Completely Solvent-free Protocols to Access Phase-Pure, Metastable Metal Halide Perovskites and Functional Photodetectors from the Precursor Salts

Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or solvent(s). Herein, we report the application of solvent-free mechanochemical ball milling for the synthesis of metal halide perovskites, to overc...

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Published iniScience Vol. 16; pp. 312 - 325
Main Authors Hong, Zonghan, Tan, Davin, John, Rohit Abraham, Tay, Yong Kang Eugene, Ho, Yan King Terence, Zhao, Xin, Sum, Tze Chien, Mathews, Nripan, García, Felipe, Soo, Han Sen
Format Journal Article
LanguageEnglish
Published United States Elsevier 28.06.2019
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Abstract Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or solvent(s). Herein, we report the application of solvent-free mechanochemical ball milling for the synthesis of metal halide perovskites, to overcome problems with solution-based syntheses. We prepared phase-pure, air-sensitive CsSnX (X = I, Br, Cl) and its mixed halide perovskites by mechanochemistry for the first time by reactions between cesium and tin(II) halides. Notably, we report the sole examples where metastable, high-temperature phases like cubic CsSnCl , cubic CsPbI , and trigonal FAPbI were accessible at ambient temperatures and pressures without post-synthetic processing. The perovskites can be prepared up to "kilogram scales." Lead-free, all-inorganic photodetector devices were fabricated using the mechanosynthesized CsSnBr Cl under solvent-free conditions and showed 10-fold differences between on-off currents. We highlight an essentially solvent-free, general approach to synthesize metastable compounds and fabricate photodetectors from commercially available precursors.
AbstractList Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or solvent(s). Herein, we report the application of solvent-free mechanochemical ball milling for the synthesis of metal halide perovskites, to overcome problems with solution-based syntheses. We prepared phase-pure, air-sensitive CsSnX (X = I, Br, Cl) and its mixed halide perovskites by mechanochemistry for the first time by reactions between cesium and tin(II) halides. Notably, we report the sole examples where metastable, high-temperature phases like cubic CsSnCl , cubic CsPbI , and trigonal FAPbI were accessible at ambient temperatures and pressures without post-synthetic processing. The perovskites can be prepared up to "kilogram scales." Lead-free, all-inorganic photodetector devices were fabricated using the mechanosynthesized CsSnBr Cl under solvent-free conditions and showed 10-fold differences between on-off currents. We highlight an essentially solvent-free, general approach to synthesize metastable compounds and fabricate photodetectors from commercially available precursors.
Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or solvent(s). Herein, we report the application of solvent-free mechanochemical ball milling for the synthesis of metal halide perovskites, to overcome problems with solution-based syntheses. We prepared phase-pure, air-sensitive CsSnX3 (X = I, Br, Cl) and its mixed halide perovskites by mechanochemistry for the first time by reactions between cesium and tin(II) halides. Notably, we report the sole examples where metastable, high-temperature phases like cubic CsSnCl3, cubic CsPbI3, and trigonal FAPbI3 were accessible at ambient temperatures and pressures without post-synthetic processing. The perovskites can be prepared up to “kilogram scales.” Lead-free, all-inorganic photodetector devices were fabricated using the mechanosynthesized CsSnBr1.5Cl1.5 under solvent-free conditions and showed 10-fold differences between on-off currents. We highlight an essentially solvent-free, general approach to synthesize metastable compounds and fabricate photodetectors from commercially available precursors. : Devices; Energy Materials; Materials Synthesis Subject Areas: Devices, Energy Materials, Materials Synthesis
Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or solvent(s). Herein, we report the application of solvent-free mechanochemical ball milling for the synthesis of metal halide perovskites, to overcome problems with solution-based syntheses. We prepared phase-pure, air-sensitive CsSnX 3 (X = I, Br, Cl) and its mixed halide perovskites by mechanochemistry for the first time by reactions between cesium and tin(II) halides. Notably, we report the sole examples where metastable, high-temperature phases like cubic CsSnCl 3 , cubic CsPbI 3 , and trigonal FAPbI 3 were accessible at ambient temperatures and pressures without post-synthetic processing. The perovskites can be prepared up to “kilogram scales.” Lead-free, all-inorganic photodetector devices were fabricated using the mechanosynthesized CsSnBr 1.5 Cl 1.5 under solvent-free conditions and showed 10-fold differences between on-off currents. We highlight an essentially solvent-free, general approach to synthesize metastable compounds and fabricate photodetectors from commercially available precursors. • Mechanochemistry provided a solvent-free perovskite and device fabrication process • Direct access to metastable phases of perovskites without post-synthetic annealing • Energy- and time-efficient synthetic protocol demonstrated up to kilogram scales • Procedures applicable for lead-based, air-sensitive tin(II), and other perovskites Devices; Energy Materials; Materials Synthesis
Author Hong, Zonghan
Tay, Yong Kang Eugene
Ho, Yan King Terence
Sum, Tze Chien
García, Felipe
Zhao, Xin
Tan, Davin
John, Rohit Abraham
Soo, Han Sen
Mathews, Nripan
AuthorAffiliation 1 Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore
5 Solar Fuels Laboratory, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
2 School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
3 Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore
4 Energy Research Institute @NTU (ERI@N), Research Techno Plaza, X-Frontier Block, Level 5, 50 Nanyang Drive, Singapore 637553, Singapore
AuthorAffiliation_xml – name: 2 School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
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– name: 5 Solar Fuels Laboratory, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
– name: 1 Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore
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  surname: Mathews
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  email: ERI@N, nripan@ntu.edu.sg
  organization: School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore; Energy Research Institute @NTU (ERI@N), Research Techno Plaza, X-Frontier Block, Level 5, 50 Nanyang Drive, Singapore 637553, Singapore. Electronic address: nripan@ntu.edu.sg
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  fullname: García, Felipe
  email: fgarcia@ntu.edu.sg
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  givenname: Han Sen
  surname: Soo
  fullname: Soo, Han Sen
  email: hansen@ntu.edu.sg
  organization: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore; Solar Fuels Laboratory, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore. Electronic address: hansen@ntu.edu.sg
BackLink https://www.ncbi.nlm.nih.gov/pubmed/31203187$$D View this record in MEDLINE/PubMed
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Snippet Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or...
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Title Completely Solvent-free Protocols to Access Phase-Pure, Metastable Metal Halide Perovskites and Functional Photodetectors from the Precursor Salts
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