Cs3Sb2I9 and Cs3Bi2I9 with the hexagonal Cs3Cr2Cl9 structure type

Chabot, B.; Parthé, E.

doi:10.1107/s0567740878003684

Cited by 138 publications

(62 citation statements)

References 7 publications

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“…It consists of 0D octahedral anionic metal halide units (Sb 2 I 9 ) 3− surrounded by three (CH 3 NH 3 ) + or Cs + cations and connected via a hydrogenbonding interaction. 15,19,32 The X-ray diffraction pattern (XRD) in Figure 1b (upper panel) of the crystalline film shown in Figure 1c confirms the hexagonal structure of the (CH 3 NH 3 ) 3 Sb 2 I 9 but shows a strong preferential growth direction along the c-axis. In order to improve the homogeneity of the films and to prevent shunting, we used solvent engineering techniques.…”

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confidence: 59%

Optoelectronic Properties of (CH₃NH₃)₃Sb₂I₉ Thin Films for Photovoltaic Applications

et al. 2016

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We present solution-based fabrication and characterization of the lead-free perovskite-related methylammonium antimony iodide (CH 3 NH 3 ) 3 Sb 2 I 9 compound. By photothermal deflection spectroscopy (PDS), we determined a peak absorption coefficient α ≈ 10 5 cm −1 and an optical band gap of 2.14 eV for amorphous films of (CH 3 NH 3 ) 3 Sb 2 I 9 . Compared to the related Bi compound, the Sb-perovskite shows no exciton peak in its absorption spectrum. The photoluminescence emission (PL) is observed at 1.58 eV, and the Urbach tail energy of this amorphous compound is E u = 62 meV, indicating a substantial amount of energetic disorder. We fabricate a planar heterojunction solar cell with a (CH 3 NH 3 ) 3 Sb 2 I 9 absorber layer that yields a power conversion efficiency of η ≈ 0.5%, already featuring a decent fill factor (FF) of 55% and open-circuit voltage of 890 mV but low photocurrent densities. The result of this basic study on (CH 3 NH 3 ) 3 Sb 2 I 9 shows that this compound is a possible starting point for further research into Sb-based lead-free perovskite solar cells.L ead-based organic−inorganic hybrid semiconductors like CH 3 NH 3 PbI 3 (MAPI) have shown high potential as efficient absorber materials for single-junction solar cells due to their outstanding optoelectronic properties 1 and the easy and cheap fabrication methods. The power conversion efficiencies of these three-dimensional (3D) perovskite solar cells have increased rapidly up to more than 22% in 2016 2−5 after only 6 years of research starting from the first reported perovskite solar cell with an efficiency of 3.8%. 6 However, the low chemical stability of this lead-based perovskite under ambient air and the toxicity of the heavy metal lead could be obstacles for commercialization. 6−11 The tin analogous perovskite compound CH 3 NH 3 SnI 3 has exhibited moderate conversion efficiencies of up to 6% but is even more unstable under air and moisture because of the rapid oxidation of the Sn 2+ state to the Sn 4+ state. 12−14 Another promising group of materials for lead-free alternatives are the zero-dimensional (0D) Biperovskites A 3 Bi 2 X 9 (e.g., A = Cs + , MA + ; X = I − , Br − ). 15−17 These materials show high band gaps of E g > 1.8 eV, 18,19 which are suitable for tandem or triple solar cells. 20,21 Bismuth is a nontoxic element, and the Bi-based perovskites showed a better chemical stability under ambient atmosphere than the MAPI perovskite. 22 However, the Bi-perovskites also show the signature of excitons in their absorption spectrum that have binding energies in the range of 400 meV. 19,22 This leads to relatively low short-circuit current densities due to insufficient exciton splitting and charge carrier extraction. Bi-perovskitebased solar cells exhibit conversion efficiencies of 1% 22 with a TiO x electron transport layer (ETL) and 0.1% 23 in planar devices with pin-architectures where the exciton splitting at the interfaces is even more critical.In this work, we present the exchange of bismuth by antimony, which is less toxic than P...

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confidence: 59%

Optoelectronic Properties of (CH₃NH₃)₃Sb₂I₉ Thin Films for Photovoltaic Applications

et al. 2016

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“…Table S1) 13 and isostructural with (CN 3 H 6 ) 3 Sb 2 I 9 and (CN 3 H 6 ) 3 Bi 2 I 9 , 14 as well as Cs 3 Bi 2 I 9 at this temperature. 15 As reported extensively by Mitzi, 16 the dimensionality of perovskite-related phases varies from 0D to 3D depending on the sizes of the ions, forming isolated polyhedra, chains, layers, or three dimensional architectures. Recently, layered perovskites have been reported in solar cell devices, demonstrating band gap tuning by changing the sizes of the cations and the dimensionality of the framework.…”

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confidence: 86%

Synthesis, crystal structure, and properties of a perovskite-related bismuth phase, (NH4)3Bi2I9

et al. 2016

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Organic-inorganic halide perovskites, especially methylammonium lead halide, have recently led to a remarkable breakthrough in photovoltaic devices. However, due to the environmental and stability concerns of the heavy metal, lead, in these perovskite based solar cells, research in the non-lead perovskite structures have been attracting increasing attention. In this study, a layered perovskite-like architecture, (NH4)3Bi2I9, was prepared in solution and the structure was solved by single crystal X-ray diffraction. The results from DFT calculations showed the significant lone pair effect of the bismuth ion and the band gap was measured as around 2.04 eV, which is lower than the band gap of CH3NH3PbBr3. Conductivity measurement was also performed to examine the potential in the applications as an alternative to the lead containing perovskites.

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“…They are (1) twoTo whom correspondence should be addressed. dimensional corrugated layer of polyanions (6-8, 10, 11), (2) one-dimensional double chains of polyanions (12)(13)(14), (3) isolated bioctahedral M X\ anion (14)(15)(16), and (4) isolated unit composed of four octahedra (17). Type (4) has been reported only for Bi compounds as far as we know.…”

Section: Academic Pressmentioning

confidence: 96%

“…The phase transformation from the dimer form to the layer form was completed after heating for 1 h at 523 K, although no apparent DTA peak could be detected if the heating rate was slow. The dimer form crystallizes in a space group P6 /mmc in which the Sb I\ anion consists of two octahedra sharing their face (16). The layer form, on the other hand, consists of SbI octahedra sharing three cis vertices with three other octahedra forming corrugated layers.…”

Section: Academic Pressmentioning

confidence: 99%

Reconstructive Phase Transformation and Kinetics of Cs3Sb2I9by Means of Rietveld Analysis of X-Ray Diffraction and127I NQR

Yamada

Sera

Sawada

et al. 1997

Journal of Solid State Chemistry

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Cs₃Sb₂I₉ and Cs₃Bi₂I₉ with the hexagonal Cs₃Cr₂Cl₉ structure type

Cited by 138 publications

References 7 publications

Optoelectronic Properties of (CH₃NH₃)₃Sb₂I₉ Thin Films for Photovoltaic Applications

Optoelectronic Properties of (CH₃NH₃)₃Sb₂I₉ Thin Films for Photovoltaic Applications

Synthesis, crystal structure, and properties of a perovskite-related bismuth phase, (NH4)3Bi2I9

Reconstructive Phase Transformation and Kinetics of Cs3Sb2I9by Means of Rietveld Analysis of X-Ray Diffraction and127I NQR

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Cs3Sb2I9 and Cs3Bi2I9 with the hexagonal Cs3Cr2Cl9 structure type

Cited by 138 publications

References 7 publications

Optoelectronic Properties of (CH3NH3)3Sb2I9 Thin Films for Photovoltaic Applications

Optoelectronic Properties of (CH3NH3)3Sb2I9 Thin Films for Photovoltaic Applications

Synthesis, crystal structure, and properties of a perovskite-related bismuth phase, (NH4)3Bi2I9

Reconstructive Phase Transformation and Kinetics of Cs3Sb2I9by Means of Rietveld Analysis of X-Ray Diffraction and127I NQR

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Cs₃Sb₂I₉ and Cs₃Bi₂I₉ with the hexagonal Cs₃Cr₂Cl₉ structure type

Optoelectronic Properties of (CH₃NH₃)₃Sb₂I₉ Thin Films for Photovoltaic Applications

Optoelectronic Properties of (CH₃NH₃)₃Sb₂I₉ Thin Films for Photovoltaic Applications