Tailoring sizes and compositions of heavy pnictogen bismuth thiohalide nanorods and nanowires <i>via</i> heat-up method

Lee, Dawon; Woo, Ho Young; Choi, Yoonjoo; Chung, Hyesun; Paik, Taejong

doi:10.1039/d2ce01588a

Cited by 9 publications

(6 citation statements)

References 54 publications

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“…45,46 Nevertheless, we cannot definitely exclude the possibility of stabilizing heavy pnicotgen chalcohalide perovskites. It is in fact possible that such compounds could be accessible by heat-up, solution phase synthetic methods, 47 exploiting, for example, the reported selectivity of metal thiocyanate precursors to obtaining quaternary heavy pnictogen chalcohalide nanomaterials, while avoiding secondary phases; 48 by ion exchange, an intrinsically kinetically driven process, also using nanostructured metal chalcogenides and halides as precursors; 49,50 more broadly, by topotactic reactions, which may allow the replacement of atoms in a perovskite (nano)crystal without altering the structure; 51,52 by entropic stabilization, which could be in principle be attained given the compositional complexity of quaternary compounds comprising alkali or alkaline-earth metals, heavy pnictogens, chalcogenides, and halides. 53,54 Moreover, ligands could be exploited to affect metal precursor reactivity and selectivity in the attempt to exert phase control in the Bi 2 E 3 −BiX 3 −CsX diagram.…”

Section: T H Imentioning

confidence: 99%

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl₂ Nanocrystals

Quarta,

Tobaldi,

Giansante

2024

J. Phys. Chem. Lett.

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Heavy pnictogen chalcohalides are often termed lead-free, perovskite-inspired materials. Despite theoretical predictions, incontrovertible experimental demonstrations of heavy pnictogen chalcohalides adopting a perovskite structure are lacking. Here we report our attempts to prepare CsBiSCl 2 adopting a perovskite structure as colloidal nanocrystals. Synthesis of nanoscale materials can indeed rely on fast, nonequilibrium reactions and on large, eventually thermodynamically favorable surface energies, leading to the possibility of stabilizing kinetically trapped or metastable phases. However, we obtained no CsBiSCl 2 , but a mixture of nanocrystals of secondary phases, namely Cs 3 BiCl 6 submicrometric polyhedra, Bi 2 S 3 nanoscopic rods, and Cs 3 Bi 2 Cl 9 nanoscopic dots, whose low polydispersity enabled an effective separation via size/shape selective precipitation. This work confirms that heavy pnictogen chalcohalides are hardly prone to adopting a perovskite structure. Nevertheless, chemistry at the nanoscale offers multiple possibilities for overcoming phase segregation and pursuing the synthesis of prospective mixed anion compound semiconductors.

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Section: T H Imentioning

confidence: 99%

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl₂ Nanocrystals

Quarta,

Tobaldi,

Giansante

2024

J. Phys. Chem. Lett.

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“… − However, aside from the preparation of Sn 2 SbS 2 I 3 thin-films employing a high temperature annealing approach, the solution-phase synthesis of tin-based chalcohalides remains relatively unexplored . Moreover, while the colloidal synthesis of bismuth-based, ternary chalcohalides such as BiSI and Bi 13 S 18 I 2 has undergone a renaissance in the past few years, − surprisingly little synthetic attention has been paid to tin-based, ternary chalcohalides such as Sn 2 SI 2 . − …”

mentioning

confidence: 99%

Lead-Free Semiconductors: Phase-Evolution and Superior Stability of Multinary Tin Chalcohalides

Roth,

Porter,

Horger

et al. 2024

Chem. Mater.

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Tin-based semiconductors are highly desirable materials for energy applications due to their low toxicity and biocompatibility relative to analogous lead-based semiconductors. In particular, tin-based chalcohalides possess optoelectronic properties that are ideal for photovoltaic and photocatalytic applications. In addition, they are believed to benefit from increased stability compared with halide perovskites. However, to fully realize their potential, it is first necessary to better understand and predict the synthesis and phase evolution of these complex materials. Here, we describe a versatile solution-phase method for the preparation of the multinary tin chalcohalide semiconductors Sn 2 SbS 2 I 3 , Sn 2 BiS 2 I 3 , Sn 2 BiSI 5 , and Sn 2 SI 2 . We demonstrate how certain thiocyanate precursors are selective toward the synthesis of chalcohalides, thus preventing the formation of binary and other lower order impurities rather than the preferred multinary compositions. Critically, we utilized 119 Sn ssNMR spectroscopy to further assess the phase purity of these materials. Further, we validate that the tin chalcohalides exhibit excellent water stability under ambient conditions, as well as remarkable resistance to heat over time compared to halide perovskites. Together, this work enables the isolation of lead-free, stable, direct band gap chalcohalide compositions that will help engineer more stable and biocompatible semiconductors and devices.

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“…27,28,29 However, aside from the preparation of Sn2SbS2I3 thin-films employing a high temperature annealing approach, 25 the solution-phase synthesis of tin-based chalcohalides remains relatively unexplored. 30 Moreover, while the colloidal synthesis of bismuth-based, ternary chalcohalides such as BiSI and Bi13S18I2 has undergone a renaissance in the past few years, 31,3233,34,35,36,37 surprisingly little synthetic attention has been paid to tin-based, ternary chalcohalides such as Sn2SI2. 38,39,40 Inspired by recent work on the solution-phase synthesis of lead-based chalcohalides, we hypothesized that the solution-phase synthesis of both quaternary and ternary tin chalcohalides could be attained using thiocyanate precursors.…”

mentioning

confidence: 99%

Lead-Free Semiconductors: Phase-Evolution and Superior Stability of Multinary Tin Chalcohalides

Roth,

Porter,

Horger

et al. 2024

Preprint

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Tin-based semiconductors are highly desirable materials for energy applications due to their low toxicity and bio-compatibility relative to analogous lead-based semiconductors. In particular, tin-based chalcohalides possess optoelectronic properties that are ideal for photovoltaic and photocatalytic applications. In addition, they are believed to benefit from increased stability compared to halide perovskites. However, to fully realize their potential, it is first necessary to better understand and predict the synthesis and phase evolution of these complex materials. Here, we describe a versatile solution-phase method for the preparation of the multinary tin chalcohalide semiconductors Sn2SbS2I3, Sn2BiS2I3, Sn2BiSI5, and Sn2SI2. We demonstrate how certain thiocyanate precursors are selective toward the synthesis of chalcohalides, thus preventing the formation of binary and other lower order impurities rather than the preferred multinary compositions. Critically, we utilize 119Sn ssNMR spectroscopy to further assess the phase purity of these materials. Further, we validate that the tin chalcohalides exhibit excellent water stability under ambient conditions, as well as remarkable resistance to heat over time compared to halide perovskites. Together, this work enables the isolation of lead-free, stable, direct band gap chalcohalide compositions that will help engineer more stable and biocompatible semiconductors and devices.

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Tailoring sizes and compositions of heavy pnictogen bismuth thiohalide nanorods and nanowires via heat-up method

Abstract: Herein, we report the size and composition-controlled synthesis of pnictogen bismuth thiohalide (BiSX) nanocrystals (NCs) via the injection-free heat-up method. Colloidal BiSX nanorods (NRs) were synthesized using bismuth halides (BiX3)...

Cited by 9 publications

References 54 publications

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl₂ Nanocrystals

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl₂ Nanocrystals

Lead-Free Semiconductors: Phase-Evolution and Superior Stability of Multinary Tin Chalcohalides

Lead-Free Semiconductors: Phase-Evolution and Superior Stability of Multinary Tin Chalcohalides

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Tailoring sizes and compositions of heavy pnictogen bismuth thiohalide nanorods and nanowires via heat-up method

Abstract: Herein, we report the size and composition-controlled synthesis of pnictogen bismuth thiohalide (BiSX) nanocrystals (NCs) via the injection-free heat-up method. Colloidal BiSX nanorods (NRs) were synthesized using bismuth halides (BiX3)...

Cited by 9 publications

References 54 publications

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl2 Nanocrystals

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl2 Nanocrystals

Lead-Free Semiconductors: Phase-Evolution and Superior Stability of Multinary Tin Chalcohalides

Lead-Free Semiconductors: Phase-Evolution and Superior Stability of Multinary Tin Chalcohalides

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Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl₂ Nanocrystals

Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl₂ Nanocrystals