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

Yamada, Koji; Sera, Hiroshi; Sawada, Syozo; Tada, Hironobu; Okuda, Takuo; Tanaka, Haruhiko

doi:10.1006/jssc.1997.7562

Cited by 69 publications

(94 citation statements)

References 22 publications

(23 reference statements)

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“…Upon cooling, the CsI film and trapped SbI 3 vapor react to form a film of the layered modification of Cs 3 Sb 2 I 9 , which shows a much less oriented grain structure. The reconstructive phase transformation of the dimer form into the layered form reported by Yamada et al 23 may not occur in the traditional sense of a phase transformation; rather, during annealing, the dimer form likely decomposes into CsI and SbI 3 vapor, which react upon subsequent cooling, thereby forming the layered modification. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 as the quenching temperature also ensures that the surface of the Cs 3 Sb 2 I 9 film is not covered with a SbI 3 film.…”

Section: Resultsmentioning

confidence: 95%

Thin-Film Preparation and Characterization of Cs₃Sb₂I₉: A Lead-Free Layered Perovskite Semiconductor

et al. 2015

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Computational, thin-film deposition and characterization approaches have been used to examine the ternary halide semiconductor Cs 3 Sb 2 I 9 . Cs 3 Sb 2 I 9 has two known structural modifications, the 0-D dimer form (space group P6 3 /mmc, No. 194) and the 2-D layered form (P3m1, No. 164), which can be prepared via solution and solid state or gas phase reactions, respectively. Our computational investigations suggest that the layered form, which is a one-third Sb-deficient derivative of the ubiquitous perovskite structure, is a potential candidate for highband-gap photovoltaic (PV) applications. In this work, we describe details of a two-step deposition approach that enables the preparation of large grain (>1 µm) and continuous thin films of the lead-free layered perovskite derivative Cs 3 Sb 2 I 9 . Depending on the deposition conditions, films that are c-axis oriented or randomly oriented can be obtained. The fabricated thin films show enhanced stability under ambient air, compared to methylammonium lead (II) iodide perovskite films stored under similar conditions, and an optical band gap value of 2.05 eV. Photoelectron spectroscopy study yields an ionization energy of 5.6 eV, with the valence band maximum approximately 0.85 eV below the Fermi level, indicating near-intrinsic, weakly p-type character. Density Functional Theory (DFT) analysis points to a nearly direct band gap for this material (less than 0.02 eV difference between the direct and indirect band gaps) and a similar high-level of absorption compared to CH 3 NH 3 PbI 3 . The photoluminescence peak intensity of Cs 3 Sb 2 I 9 is substantially suppressed compared to that of CH 3 NH 3 PbI 3 , likely reflecting the presence of deep level defects that result in non-radiative recombination in the film, with computational results pointing to I i , I Sb , and V I as being likely candidates. A key further finding from this study is that, despite a distinctly layered structure, the electronic transport anisotropy is less pronounced due to the high ionicity of the I atoms and the strong antibonding interactions between the Sb s lone pair states and I p states, which leads to a moderately dispersive valence band.

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Section: Resultsmentioning

confidence: 95%

Thin-Film Preparation and Characterization of Cs₃Sb₂I₉: A Lead-Free Layered Perovskite Semiconductor

et al. 2015

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“…Cs 3 Sb 2 I 9 exists in two polymorphs: (1) a zero-dimensional dimer modification (hexagonal) featuring Sb 2 I 9 3− bi-octahedral units and (2) a two-dimensional layered modification (trigonal) [163]. The dimer can be synthesized via solution-based methods using polar solvents, while the layered modification is obtained through solid-state reactions, gas phase reactions (e.g.…”

Section: Heterovalent Substitution With Mono- Tri- and Tetravalent Cmentioning

confidence: 99%

“…0.5[55, 163][NH 2 (CH 3 ) 2 ] 3 Sb 2 Cl 9 Exp.Monoclinic ( Pc ) at 200 K–––[159]Monoclinic ( P 2 1 / c ) at 298 K2D––[159, 168][NH 2 (CH 3 ) 2 ] 3 Sb 2 Br 9 Exp.Monoclinic ( P 2 1 / c )–––[167][NH(CH 3 ) 3 ] 3 Sb 2 Cl 9 Exp.Monoclinic ( Pc )2D––[160][N(CH 3 ) 4 ] 3 Sb 2 Cl 9 Exp.Hexagonal ( P 6 3 / mmc )0D––[158][N(CH 3 ) 4 ] 3 Sb 2 Br 9 Exp.Hexagonal ( P 6 3 / mmc )0D––[170](C 5 H 5 NH) 3 Sb 2 Cl 9 Exp.Monoclinic ( C 2/ c )1D––[170]Rb 3 Sb 2 Br 9 Exp.Trigonal ( P m 1)–2.48–[162]Rb 3 Sb 2 I 9 Sim./exp.Monoclinic ( Pc )2D2.10.66[35]Monoclinic ( Pc )–1.94–[162]…”

Section: Heterovalent Substitution With Mono- Tri- and Tetravalent Cmentioning

confidence: 99%

Progress on lead-free metal halide perovskites for photovoltaic applications: a review

2017

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Metal halide perovskites have revolutionized the field of solution-processable photovoltaics. Within just a few years, the power conversion efficiencies of perovskite-based solar cells have been improved significantly to over 20%, which makes them now already comparably efficient to silicon-based photovoltaics. This breakthrough in solution-based photovoltaics, however, has the drawback that these high efficiencies can only be obtained with lead-based perovskites and this will arguably be a substantial hurdle for various applications of perovskite-based photovoltaics and their acceptance in society, even though the amounts of lead in the solar cells are low. This fact opened up a new research field on lead-free metal halide perovskites, which is currently remarkably vivid. We took this as incentive to review this emerging research field and discuss possible alternative elements to replace lead in metal halide perovskites and the properties of the corresponding perovskite materials based on recent theoretical and experimental studies. Up to now, tin-based perovskites turned out to be most promising in terms of power conversion efficiency; however, also the toxicity of these tin-based perovskites is argued. In the focus of the research community are other elements as well including germanium, copper, antimony, or bismuth, and the corresponding perovskite compounds are already showing promising properties.Graphical abstract

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“…A similar concept is applied for perovskite with general formula A 3 B 2 X 9 where a vacancy replaces one every three octahedral B cation. In this case, the electrical charge of the B cation is +3, and the atom species are usually Bi or Sb like in Cs 3 Bi 2 I 9 , Cs 3 Sb 2 I 9 , Rb 3 Bi 2 I 9 , and Rb 3 Sb 2 I 9 . The structure obtained is usually referred to as “2D layered perovskite.” The bandgap of these materials was comprised between 2.05 and 2.24 eV, and the efficiency remained very low (i.e., around or below 1%) …”

Section: Lead‐free Alternativesmentioning

confidence: 99%

Tin Halide Perovskite (ASnX₃) Solar Cells: A Comprehensive Guide toward the Highest Power Conversion Efficiency

Nasti

Abate

2019

Advanced Energy Materials

137

132

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ASnX3 perovskite solar cells (Sn‐PSC) have the potential to deliver the most efficient solar cell technology with safe materials. In this review, a comprehensive introduction of the field is given, that is suitable for nonexperts, gradually leading the reader to a narrower and detailed analysis of the most recent and significant advances. A brief description is given of the leading alternatives for lead‐free PSC and the reasons for ASnX3 compounds' status as one of the most promising candidates are presented. The last part of the review focuses on the stabilization of ASnX3, which is the most compelling challenge to achieve the highest efficiency PSCs. The most promising approaches toward stable and efficient ASnX3 PSCs are identified and discussed.

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

Cited by 69 publications

References 22 publications

Thin-Film Preparation and Characterization of Cs₃Sb₂I₉: A Lead-Free Layered Perovskite Semiconductor

Thin-Film Preparation and Characterization of Cs₃Sb₂I₉: A Lead-Free Layered Perovskite Semiconductor

Progress on lead-free metal halide perovskites for photovoltaic applications: a review

Tin Halide Perovskite (ASnX₃) Solar Cells: A Comprehensive Guide toward the Highest Power Conversion Efficiency

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

Cited by 69 publications

References 22 publications

Thin-Film Preparation and Characterization of Cs3Sb2I9: A Lead-Free Layered Perovskite Semiconductor

Thin-Film Preparation and Characterization of Cs3Sb2I9: A Lead-Free Layered Perovskite Semiconductor

Progress on lead-free metal halide perovskites for photovoltaic applications: a review

Tin Halide Perovskite (ASnX3) Solar Cells: A Comprehensive Guide toward the Highest Power Conversion Efficiency

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Thin-Film Preparation and Characterization of Cs₃Sb₂I₉: A Lead-Free Layered Perovskite Semiconductor

Thin-Film Preparation and Characterization of Cs₃Sb₂I₉: A Lead-Free Layered Perovskite Semiconductor

Tin Halide Perovskite (ASnX₃) Solar Cells: A Comprehensive Guide toward the Highest Power Conversion Efficiency