Design Principles for Narrow-Gap Hybrid Semiconductors: Insights from Viologen-Tin and Viologen-Lead Iodides
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| Názov: | Design Principles for Narrow-Gap Hybrid Semiconductors: Insights from Viologen-Tin and Viologen-Lead Iodides |
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| Autori: | Reynolds, Robert, Persaud, Jessica, Volonakis, George, Torma, Andrew, Meza, Patricia, Kelly, Zek, Stoumpos, Constantinos, Dravid, Vinayak, Katan, Claudine, Mohite, Aditya, Kanatzidis, Mercouri |
| Prispievatelia: | KATAN, Claudine |
| Zdroj: | Journal of the American Chemical Society. 147:24573-24593 |
| Informácie o vydavateľovi: | American Chemical Society (ACS), 2025. |
| Rok vydania: | 2025 |
| Predmety: | Hybrid Lead Iodides Viologens, [CHIM.MATE] Chemical Sciences/Material chemistry, Hybrid Lead Iodides, Electronically Active Organics, Anomalous Band-bowing, Charge-Transfer, Optoelectronics, Hybrid Tin Iodides, Infrared, Infrared Optoelectronics, Viologens, [PHYS.COND] Physics [physics]/Condensed Matter [cond-mat] |
| Popis: | Hybrid metal halide semiconductors containing “electronically active” organics are an arising subclass of materials that derive remarkable emergent optical properties from blending organic orbitals with the photophysics of metal halide semiconductors. Although this subclass has been known for some time, the majority of reported compounds are lead halides, and there is a paucity of systematic studies investigating the influence of structure and composition on organic energy levels in these materials. Herein we report the first viologen tin hybrids to be published in the form of: HVSnI4 (HV = hydroviologen), MeVSn2I6 (MeV = methylviologen), and EtVSn2I6 (EtV = ethylviologen). These materials exhibit emergent electronic structures where charge-transfer from the inorganic lattice to viologen LUMO states results in optical gaps as narrow as 1.10eV. Through comparison of these compounds with their lead analogs and viologen iodide salts, we develop a systematic understanding of energy levels and lead/tin systems, which allows us to identify key chemical principles for future narrow-gap hybrid materials. We find that organic LUMO states in these materials are relatively immobile under the exchange of lead with tin but are strongly influenced by substituent choice, conformation, π-π stacking, and the polarizability of the inorganic lattice. We further study the energetic landscape of these materials in a set of lead/tin alloys (EtVPb2-xSnxI6) which do not exhibit the anomalous band-bowing typically associated with lead/tin alloys, providing a new point of evidence that this phenomenon generally relies on concomitant motions of the inorganic conduction and valence band. Photoresponse of HVSnI4 pressed pellet devices to 1064nm light establishes the potential of these materials for NIR optoelectronic applications. |
| Druh dokumentu: | Article |
| Popis súboru: | application/pdf |
| Jazyk: | English |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.5c05202 |
| Rights: | STM Policy #29 |
| Prístupové číslo: | edsair.doi.dedup.....b6a2054e0701d2e816a48fee97fb81cf |
| Databáza: | OpenAIRE |
Nájsť tento článok vo Web of Science | Abstrakt: | Hybrid metal halide semiconductors containing “electronically active” organics are an arising subclass of materials that derive remarkable emergent optical properties from blending organic orbitals with the photophysics of metal halide semiconductors. Although this subclass has been known for some time, the majority of reported compounds are lead halides, and there is a paucity of systematic studies investigating the influence of structure and composition on organic energy levels in these materials. Herein we report the first viologen tin hybrids to be published in the form of: HVSnI4 (HV = hydroviologen), MeVSn2I6 (MeV = methylviologen), and EtVSn2I6 (EtV = ethylviologen). These materials exhibit emergent electronic structures where charge-transfer from the inorganic lattice to viologen LUMO states results in optical gaps as narrow as 1.10eV. Through comparison of these compounds with their lead analogs and viologen iodide salts, we develop a systematic understanding of energy levels and lead/tin systems, which allows us to identify key chemical principles for future narrow-gap hybrid materials. We find that organic LUMO states in these materials are relatively immobile under the exchange of lead with tin but are strongly influenced by substituent choice, conformation, π-π stacking, and the polarizability of the inorganic lattice. We further study the energetic landscape of these materials in a set of lead/tin alloys (EtVPb2-xSnxI6) which do not exhibit the anomalous band-bowing typically associated with lead/tin alloys, providing a new point of evidence that this phenomenon generally relies on concomitant motions of the inorganic conduction and valence band. Photoresponse of HVSnI4 pressed pellet devices to 1064nm light establishes the potential of these materials for NIR optoelectronic applications. |
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| ISSN: | 15205126 00027863 |
| DOI: | 10.1021/jacs.5c05202 |