Journal of Alloys and Compounds 787 (2019) 17e26

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Synthesis of ligand-free, large scale with high quality all-inorganic

CsPbI3 and CsPb2Br5 nanocrystals and fabrication of all-inorganic
perovskite solar cells
Govindhasamy Murugadoss a, *, Rangasamy Thangamuthu a,
Sakkarapalayam Murugesan Senthil Kumar a, Narayanasamy Anandhan b,
Manavalan Rajesh Kumar c, Arumugam Rathishkumar d
a
Electrochemical Materials Science Division, CSIR-Central Electrochemical Research Institute, Karaikudi, 630 003, Tamilnadu, India
b
Department of Physics, Advanced Materials and Thin Film Laboratory, Science Campus, Alagappa University, Karaikudi, 630 003, Tamilnadu, India
c
Institute of Natural Science and Mathematics, Ural Federal University, Mira 19, Yekaterinburg, Russia
d
Central Instrumentation Facility, CSIR-Central Electrochemical Research Institute, Karaikudi, 630 003, Tamilnadu, India

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

Article history: All-inorganic based cesium lead-halide (CsPbX3) perovskite nanocrystals have emerged as an attractive
Received 2 September 2018 nanomaterials owing to their stability and excellent optoelectronic properties. Here, we report synthesis
Received in revised form of high quality orthorhombic phase of CsPbI3 and tetragonal structure of the CsPb2Br5 nanostructures by
29 January 2019
various methods. In addition, we fabricated all inorganic based solar cell devices using highly stable
Accepted 3 February 2019
Available online 7 February 2019
CuSCN as hole transport material (HTM) and cost effective carbon-graphite composites as contact layer.
Currentevoltage measurements shows 0.74% efficiency for a yellow phase CsPbI3 perovskite while the
power conversion efficiency of black phase CsPbI3 reach 6.9%. Moreover, tetragonal structure of CsPb2Br5
Keywords:
Perovskite
shows 2.82% using the similar architecture. Sandwich type architecture (FTO/bl-TiO2/m-TiO2/Perovskite/
Energy CuSCN/C:G) employed for the fabrication of both devices. This work offer a new avenue to prepare large
Nanostructure scale with high-quality inorganic perovskite materials and fabrication of high efficiency all-inorganic
Photovoltaic perovskite solar cells (PSCs).
© 2019 Elsevier B.V. All rights reserved.

1. Introduction with cesium (Cs) at the A-site, an all-inorganic perovskite can be

formed, obviating the problems of volatility and chemical decom-
Recently, hybrid organic-inorganic perovskite solar cells have position. Perovskite nanocrystals with all-inorganic cations have
received great attention in the photovoltaic research community been receiving significant attention, partly due to their high sta-
due to their high efficiency, low cost, easy solution process and bility compared with the hybrid organic-inorganic perovskites.
large scale applications [1,2]. On the basis of the excellent optical CsPbX3 perovskites are direct bandgap semiconductor exists in
and electric properties of perovskite materials, such as high ab- orthorhombic, tetragonal, and cubic crystal phases. The structural
sorption coefficient, tunable direct band gap and long carrier transformation is depending on applied temperature, for example a
diffusion length [3,4], the power conversion efficiency (PCE) of cubic face formed at high temperature (above 130
C for CsPbBr3).
photovoltaic devices (PVs) has ascended from 3.8 to above 22% in In the recent past, more attention has been focused on the syn-
just 4 years [5,6]. The perovskite materials have the formula ABX3, A thesis of CsPbX3 perovskite nanocrystals and tuning of their optical
is methylammonium (MA) or formamidinium (FA), B is lead, and X band gap by controlling the particle size or introducing different
is halides (e.g., MAPbI3). However, the organic component is highly halide anions. Generally, octadecene (ODE), oleic acid (OA), and
hygroscopic in nature, which leads to easy decomposition in oleylamine (OLA) are used as additive agents for the synthesis of
ambient air atmosphere [7,8]. By replacing the organic component CsPbX3 perovskite in order to control size and tuning morphology.
The past research demonstrates the unique and interesting prop-
erties of cesium lead halide perovskite nanoparticles and their
* Corresponding author. potential to be used in optoelectronic applications. However, the
E-mail address: [email protected] (G. Murugadoss).

https://doi.org/10.1016/j.jallcom.2019.02.018
0925-8388/© 2019 Elsevier B.V. All rights reserved.
18 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26

synthesis of ligand-free CsPbX3 perovskite nanostructures with settled down colloidal precipitate was collected and washed with
facile methods is still under exploration. Solar cells with CsPbI3 and toluene and then it was dried at 130
C for 10 min.
CsPb2Br5 as light absorbing layers have been reported recently
[9,10]. To completely remove the unstable organic component and 2.4. Hydrothermal method
maximally enhance the thermal stability, all-inorganic cubic CsPbI3
and orthorhombic CsPb2Br5 were used in PSCs, and achieved pre- An equal molar concentration of perovskite precursors was first
liminary PCE of 2.9% and above 10%, respectively [9,10]. Especially dissolved in DMF and then the solution was dropped into toluene in
interesting is that unlike CsPbBr3 that requires high temperature a 1:5 vol ratio with a Teflon-lined autoclave (50 mL). The autoclave
for the synthesis, CsPb2Br5 can be prepared in a facile way at room was tightly closed and heated to 130
C for 8 h. After cooling down
temperature, which is very attractive for the future applications. to room temperature and depressurizing the autoclave, the prod-
Besides photovoltaics, these inorganic perovskites have also been ucts were separated by filtration, washed with toluene, and dried in
explored for their potential in other applications such as water air at 130
C for 10 min for further characterization.
splitting, light emitting diodes and photodetectors [11]. In addition,
the inorganic based d-CsPbI3 and CsPb2Br5 have been demonstrated 2.5. Solar cell fabrication
as more resistant to moisture, humidity and light illumination
compared to organic based hybrid perovskite [8,12]. Hence, high- The devices were fabricated using fluorine-doped tin oxide
end sophisticated lab facility is not required to prepare the Cs (FTO) coated glass substrates employing a stack of compact TiO2/
based perovskite. mesoporous TiO2/perovskite/CuSCN/carbon-graphite composites.
Even though PSCs achieving high power conversion efficiency Conductive FTO glass (Xinyan tech. Ltd, HK) was sequentially
within a short period, improvement are not yet reached for large cleaned by detergent and isopropanol in an ultrasonic bath for
area installations. For example, in the conventional device noble 30 min before exposure to UV-ozone treatment for 15 min. The
metals such as Au or Ag were used as counter electrodes (CEs) and compact TiO2 film was applied on FTO substrates by spin coating
2,20 ,7,70 -Tetrakis-(N, N-di-4-methoxyphenylamino)-9,90 -spirobi- from a precursor solution containing 1 mL of titanium di-
fluorene (Spiro-OMeTAD) or poly[bis(4-phenyl)(2,4,6-trimethyl- isopropoxidebis(acetylacetonate) in 9 mL of ethanol, followed by
phenyl)amine] [PTAA] have been used as hole transport materials, annealing for 15 min at 125
C. Then, mesoporous TiO2 layer with a
which are indispensable in these high-performance photovoltaic thickness of around 400 nm was deposited by spin coating from a
devices, however, not favourable for large-scale production. Be- dispersion of TiO2 nanoparticles (DYESOL, 18 NR-T) in ethanol. The
sides, high-energy-consumption vacuum evaporation method of substrates were then annealed at 450
C for 30 min, cooled to room
preparing costly metal cathodes and organic molecule in HTM re- temperature. Perovskite solution was directly prepared by one step
strains its commercialization as well. In this work, we report a facile method from the corresponding perovskite (CsPbI3 or CsPb2Br5)
synthesis in which ligand-free process yields high crystalline powders which were already prepared by hydrothermal method.
orthorhombic CsPbI3 and tetragonal CsPb2Br5 powders in different The perovskite layers were fabricated by a single-step spin-coating
structures. Photovoltaic performance of the all-inorganic based procedure based on the anti-solvent addition as reported in the
PSCs using CuSCN as HTM and carbon-graphite as counter electrode previous work [13]. For solar cell fabrication, perovskite solution
is investigated. was prepared by simply mixing the perovskite powder in
DMF:DMSO (4:1 vol ratio) mixed solvent. Then, the perovskite
2. Experimental precursor solution was spun at 3000 rpm for 30 s, with an accel-
eration of 1000, and 10 s prior to the end, 500 mL of chlorobenzene
2.1. Materials was added onto the spinning film to obtain dense, pinhole-free
perovskite layers. The spin coated films were annealed at 130
C
All chemicals were purchased from commercial sources and for 15 min prior to the deposition of the HTM layer. For CuSCN
used without further purification. Lead iodide (PbI2, Aldrich, 99%), deposition, a solution containing 8 mg/mL of CuSCN in dipro-
lead bromide (PbBr2, Afla Aesar, 98%), cesium iodide (CsI, Afla Aesar, pylsulfide solvent (TCI, purity 98%) was stirred overnight and then
99.9%), cesium bromide (CsBr, Aldrich, 99%), copper (I) thiocyanate HTM layer was deposited by doctor-blade method under 80
C of
(CuSCN, Aldrich, 99%) toluene (Merck, 99.5%), dimethylformamide substrate temperature. Finally, devices were completed by depos-
(DMF, TCI, 99.5%) are used. iting commercial carbon-graphite paste on the top of the HTM film
To synthesis CsPbI3, CsI and PbI2 precursors were used equal by the doctor-blading technique, followed by heat-treatment at
molar ratio. Similarly, 0.25 M solution of CsBr and PbBr2 were used 100
C for 30 min. The performance of devices were evaluated
for CsPb2Br5 preparation. Dimethylformamide (DMF) used as sol- under simulated AM 1.5 G, 100 mW cm2 sun light with an active
vent for both perovskite preparation and the perovskite solutions area of 0.25 cm2.
were prepared under 70
C with continuous stirring. Different
methods were used for the preparation of Cs based perovskite. 2.6. Characterization

XRD pattern of CsPbI3 and CsPb2Br5 was recorded using PAN

2.2. Drop casting method Analytical X' pert PRO Model X-ray diffractometer with mono-
chromated Cu Ka irradiation (l ¼ 1.5418 Å). Surface and cross-
As shown in Fig. 1, the hot (130
C) perovskite solution dropped sectional image was measured by FE-SEM (JEOL JSM-6700F) oper-
on the top surface of hot (130
C) glass slide, after 2 min, the slide ated at 10 and 30 kV. High Resolution Transmission Electron Mi-
was taken out and then the samples were collected from slide by croscopy (HR-TEM) images were taken using Tecnai G2 20 and
scraping. Tecnai G2 F20 S-Twin working at an accelerating voltage of 200 kV,
respectively. Diffuse reflectance spectra were recorded using a UV-
2.3. Anti-solvent treatment method VIS-NIR double beam spectrophotometer (VARIAN, Cary 5000).
Fourier transform infrared (FT-IR) analysis was conducted using a
The hot perovskite precursor solution was dropped into a hot Bruker optic GmbH TENSOR-27 spectrometer from Thermos elec-
petridish (130
C) which contains hot toluene, after 2 min, the tron at room temperature. Photocurrent-voltage (J-V)
 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26 19

Fig. 1. Schematic illustration of the various methods, which enables to synthesis different morphology with, stands unique crystal quality of CsPbI3 and CsPb2Br5 by solution
processing in powder form. All the synthesis procedures were done in the ambient atmosphere without using any ligands to modify the structure. For all the preparation methods,
1:1 M ratio of precursors were mixed in the DMF and stirred initially at 70
C which was raised to 130
C before start the reaction. In the first drop casting method, no anti-solvent
(toluene) used, but other two methods about 10 times volume of toluene (compared to precursors solvent) used to trigger the reaction very fast.

measurement for the perovskite devices performed under AM 1.5 demonstrated various methods such as drop casting, anti-solvent
sun irradiation (100 mW cm2) using a 100e220 W small beam treatment and hydrothermal used for the synthesis of CsPbI3 and
simulator (Photo Emission Tech., Inc., model SS80AAA). CsPb2Br5 perovskite at an ambient air atmosphere. After synthesis
of the perovskite powders, solar cells were fabricated using con-
3. Results and discussion ventional one step method by simply mixing the perovskite pow-
ders into a desired solvent followed by spin coating. To fabricate all
In this work, initially synthesis of the CsPbI3 and CsPb2Br5 inorganic PSCs, CuSCN and carbon-graphite (1:3) were used as hole
perovskite were investigated by analyzing morphological as well as transport layer and counter electrode, respectively.
structural variations of the different preparation methods. The The structure of all powders was examined via X-ray diffraction,
growth process and shape evolution of the perovskite crystals were and all relevant XRD spectra are presented in Fig. 2a and b. The
tracked using HR-TEM, XRD and optical spectra obtained for as- measured spectra for yellow phase CsPbI3 (d- CsPbI3) shown here
synthesized powder samples. It is worth to mention here that in (Fig. 2a) is in good agreement with literature data for the ortho-
our perovskite synthesis process no ligand or shape controlling rhombic perovskite structure [14] prepared by the different
parameters such as temperature, concentrations were employed. methods. The diffraction patterns of the powder samples were
The shape of the perovskites was mainly depending on the prep- assigned to orthorhombic phase CsPbI3 (Fig. 2a); no patterns from
aration methods. To the best of our knowledge, these three the PbI2 or CsI starting materials were observed. The diffraction
methods are rapid as well as large scale production of perovskite pattern shows the presence of pure orthorhombic structure, which
could be achieved. All the preparation process can be completed in is substantially similar for all three methods. Similar diffraction
ambient atmosphere indicating the feasibility of generation of patterns were observed even though various morphology obtained
various structures of CsPbI3 and CsPb2Br5. The synthesis of Cs based by different methods. Moreover, it shows overall shapes of all XRD
perovskite by these facile methods is easy to be scaled up. Fig. 1 spectra are similar. A similar orthorhombic structure was reported
20 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26

Fig. 2. The X-ray diffraction pattern of orthorhombic and cubic structure of (a) d-CsPbI3 and (b) CsPb2Br5 perovskite prepared by various methods. Interconversion between the two
structures occurs through rotation of the PbBr6 octahedra. (c, d) Optical absorption and corresponding band gap curves derived from the optical absorption values, respectively. The
absorption spectra of all perovskite samples were determined from diffuse reflectance. The marks indicate overall absorption onset of d-CsPbI3 and CsPb2Br5, as 480 nm and 550 nm
with the corresponding band gap of 2.24 eV and 2.58 eV, respectively. (e, f) Photoluminescence (PL) spectra of d-CsPbI3 and CsPb2Br5 perovskites, prepared by various methods,
excited with 400 and 450 nm, respectively. All the spectra were recorded in the powder form in the ambient atmosphere.

for CsPbI3 nanowires [14e16], but the nanowires obtained using 480 nm and 550 nm, respectively. It is in good agreement with
oleic acid (OA) and oleylamine (OLA) as ligands to control size and previous observations and indicates that materials with bandgap of
morphology. The XRD pattern of Fig. 2b demonstrated that high 2.58 eV and 2.24 eV (Fig. 2d), respectively [19]. The absorption of
crystalline and pure tetragonal CsPb2Br5 (PDF: 25e0211) structure the samples obtained by hydrothermal method has slightly red
those were synthesized in the three methods. We believe that shifted than other samples which may be due to size dependant
applied temperature (130
C) may have influenced the unique properties. Photoluminescence (PL) spectra of d-CsPbI3 and
tetragonal structure of CsPb2Br5 in all the three methods. Only few tetragonal CsPb2Br5 powder samples are also investigated and
groups were reported similar tetragonal structure with sheet like presented in Fig. 2e and f, respectively. From Fig. 2e, we can clearly
morphology but they were used organic legends to control the observe the intense PL emission with peak position at 485 nm and
reaction rate [17,18]. It is worth to mention here that for the first 545 nm with shoulder peaks at 460 nm and 530 nm, respectively.
time we report CsPb2Br5 nanowire growth without employing any Recently, Lai et al. observed a broad emission for d-CsPbI3 perov-
ligands in a hydrothermal method. skite from 400 to 700 nm which contains two peaks at 450 and
The optical absorption and corresponding band gap curves (Tauc 530 nm [20]. In this work, we observed intense emission with
plot) derived from the absorption value of CsPbI3 and CsPb2Br5 distinct doublet peaks in the blue (460, 485 nm) and green region
powders are presented in Fig. 2c and d, respectively. The absorption (545, 530 nm) for d-CsPbI3 phase. The high-energy peaks likely
onsets (shaded) for the CsPbI3 and CsPb2Br5 NWs were found to be originate from excitonic emission, but the low-energy peak
 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26 21

observed for CsPbI3 is due to probably self-trapped excitons [20,21]. The morphology of perovskite crystals was investigated by FE-
The d-CsPbI3 powders show good optical properties in shorter SEM measurement. For comparison purpose, the FE-SEM images
wavelength region which can be used in optoelectronic devices. In of CsPbI3 and CsPb2Br5 perovskite are presented together in Fig. 3a-
addition, the PL measurements performed also for tetragonal f. In the drop casting method, CsPbI3 rods formed in micrometre
structured CsPb2Br5 under similar condition. It was found a strong scale with defective and aggregate (Fig. 3a) leaf like structure,
green emission around 525 nm, which is in good agreement with however, microsphere obtained for CsPb2Br5 (Fig. 3b). For the anti-
previously reported value [10,20] and this absorption value is solvent treatment method, distinct nanorods (CsPbI3) and isolated
similar to the cubic CsPbBr3 [22]. Until now, the CsPb2Br5 perovskite microsphere (CsPb2Br5) are shown as in Fig. 3c and d, respectively.
was prepared in two different structures namely nanotubes [20] Typical thickness and length of the obtained nanorods (NRs) is to be
and nanoplate [17] using some organic ligands. The above results ~400 nm and 5e10 mm, respectively. For the first time, well crys-
revealed that various methods adopted are capable of yielding talline CsPbI3 nanowires (NWs) and CsPb2Br5 nanorods (NRs) pre-
highly PL active Cs based perovskite in large scale. pared by hydrothermal method without involving any catalyst as

Fig. 3. (aef) FE-SEM images of the CsPbI3 and CsPb2Br5 nanocrystal prepared by various methods with different morphology. (i) CsPbI3: (a) Aggregated, indistinguishable rods
containing small grains (drop casting), (c) well defined nanorods (anti-solvent treatment) and (e) high quality yellow phase nanowires (hydrothermal). (ii) CsPb2Br5: (b) micro-
spheres (drop casting), (d) aggregated particles (anti-solvent treatment) and (f) well crystalline nanorods (hydrothermal). For the electron microscopy study, the powder samples
were directly pressed on the grid. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
22 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26

shown in Fig. 3e and f, respectively. The PbI2 octahedra are edge- color) and CsPb2Br5 (red color) powders. Two prominent peaks
shared in CsPbI3, forming a 1D chain structure along the [0 1 0] observed in the whole FT-IR spectra: (i) A broad peak centred
direction. The anisotropic crystal structure was attributed to the around 3450 cm1 (green color shade) is produced in all the sam-
growth of nanowires in a preferred direction. These single- ples, signally the presence of OeH stretch. (ii) A strong and sharp
crystalline NWs and NRs could serve as an ideal platform for band appears at 1576 cm1 (red color shade) which can be assigned
further investigation of structurefunction relationships which is to C]O stretching. No other organic signal observed in both CsPbI3
critical for the development of future applications in nanoscale and CsPb2Br5 surface which revealed that three proposed solution
optoelectronics. methods are more favourable for preparation of high purity and of
High Resolution Transmission electron microscopy (HR-TEM) the stable, organic free nanocrystals in large scale. The results
was performed to verify the structural characteristics of the as- showed that the prepared perovskite is not required any further
prepared Cs based perovskite. The synthesized CsPbI3 (NWs) and purification.
CsPb2Br5 (NRs) were measured with various magnifications as The surface chemical element and valence states of the involved
shown in Fig. 4a, b and Fig. 4c, b, respectively. The selected area compositions are analysed by employing X-ray photoelectron
electron diffraction (SAED) result is shown as the inset in Fig. 4b spectroscopy (XPS) study. Fig. S2 and Fig. S3 show XPS spectra of
and d. The SAED pattern indicates the nanostructures were in well the a-CsPbI3 and CsPb2Br5 perovskite, respectively. The energy
crystalline nature and can be indexed to an orthorhombic phase of bands of Cs, Pb and I can be clearly identified in the survey XPS
CsPbI3 with [1 0 1] zone index and tetragonal phase of CsPb2Br5 spectrum (Fig. S3a). A small peak of C 1s originating from adven-
with [2 0 0] index, which agrees well with the previous reports titious carbon was also observed and set to 284.8 eV. The binding
[17,18]. The magnified images of Fig. 4b and d exhibit the CsPbI3 and energies of Cs 3d3/2 (738.7 eV), Cs 3d5/2 (724.8 eV), Pb 4f5/2
CsPb2Br5 nanowires were grown by assembled tiny particles. The (143.3 eV), Pb 4f7/2 (138.4 eV), I 3d3/2 (630.8 eV) and I 3d5/2
above results claim that a possibility of the Cs based one-dimension (619.3 eV) bands were determined after calibration, as shown in
structure by simple hydrothermal method. Fig. S2 (bed). Similarly, Fig. S3 (aed) shows the survey and high
To identify the chemical functional groups on the surface, we resolution XPS spectra of Cs, Pb, and Br atoms, respectively. The
measured the FT-IR spectra for all perovskite powder samples. binding energy curves of Cs 3d3/2 and Cs 3d5/2 are observed at 737.8
Fig. S1 (Supplementary data) shows FT-IR spectra of CsPbI3 (blue and 723.1 eV. Meanwhile, the peaks of Pb 4f5/2 and Pb 4f7/2 are

Fig. 4. Typical HR-TEM images of CsPbI3 (a,b) and CsPb2Br5 (c,d) nanowires with various magnification, corresponding SAED patterns are shown as inset in (b) and (d), respectively.
The clear spot lines in the SAED pattern dictates both are in well crystalline nature. The inter-planar value of 0.45 nm for (1 0 1) plane of yellow phase and 0.41 nm of (2 0 0) for
tetragonal structure CsPb2Br5 are marked in the magnified images (b, d). (For interpretation of the references to color in this figure legend, the reader is referred to the Web version
of this article.)
 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26 23

located at 142.2 and 137.3 eV, respectively. The weak intensity higher temperature. Similarly, DTA curve of CsPb2Br5 shows sig-
profile of Br 3d3/2 and Br 3d5/2 are centred at 70.1 and 67.8 eV, nificant changes at low temperature while stable TG curve until
respectively. These results corroborate that all the elements of the 550
C. In general, CsPbBr3 has two-phase transitions, the first one
two perovskite involved (Cs, Pb, Br and I) in the compositions are is at 130
C, which suggests that the tetragonal-to-cubic phase
1þ, 2þ, 1- and, 1- of their formal valence states [23]. transition is a first order, whereas the orthorhombic-to-tetragonal
Thermogravimetric and differential thermal analysis (TGeDTA) one is a second order [25]. In our case, we employed 130
C for
were used to study the thermal decomposition, phase change and synthesis, hence any exothermic peak related to phase transition at
crystallization behaviour of the CsPbI3 and CsPb2Br5 powders. The low temperature was not appeared. It was found that only a sharp
synthesized perovskite powders were heated from room temper- exothermic peak appeared at 360
C which may be trigged the
ature to 800
C with an increment of 10
C/min in nitrogen atmo- melting of perovskite or improving the crystallinity of the perov-
sphere. Fig. 5 shows combined plots of TG and DTA of the CsPbI3 skite, and a small exothermic (~470
C) with broad endothermic
and CsPb2Br5 powders. From the TG data plots, it is noticed that no peak appeared (~510
C) in the higher temperature due to melting
weight loss found up to 550
C for both perovskites. However, of the sample [24]. The overall TG-DTA results showed high thermal
notable changes were observed in the DTA curves for both samples stability of the all inorganic Cs based perovskite which are more
as shown in Fig. 5a and b. The CsPbI3 and CsPb2Br5 shows a sharp, favourable to fabricate highly stable PSCs and optoelectronic
single-stage degradation (TG) at ~550
C, without any lower tem- devices.
perature features, indicating that the materials are stable close to Recently, the design and preparation of novel Cs based perov-
that temperature. In DTA curve of CsPbI3, it showed three sharp skites have drawn great attention because the performances of
exothermic peak at 328
C, 440
C and 484
C, the first peak is due PSCs based on inorganic perovskites exhibited rapid progress over
to phase transition of d-CsPbI3 to a-CsPbI3, this phase transition is the past few years [9,12,19,25e29]. It is well-known that the
in good agreement with literature [10,24], the other exothermic organic CH3NHþ 3 cation has a higher volatility and hydrophilicity
peaks may be due to decomposition and melting of material at the than the inorganic Csþ cation. It tends to deviate from CH3NH3PbI3
crystalline structure under the environment of relatively high RH
and temperature. Such circumstances lead to the degradation of
CH3NH3PbI3 which results the decay of device performance. The
remarkable stability of Cs based perovskite is an important factor
that ensures the reproducibility and excellent stability of the all
inorganic PSCs [24]. In addition, organic hole transport materials
2,20 ,7,70 -tetrakis(N,N0 -di-p-methoxyphenylamine)-9,90 -spirobi-
fluorene (Spiro-OMeTAD) or polytriarylamine (PTAA), and organic
additives in hole transport materials (mainly lithium bis(tri-
fluoromethanesulfonyl)imide or tert-butylpyridine), are additional
major issues, especially the high cost and the performance insta-
bility against high temperature and moisture.
In order to investigate photovoltaic performance of all inorganic
based PSCs, CuSCN and carbon-graphite composites mixed pastes
were used as HTM and contact layer, respectively. The inorganic
based HTM and carbon-graphite counter electrode can further
improve the stability of the inorganic PSCs. More recently, a-CsPbI3
(black phase- CsPbI3) and CsPbBr3 were used for the fabrication of
all-inorganic PSCs. However, the a-CsPbI3 is not stable at room
temperature. Fig. 6 display schematic illustration of the all inor-
ganic based PSCs fabrication procedure. For J-V measurements, the
d-CsPbI3 (yellow phase CsPbI3) and CsPb2Br5 devices were directly
measured after sealing the carbon based counter electrode with the
photo-anode. However, the whole device of the a-CsPbI3 perovskite
was again sintered at 330
C for 10 min before measuring the
photovoltaic parameters in order to attain black phase of the
perovskite (instantly, the dark color of the pre-sintered a-CsPbI3
layer was transferred into yellow color during the HTM deposition
because the deposition time took about 5e10 min). The applied
temperature was selected by thermal study (Fig. 5a). Fortunately,
the other layers (FTO/TiO2, CuSCN and C:G counter electrode) in the
device are high thermal stable which is helpful to regenerate the
active black phase of the perovskite within the device architecture.
In general, perovskite film surface plays a crucial role in deter-
mining device performance. In order to study the surface infor-
mation, FE-SEM images recorded for CsPbI3 and CsPb2Br5
perovskite on FTO/TiO2 film. Fig. 7a, b and c display top view of the
CsPb2Br5, d-CsPbI3 and a-CsPbI3 perovskite, respectively. The FE-
Fig. 5. Combined study of thermogravimetric and differential thermal analysis SEM image in Fig. 7(a) and (b) presents a non-uniform but
(TGeDTA) for (a) CsPbI3 and (b) CsPb2Br5 powders prepared by hydrothermal method. smooth film consisting of different sized crystal grains with the
The temperature was applied from RT to 800
C under N2 atmosphere. The red color
dotted line represent thermogravimetric and blue color dotted line represent DTA
sizes ranging from 50 to 400 nm. In Fig. 7(a), it was found two
results. (For interpretation of the references to color in this figure legend, the reader is different structures, big crystals and tiny particles underneath the
referred to the Web version of this article.)
24 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26

Fig. 6. Schematic illustration of device fabrication procedure of corban based counter electrode of sandwich type device. The film color represents from top to bottom, d-CsPbI3
(light yellow color), a-CsPbI3 (dark brown) and CsPb2Br5 (yellow). Hole transport layer and counter electrode were simply prepared by doctor blade technique. The schematic also
demonstrate the structural changes of the CsPbI3 by color change from yellow to dark under temperature. Before measuring the photovoltaic performance, the CsPbI3 film within
the device was again sintered at high temperature in order to get back the photoactive phase. Improved device performance reflected the phase changes of the perovskite. (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

big crystals. Similarly, two different structures were found for d- measuring the J-V study, the whole device was sintered at 330
C in
CsPbI3 (Fig. 7b), small group of crystals and with highly uniform a hot plate for 10 min in order to regenerate the photoactive phase
spherical particles. Fig. 7c clearly show the compact and rigidly (a-CsPbI3). The high efficiency of the sintered device reflects the
packed surface covered with large grains in the range of phase transition of the perovskite, moreover, the experiment re-
50e150 nm. The average grain size of perovskites in a-CsPbI3 film is sults showed that all inorganic based device has excellent stability
estimated to be ~100 nm. The schematic cross-sectional view of a- at high temperature. The photovoltaic devices based on d-CsPbI3
CsPbI3-based all inorganic PSCs with the structures of FTO/bl-TiO2/ absorber layer produced Voc ¼ 0.55 V and Jsc ¼ 2.0 mA cm2, with
m-TiO2/a-CsPbI3/carbon in low and high magnified images shown FF ¼ 0.66, corresponding to a PCE of 0.74%, with a dramatic decline
in Fig. 7d and (e), respectively. The magnified cross-sectional im- in short-circuit current densities (Jsc), being close to 2 mA cm2.
ages clearly showed each layer clearly on the FTO. Fig. 7f exhibits The result of d-phase CsPbI3 is in good agreement with recent
the energy band levels of all inorganic perovskite solar cell, report using the similar carbon based counter electrode [25].
revealing the electron extraction from the inorganic perovskite However, an impressive improvement in the photoconversion ef-
conduction band to the TiO2 conduction band and the hole ficiency is recorded for the sintered device, achieving nearby 6.9%
extraction from the inorganic perovskite valence band to the car- (see Table 1). The following sandwich type architecture was used
bon electrode through CuSCN HTM [29e33]. Fig. 7g shows com- for all the perovskites, <FTO/bl-TiO2/m-TiO2/inorganic perovskite/
bined UVevis spectra of the d phase and a phase of the CsPbI3 and CuSCN/carbon-graphite/FTO>. High current density
CsPb2Br5, the absorption edge (~730 nm) of the a-CsPbI3 is signif- (13.8 mA cm2) was observed for this cell which shows high ab-
icantly shifted to longer wavelength region compared to d-CsPbI3 sorption of the perovskite film (Fig. 7g). Furthermore, the
(~450 nm). Taking into account of the peak close to infrared region, enhancement in Jsc was verified by the incident photon-to-current
the optical bandgap is measured and found as 1.7 eV. The stable efficiency (IPCE) spectra. The IPCEs of the a-CsPbI3 under study are
CsPb2Br5 shows a strong absorption at 540 nm. plotted in Fig. 7i. A major improvement within the wavelength
To prepare CuSCN solution propylsufide used as a solvent. The range from 375 to 700 nm is observed for a-CsPbI3 perovskite solar
carbon-graphite composites paste was prepared in chlorobenzene cell compared with a reduced width (375e450 nm) for the d-CsPbI3
by applying sonication and stirring for several times until getting perovskite solar cell. Table 1 summarizes the Jsc calculated from the
well dispersion and colloidal paste form. The JeV curves of the IPCE spectra which are well consistent with the values obtained
three perovskites under simulated AM1.5G (100 mW cm2) illu- from JeV curves in Fig. 7h.
mination are represented in Fig. 7h and all photovoltaic parameters It could be found that CsPb2Br5 device showed a decent per-
are summarized in Table 1. It is noteworthy that all of the fabrica- formance using the all inorganic based device structure
tion steps for the all-inorganic PSCs were done in ambient air with (Voc ¼ 0.82 V, Jsc ¼ 5.7 mA cm2, FF ¼ 0.59 and PCE ¼ 2.82). Our
no additional humidity or temperature control. It is worth to experiment result of tetragonal CsPb2Br5 perovskite solar cell is
mention that the observed cell performances are insensitive for the comparable with cubic CsPbBr3 perovskite solar cell [34]. For the
two stable perovskite (d-CsPbI3 and CsPb2Br5) solar cells against the first time, tetragonal CsPb2Br5 perovskite was used as photoactive
environment which is an additional advantage for practical appli- materials in perovskite solar cell and successfully achieved a
cations. Therefore, both devices were not subjected to temperature reasonable device performance using all inorganic based device
after sealing the counter electrode with photoanode. In contrast, a- structure. Our present works have well demonstrated the possi-
CsPbI3 is highly moisture sensitivity thus it can easily regenerate to bility of fabricating high efficiency all inorganic based PSCs using
non-perovskite yellow phase at room temperature. Hence, before inorganic CuSCN HTM and carbon-based counter electrode for the
 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26 25

Fig. 7. Surface images of (a) CsPb2Br5, (b) d-CsPbI3 and (c) a-CsPbI3 phase perovskite films, those were prepared by spin coating on FTO/bl-TiO2/m-TiO2 layer. The scale bar rep-
resents 200 nm for all three images. (d) Cross-sectional image of the lower magnification and (e) higher magnification of the FTO/bl-TiO2 (50 nm)/m-TiO2 infiltrated with a-CsPbI3
(400 nm)/CuSCN (450 nm)/C:G (14 mm) device, the scale bar represent 2 mm and 200 nm, respectively. (f) Energy band diagram of the a-CsPbI3 and CsPb2Br5 based all-inorganic
perovskite solar cells, showing the electron injection and hole extraction routes. (g) Combined UVevis spectra of d-CsPbI3, a-CsPbI3 and CsPb2Br5 perovskite. (h) Current
densityevoltage measurement of the three different perovskites (d-CsPbI3, a-CsPbI3 and CsPb2Br5), 0.25 cm2 active area used for all the devices. (i) IPCE measurements of the
devices.

Table 1 properties even they had been in different morphology. We have

Parameters of the solar cells. demonstrated high photoconversion efficiencies under 1 sun illu-
Perovskite Jsc (mA cm2) Voc (V) FF PCE (%) mination in organic free lead halide PSCs. For the first time, CuSCN
d-CsPbI3 2.0 0.55 0.66 0.74
used as HTM in Cs based all inorganic device and successfully
a-CsPbI3 13.8 0.94 0.52 6.90 achieved high efficiencies. These devices yielded efficiencies of
CsPb2Br5 5.7 0.82 0.59 2.82 0.74%, 6.9% and 2.82% for d-CsPbI3, a-CsPbI3 and CsPb2Br5, respec-
tively. The all inorganic PSCs not only showed high photovoltaic
performance but also showed an excellent thermal stability. This
Cs based perovskite. type of high temperature stable all-inorganic based PSCs can be
used in aerospace and desert area in the future. Future research
with the CsPbI3 and CsPb2Br5 will be focused on photovoltaic per-
4. Conclusions formance for further improving PCE in large area devices. In addi-
tion, while this work focuses on the CsPbI3 and CsPb2Br5
In summary, ligand-free, large scale solution-phase synthetic nanostructures, the synthetic methods reported here can poten-
approaches have been developed to obtain single-crystalline d- tially be applied to other inorganic perovskites, such as tin or Bi
CsPbI3 and tetragonal CsPb2Br5 nanostructures. The various based perovskites, which will be less toxic.
methods such as drop casting, anti-solvent treatment and hydro-
thermal are demonstrated to prepare well crystalline Cs based
perovskite in large scale with morphologies such as microsphere, Acknowledgements
nanorods and nanowires. Optical results indicated that both d-
CsPbI3 and CsPb2Br5 are PL active, and exhibit unique optical The authors are grateful to the Science and Engineering
26 G. Murugadoss et al. / Journal of Alloys and Compounds 787 (2019) 17e26

Research Board (SERB), Department of Science and Technology [15] Y. Zhou, D.-D. Zhou, B.-M. Liu, L.-N. Li, Z.-J. Yong, H. Xing, Y.-Z. Fang, J.-S. Hou,
H.-T. Sun, Ultrabroad near-infrared photoluminescence from bismuth doped
(DST), India for awarding Young Scientist Project to Dr. G. Mur-
CsPbI3: polaronic defects vs. bismuth active centers, J. Mater. Chem. C 4 (2016)
ugadoss under, grant agreement no. SB/FTB/PS/158/2013 (GAP 06/ 2295e2301.
15). One of the authors (Manavalan Rajesh Kumar) thanks to the [16] C. Wang, A.S.R. Chesman, J.J. Jasieniak, Stabilizing the cubic perovskite phase
contract no. 40/is2. of CsPbI3 nanocrystals by using an alkyl phosphinic acid, Chem. Commun. 53
(2017) 232e235.
[17] G. Li, H. Wang, Z. Zhu, Y. Chang, T. Zhang, Z. Song, Y. Jiang, Shape and phase
Appendix A. Supplementary data evolution from CsPbBr3 perovskite nanocubes to tetragonal CsPb2Br5 nano-
sheets with an indirect bandgap, Chem. Commun. 52 (2016) 11296e11299.
[18] K.-H. Wang, L. Wu, L. Li, H.-B. Yao, H.-S. Qian, S.-H. Yu, Large-scale synthesis of
Supplementary data to this article can be found online at highly luminescent perovskite-related CsPb2Br5 nanoplatelets and their fast
https://doi.org/10.1016/j.jallcom.2019.02.018. anion exchange, Angew. Chem. Int. Ed. 55 (2016) 8328e8332.
[19] P. Luo, W. Xia, S. Zhou, L. Sun, J. Cheng, C. Xu, Y. Lu, Solvent engineering for
ambient-air-processed, phase-stable CsPbI3 in perovskite solar cells, J. Phys.
References Chem. Lett. 7 (2016) 3603e3608.
[20] M. Lai, Q. Kong, C.G. Bischak, Y. Yu, L. Dou, S.W. Eaton, N.S. Ginsberg, P. Yang,
[1] J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M.K. Nazeeruddin, Structural, optical, and electrical properties of phase controlled cesium lead
M. Gratzel, Sequential deposition as a route to high-performance perovskite- iodide nanowires, Nano Res. 10 (2017) 1107e1114.
sensitized solar cells, Nature 499 (2013) 316e319. [21] M. Nikl, K. Nitsch, F. Somma, P. Fabeni, G.P. Pazzi, X.Q. Feng, Luminescence of
[2] A.A. Mamun, T.T. Ava, H.R. Byun, H.J. Jeong, M.S. Jeong, L. Nguyen, C. Gausin, ternary nanoaggregates in CsIePbI2 thin films, J. Lumin. 8789 (2000) 372.
G. Namkoong, Unveiling the irreversible performance degradation of organo- [22] P. Cottingham, R.L. Brutchey, On the crystal structure of colloidally prepared
inorganic halide perovskite films and solar cells during heating and cooling CsPbBr3 quantum dots, Chem. Commun. 52 (2016) 5246e5249.
processes, Phys. Chem. Chem. Phys. 19 (2017) 19487e19495. [23] X. Li, Y. Wu, S. Zhang, B. Cai, Y. Gu, J. Song, H. Zeng, CsPbX3 quantum dots for
[3] S.D. Stranks, G.E. Eperon, G. Grancini, C. Menelaou, M.J.P. Alcocer, T. Leijtens, lighting and displays: room-temperature synthesis, photoluminescence su-
L.M. Herz, A. Petrozza, H.J. Snaith, Electron-hole diffusion lengths exceeding 1 periorities, underlying origins and white light-emitting diodes, Adv. Funct.
micrometer in an organometal trihalide perovskite absorber, Science 342 Mater. 26 (2016) 2435.
(2013) 341e344. [24] C.C. Stoumpos, C.D. Malliakas, J.A. Peters, Z. Liu, M. Sebastian, J. Im,
[4] Y. Liu, I. Shin, I.-W. Hwang, J. Lee, S. Kim, D.Y. Lee, S.-H. Lee, J.-W. Jang, T.C. Chasapis, A.C. Wibowo, D.Y. Chung, A.J. Freeman, B.W. Wessels,
Y.K. Jung, J.H. Jeong, S.H. Park, K.H. Kim, Effective hot-air annealing for M.G. Kanatzidis, Crystal growth of the perovskite semiconductor CsPbBr3: a
improving the performance of perovskite solar cells, Sol. Energy 146 (2017) new material for high-energy radiation detection, Cryst. Growth Des. 13
359e367. (2013) 2722e2727.
[5] A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, Organometal halide perovskites [25] J. Liang, C. Wang, Y. Wang, Z. Xu, Z. Lu, Y. Ma, H. Zhu, Y. Hu, C. Xiao, X. Yi,
as visible-light sensitizers for photovoltaic cells, J. Am. Chem. Soc. 131 (2009) G. Zhu, H. Lv, L. Ma, T. Chen, Z. Tie, Z. Jin, J. Liu, All-inorganic perovskite solar
6050e6051. cells, J. Am. Chem. Soc. 138 (2016) 15829e15832.
[6] M. Saliba, T. Matsui, J.Y. Seo, K. Domanski, J.P. Correa-Baena, [26] J. Liang, C. Wang, Y. Wang, Z. Xu, Z. Lu, Y. Ma, H. Zhu, Y. Hu, C. Xiao, X. Yi,
M.K. Nazeeruddin, S.M. Zakeeruddin, W. Tress, A. Abate, A. Hagfeldt, G. Zhu, H. Lv, L. Ma, T. Chen, Z. Tie, Z. Jin, J. Liu, Correction to “All-Inorganic
M. Gra €tzel, Cesium-containing triple cation perovskite solar cells: improved perovskite solar cells”, J. Am. Chem. Soc. 139 (2017) 2852.
stability, reproducibility and high efficiency, Energy Environ. Sci. 9 (2016) [27] G.E. Eperon, G.M. Paterno, R.J. Sutton, A. Zampetti, A.A. Haghighirad, F. Cacialli,
1989e1997. H.J. Snaith, Inorganic caesium lead iodide perovskite solar cells, J. Mater.
[7] J. Chen, N.-G. Park, Inorganic hole transporting materials for stable and high Chem. A 3 (2015) 19688e19695.
efficiency perovskite solar cells, J. Phys. Chem. C 122 (2018) 14039e14063. [28] A. Swarnkar, A.R. Marshall, E.M. Sanehira, B.D. Chernomordik, D.T. Moore,
[8] G. Murugadoss, S. Tanaka, G. Mizuta, S. Kanaya, H. Nishino, T. Umeyama, J.A. Christians, T. Chakrabarti, J.M. Luther, Quantum doteinduced phase sta-
H. Imahori, S. Ito, Light stability tests of methylammonium and for- bilization of a-CsPbI3 perovskite for high-efficiency photovoltaics, Science 354
mamidinium Pb-halide perovskites for solar cell applications, Jpn. J. Appl. (2016) 92e95.
Phys. 54 (2015), 08KF08. [29] J. Liang, C. Wang, P. Zhao, Z. Lu, Y. Ma, Z. Xu, Y. Wang, H. Zhu, Y. Hu, G. Zhu,
[9] M. Kulbak, D. Cahen, G. Hodes, How important is the organic part of the lead L. Ma, T. Chen, Z. Tie, J. Liu, Z. Jin, Solution synthesis and phase control of
halide perovskite photovoltaic cells? Efficient CsPbBr3 cells, J. Phys. Chem. inorganic perovskites for high-performance optoelectronic devices, Nanoscale
Lett. 6 (2015) 2452e2456. 9 (2017) 11841e11845.
[10] A. Swarnkar, A.R. Marshall, E.M. Sanehira, B.D. Chernomordik, D.T. Moore, [30] A. Mei, X. Li, L. Liu, Z. Ku, T. Liu, Y. Rong, M. Xu, M. Hu, J. Chen, Y. Yang,
J.A. Christians, T. Chakrabarti, J.M. Luther, Quantum doteinduced phase sta- M. Graetzel, H. Han, A hole-conductorefree, fully printable mesoscopic
bilization of a-CsPbI3 perovskite for high-efficiency photovoltaics, Science 354 perovskite solar cell with high stability, Science 345 (2014) 295e298.
(2016) 92e95. [31] W.S. Yang, J.H. Noh, N.J. Jeon, Y.C. Kim, S. Ryu, J. Seo, S.I. Seok, High-perfor-
[11] P. Ramasamy, D.-H. Lim, B. Kim, S.-H. Lee, M.-S. Lee, J.-S. Lee, All-inorganic mance photovoltaic perovskite layers fabricated through intramolecular ex-
cesium lead halide perovskite nanocrystals for photodetector applications, change, Science 348 (2015) 1234e1237.
Chem. Commun. 52 (2016) 2067e2070. [32] G. Li, F.W.R. Rivarola, N.J.L.K. Davis, S. Bai, T.C. Jellicoe, F. de la Pena, S. Hou,
[12] M. Kulbak, S. Gupta, N. Kedem, I. Levine, T. Bendikov, G. Hodes, D. Cahen, C. Ducati, F. Gao, R.H. Friend, N.C. Greenham, Z.-K. Tan, Highly efficient
Cesium enhances long-term Stability of lead bromide perovskite-based solar perovskite nanocrystal light-emitting diodes enabled by a universal cross-
cells, J. Phys. Chem. Lett. 7 (2016) 167e172. linking method, Adv. Mater. 28 (2016) 3528e3534.
[13] G. Murugadoss, R. Thangamuthu, M. Rajesh Kumar, S.M.S. Kumar, V. Prabu, Air [33] G. Murugadoss, R. Thangamuthu, S.M.S. Kumar, Fabrication of CH3NH3PbI3
free fast solution annealing method for perovskite solar cells, Mater. Lett. 205 perovskite-based solar cells: developing various new solvents for CuSCN hole
(2017) 130e133. transport material, Sol. Energy Mater. Sol. Cells 164 (2017) 56e62.
[14] R.E. Beal, D.J. Slotcavage, T. Leijtens, A.R. Bowring, R.A. Belisle, W.H. Nguyen, [34] X. Chang, W. Li, L. Zhu, H. Liu, H. Geng, S. Xiang, J. Liu, H. Chen, Carbon-based
G.F. Burkhard, E.T. Hoke, M.D. McGehee, Cesium lead halide perovskites with CsPbBr3 perovskite solar cells: all-ambient processes and high thermal sta-
improved stability for tandem solar cells, J. Phys. Chem. Lett. 7 (2016) bility, ACS Appl. Mater. Interfaces 8 (2016) 33649e33655.
746e751.