Cs₃Cu₄In₂Cl₁₃ Nanocrystals : A Perovskite-Related Structure with Inorganic Clusters at A Sites

Summary, in English

An effort to synthesize the Cu(I) variant of a lead-free double perovskite isostructural with Cs₂AgInCl₆ resulted in the formation of Cs₃Cu₄In₂Cl₁₃ nanocrystals with an unusual structure, as revealed by single-nanocrystal three-dimensional electron diffraction. These nanocrystals adopt a A₂BX₆ structure (K₂PtCl₆ type, termed vacancy ordered perovskite) with tetrahedrally coordinated Cu(I) ions. In the structure, 25% of the A sites are occupied by [Cu₄Cl]³⁺ clusters (75% by Cs⁺), and the B sites are occupied by In³⁺. Such a Cs₃Cu₄In₂Cl₁₃ compound prepared at the nanoscale is not known in the bulk and is an example of a multinary metal halide with inorganic cluster cations residing in A sites. The stability of the compound was supported by density functional theory calculations that also revealed that its bandgap is direct but parity forbidden. The existence of the Cs₃Cu₄In₂Cl₁₃ structure demonstrates that small inorganic cluster cations can occupy A sites in multinary metal halides.

• Author: Roman Kaiukov; Guilherme Almeida; Sergio Marras; Zhiya Dang; Dmitry Baranov; Urko Petralanda; Ivan Infante; Enrico Mugnaioli; Andrea Griesi; Luca De Trizio; Mauro Gemmi; Liberato Manna
• Publishing year: 2020-01-06
• Language: English
• Pages: 548-554
• Publication/Series: Inorganic Chemistry
• Volume: 59
• Issue: 1
• Links: http://dx.doi.org/10.1021/acs.inorgchem.9b02834
• Document type: Journal article
• Publisher: The American Chemical Society (ACS)
• Topic: Inorganic Chemistry
• Status: Published
• ISBN/ISSN/Other: ISSN: 0020-1669