Direct Band Gap Chalcohalide Semiconductors: Quaternary AgBiSCl<sub>2</sub> Nanocrystals

Quarta, Danila; Toso, Stefano; Fieramosca, Antonio; Dominici, Lorenzo; Caliandro, Rocco; Moliterni, Anna; Tobaldi, David Maria; Saleh, Gabriele; Gushchina, Irina; Brescia, Rosaria; Prato, Mirko; Infante, Ivan; Cola, Adriano; Giannini, Cinzia; Manna, Liberato; Gigli, Giuseppe; Giansante, Carlo

doi:10.1021/acs.chemmater.3c01403

Cited by 5 publications

(5 citation statements)

References 31 publications

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“…The colloidal NCs were synthesized in three-neck flasks connected to a standard Schlenk line under oxygen- and moisture-free conditions, in analogy to previously reported procedures. − In a typical synthesis attempting to obtain colloidal CsBiSCl 2 NCs, the metal precursor solutions were prepared separately and then mixed. The Bi precursor was prepared as follows: 0.15 mmol (60 mg) of Bi(Ac) 3 and 10 equiv (1.5 mmol, 430 mg) of OlCOOH were mixed in 1.5 g of 1-octadecene; the mixture was vigorously stirred and deaerated through repeated cycles of vacuum application and purging with nitrogen at about 80 °C; the mixture was then heated to above 100 °C to dissolve Bi(Ac) 3 until the solution became colorless and optically transparent, suggesting the complete formation of the bismuth(III)–oleate complex(es).…”

Section: Methodsmentioning

confidence: 99%

“…Here we apply a synthetic method, successfully used to prepare colloidal dispersions of phase pure ternary (orthorhombic BiEX and hexagonal Bi 13 S 18 X 2 ) , and quaternary (orthorhombic AgBiSCl 2 ) heavy pnictogen chalcohalide NCs, to exploring the Cs–Bi–S–Cl phase space (represented in Figure a) and so pursuing the synthesis of colloidal NCs of a prospective AM(E,X) 3 compound adopting a perovskite structure: CsBiSCl 2 (depicted, using VESTA software, as generated by the CrystaLLM model, in Figure b).…”

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confidence: 99%

“…In order to pursue the preparation of CsBiSCl 2 chalcohalide perovskite under far from equilibrium reaction conditions, we used a synthetic approach peculiar to the chemistry of colloidal NCs. − Our synthetic approach to attain CsBiSCl 2 as colloidal NCs involved the co-injection of the S and Cl precursors protected by trimethylsilyl groups ((Me 3 Si) 2 S and (Me 3 Si)Cl, respectively) to a hot solution containing previously prepared Cs– and Bi–carboxylate complexes (details are given in the Supporting Information). The use at relatively high temperatures (180 °C) of highly reactive precursors of the nonmetal elements, due to the Me 3 Si– group that is highly labile especially in the presence of excess oleic acid ligands employed in our protocol, is expected to set the precursor conversion in the diffusion-limited regime.…”

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confidence: 99%

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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: Methodsmentioning

confidence: 99%

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

Quarta,

Tobaldi,

Giansante

2024

J. Phys. Chem. Lett.

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“…In the search for alternatives, chalcohalides are quickly gaining attention as semiconductors for multiple applications. − For example, quaternary lead-free Sn 2 PnS 2 I 3 (where Pn = Sb or Bi) chalcohalides display some of the most desirable features of chalcogenide and halide materials, including direct, visible band gaps (<1.6 eV). − Following their original discovery and crystallographic determination, these materials have earned renewed interest in photovoltaics, thermoelectrics, and catalysis applications. − Furthermore, based on preliminary solar devices, tin chalcohalides are believed to exhibit inherently high stability and power conversion efficiency (PCEs), highlighting their potential as valuable materials for energy conversion. , …”

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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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“…3,4,5 In the search for alternatives, chalcohalides are quickly gaining attention as semiconductors for multiple applications. 6,7,8,9,10,11,12,13 For example, quaternary lead-free Sn2PnS2I3 (where Pn = Sb or Bi) chalcohalides display some of the most desirable features of chalcogenide and halide materials, including direct, visible band gaps (< 1.6 eV). 14,15,16,17,18,19 Following their original discovery and crystallographic determination, these materials have earned renewed interest in photovoltaics, thermoelectrics, and catalysis applications.…”

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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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Direct Band Gap Chalcohalide Semiconductors: Quaternary AgBiSCl₂ Nanocrystals

Cited by 5 publications

References 31 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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Direct Band Gap Chalcohalide Semiconductors: Quaternary AgBiSCl2 Nanocrystals

Cited by 5 publications

References 31 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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Direct Band Gap Chalcohalide Semiconductors: Quaternary AgBiSCl₂ Nanocrystals

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

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