Air-Stable Direct Bandgap Perovskite Semiconductors

All-Inorganic Tin-Based Heteroleptic Halides AxSnClyIz (A = Cs, Rb)

Jiangwei Li, Constantinos C. Stoumpos, Giancarlo G. Trimarchi, In Chung, Lingling Mao, Michelle Chen, Michael R Wasielewski, Liduo Wang, Mercouri G Kanatzidis

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Abstract

Semiconducting halide perovskites are a class of materials with exciting photoelectronic properties. Compared to the widely studied hybrid organic-inorganic perovskites, the all-inorganic derivatives are less well understood even as they promise high inherent stability. Currently, such materials are limited due to the fact that there is a very narrow choice of inorganic cations that can stabilize the desirable perovskite structure. Herein we report on the synthesis and characterization of novel all-inorganic tin-based perovskites and perovskitoids that can be stabilized by the heteroleptic coordination of chloride and iodide anions, Cs2SnCl2I2 (1) and Cs2.38Rb1.62Sn3Cl8I2 (2), consist of two-dimensional (2D) layers of [SnCl4I2]4- octahedra with different connectivity modes. Compound 1 is an n = 1 Ruddlesden-Popper type perovskite adopting the tetragonal archetype structure (I4/mmm space group; a = 5.5905(3) Å, c = 18.8982(13) Å), while compound 2 crystallizes as an orthorhombic modification (Cmcm space group; a = 5.6730(11) Å, b = 25.973(5) Å, c = 16.587(3) Å) with corrugated layers. The crystal chemistry changes drastically when Cs+ is replaced by the smaller Rb+ cation which leads to the isolation of the low dimensional compounds Rb3SnCl3I2 (3a), Rb3SnCl2.33I2.67 (3b) and Rb7Sn4.25Cl12I3.5 (4), thus illustrating the importance of the A-cation size in the formation of perovskites. The 2D perovskites show wide band gaps and relatively large resistivities, associated with their chemical stability against the oxidation of Sn2+. The chemical stability is coupled with remarkable electronic properties that derive from the perovskite structure. DFT calculations suggest that both compounds are direct band gap semiconductors with large bandwidths, consistently with the experimentally determined band gaps of Eg = 2.62 and 2.81 eV for 1 and 2, respectively. The combination of stability and favorable electronic structure in heteroleptic-halide perovskites presents a new direction toward the realization of functional devices made exclusively from inorganic perovskites.

Original languageEnglish
Pages (from-to)4847-4856
Number of pages10
JournalChemistry of Materials
Volume30
Issue number14
DOIs
Publication statusPublished - Jul 24 2018

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Tin
Perovskite
Cations
Energy gap
Positive ions
Chemical stability
Semiconductor materials
Air
Crystal chemistry
Iodides
Discrete Fourier transforms
Electronic properties
Electronic structure
Anions
Chlorides
Negative ions
Derivatives
Bandwidth
Oxidation
perovskite

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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Air-Stable Direct Bandgap Perovskite Semiconductors : All-Inorganic Tin-Based Heteroleptic Halides AxSnClyIz (A = Cs, Rb). / Li, Jiangwei; Stoumpos, Constantinos C.; Trimarchi, Giancarlo G.; Chung, In; Mao, Lingling; Chen, Michelle; Wasielewski, Michael R; Wang, Liduo; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 30, No. 14, 24.07.2018, p. 4847-4856.

Research output: Contribution to journalArticle

Li, Jiangwei ; Stoumpos, Constantinos C. ; Trimarchi, Giancarlo G. ; Chung, In ; Mao, Lingling ; Chen, Michelle ; Wasielewski, Michael R ; Wang, Liduo ; Kanatzidis, Mercouri G. / Air-Stable Direct Bandgap Perovskite Semiconductors : All-Inorganic Tin-Based Heteroleptic Halides AxSnClyIz (A = Cs, Rb). In: Chemistry of Materials. 2018 ; Vol. 30, No. 14. pp. 4847-4856.
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abstract = "Semiconducting halide perovskites are a class of materials with exciting photoelectronic properties. Compared to the widely studied hybrid organic-inorganic perovskites, the all-inorganic derivatives are less well understood even as they promise high inherent stability. Currently, such materials are limited due to the fact that there is a very narrow choice of inorganic cations that can stabilize the desirable perovskite structure. Herein we report on the synthesis and characterization of novel all-inorganic tin-based perovskites and perovskitoids that can be stabilized by the heteroleptic coordination of chloride and iodide anions, Cs2SnCl2I2 (1) and Cs2.38Rb1.62Sn3Cl8I2 (2), consist of two-dimensional (2D) layers of [SnCl4I2]4- octahedra with different connectivity modes. Compound 1 is an n = 1 Ruddlesden-Popper type perovskite adopting the tetragonal archetype structure (I4/mmm space group; a = 5.5905(3) {\AA}, c = 18.8982(13) {\AA}), while compound 2 crystallizes as an orthorhombic modification (Cmcm space group; a = 5.6730(11) {\AA}, b = 25.973(5) {\AA}, c = 16.587(3) {\AA}) with corrugated layers. The crystal chemistry changes drastically when Cs+ is replaced by the smaller Rb+ cation which leads to the isolation of the low dimensional compounds Rb3SnCl3I2 (3a), Rb3SnCl2.33I2.67 (3b) and Rb7Sn4.25Cl12I3.5 (4), thus illustrating the importance of the A-cation size in the formation of perovskites. The 2D perovskites show wide band gaps and relatively large resistivities, associated with their chemical stability against the oxidation of Sn2+. The chemical stability is coupled with remarkable electronic properties that derive from the perovskite structure. DFT calculations suggest that both compounds are direct band gap semiconductors with large bandwidths, consistently with the experimentally determined band gaps of Eg = 2.62 and 2.81 eV for 1 and 2, respectively. The combination of stability and favorable electronic structure in heteroleptic-halide perovskites presents a new direction toward the realization of functional devices made exclusively from inorganic perovskites.",
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T2 - All-Inorganic Tin-Based Heteroleptic Halides AxSnClyIz (A = Cs, Rb)

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AU - Stoumpos, Constantinos C.

AU - Trimarchi, Giancarlo G.

AU - Chung, In

AU - Mao, Lingling

AU - Chen, Michelle

AU - Wasielewski, Michael R

AU - Wang, Liduo

AU - Kanatzidis, Mercouri G

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AB - Semiconducting halide perovskites are a class of materials with exciting photoelectronic properties. Compared to the widely studied hybrid organic-inorganic perovskites, the all-inorganic derivatives are less well understood even as they promise high inherent stability. Currently, such materials are limited due to the fact that there is a very narrow choice of inorganic cations that can stabilize the desirable perovskite structure. Herein we report on the synthesis and characterization of novel all-inorganic tin-based perovskites and perovskitoids that can be stabilized by the heteroleptic coordination of chloride and iodide anions, Cs2SnCl2I2 (1) and Cs2.38Rb1.62Sn3Cl8I2 (2), consist of two-dimensional (2D) layers of [SnCl4I2]4- octahedra with different connectivity modes. Compound 1 is an n = 1 Ruddlesden-Popper type perovskite adopting the tetragonal archetype structure (I4/mmm space group; a = 5.5905(3) Å, c = 18.8982(13) Å), while compound 2 crystallizes as an orthorhombic modification (Cmcm space group; a = 5.6730(11) Å, b = 25.973(5) Å, c = 16.587(3) Å) with corrugated layers. The crystal chemistry changes drastically when Cs+ is replaced by the smaller Rb+ cation which leads to the isolation of the low dimensional compounds Rb3SnCl3I2 (3a), Rb3SnCl2.33I2.67 (3b) and Rb7Sn4.25Cl12I3.5 (4), thus illustrating the importance of the A-cation size in the formation of perovskites. The 2D perovskites show wide band gaps and relatively large resistivities, associated with their chemical stability against the oxidation of Sn2+. The chemical stability is coupled with remarkable electronic properties that derive from the perovskite structure. DFT calculations suggest that both compounds are direct band gap semiconductors with large bandwidths, consistently with the experimentally determined band gaps of Eg = 2.62 and 2.81 eV for 1 and 2, respectively. The combination of stability and favorable electronic structure in heteroleptic-halide perovskites presents a new direction toward the realization of functional devices made exclusively from inorganic perovskites.

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