ic9b02834_si_001.pdf (1.14 MB)
Cs3Cu4In2Cl13 Nanocrystals: A Perovskite-Related Structure with Inorganic Clusters at A Sites
journal contribution
posted on 2019-12-12, 20:13 authored by Roman Kaiukov, Guilherme Almeida, Sergio Marras, Zhiya Dang, Dmitry Baranov, Urko Petralanda, Ivan Infante, Enrico Mugnaioli, Andrea Griesi, Luca De Trizio, Mauro Gemmi, Liberato MannaAn 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.