Inset shows the optical
image of the device. (c) Photoswitching behaviour at ~ 0.9 V
revealing fast switching ON and OFF states with time inter-
ing to
pattern of NRs features diffraction spots corresponding to
the trigonal and orthorhombic bulk phases of Cs Sb Cl (Fig-
plane of bulk trigonal phase (ICSD 22075). SAED
3
2
9
ure 3c). STEM-HAADF EDX elemental mapping shows ho-
mogeneous distribution of the constituting elements in the
NRs (Figure 3d-g). We have investigated the effect of anneal-
ing time on the growth evolution of NRs. We found fast for-
mation of the NRs within 1 min of reaction time with length
val of ~ 500 ms. (d) Rise (t
r d
) and decay (t ) time of a single
ON-OFF cycle.
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Chemistry of Materials
ACKNOWLEDGMENT
sensitivity, stability and repeatability of the device, we have
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conducted photoswitching measurements of the CSC based
photodetectors using white light (Figure S15, SI). Highly sen-
sitive photodetecting response is observed over repetitive
light ON and OFF cycles of illumination (Figure 4c, Figure
G.S.K. acknowledges DST INSPIRE, India for fellowship. We
thank B. Satpati, Saha Institute of Nuclear Physics, India and
A. H. Khan, Istituto Italiano di Tecnologia, Italy for TEM
analyses and useful discussions. SERB, DST is gratefully
acknowledged for the financial support.
S16, SI). The rise time (t
0.23 s respectively at a bias voltage of 0.9 V (Figure 4d),
which is similar to reported perovskite based photodetec-
r d
) and decay time (t ) are ∼0.13 s and
∼
1
9,59,60
ABBREVIATIONS
tors.
The photoswitching properties are stable and re-
peatable suggesting CSC as a potential optoelectronic mate-
rial. We have calculated the figure of merits like responsivity,
detectivity, and EQE of the photodetector using a specific
wavelength of light (~ 410 nm), which was obtained using a
monochromator. Schematic diagram of the photocurrent
measurements using a monochromator is shown in the sup-
porting information (Figure S15, SI). The responsivity, detec-
tivity and EQE of the CSC NWs photodetector under the
illumination of monochromatic light source ~ 410 nm with 70
NCs, nanocrystals; NWs, nanowires; NRs, nanorods; CSC,
Cs
3
Sb
2
Cl
9
;
OLAc, oleic acid, HDA, hexadecylamine;
hexadecylammonium chloride; OLAm,
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HDA.HCl,
oleylamine; TGA, thermogravimetric analysis.
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CONCLUSIONS
In conclusion, we have reported on a new class of all-
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Supporting Information
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Corresponding Author
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*Email: camsa2@iacs.res.in (Prof. Somobrata Acharya)
ORCID
(11) Jellicoe, T. C.; Richter, J. M.; Glass, H. F. J.; Tabachnyk, M.;
Bapi Pradhan: 0000-0002-6202-7343
Somobrata Acharya: 0000-0001-5100-5184
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Greenham, N. C.; Böhm, M. L. Synthesis and Optical Properties
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The authors declare no competing financial interests.
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One-dimensional all-inorganic cesium antimony chloride perovskite nanowires and nanorods have been synthesized using col-
loidal synthesis technique. Rietveld refinement reveals coherent existence of major trigonal and minor orthorhombic phases in
the nanocrystals. Excellent photosensitivity, fast switching speed and repeatability suggest promises for optoelectronic applica-
tions.
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