Issue 37, 2020

Hydrothermal growth of facet-tunable fluoride perovskite crystals KMF3 (M = Mg, Mn, Co, Ni and Zn)

Abstract

Perovskite-structured ABX3 halides are one of the most promising families of materials with many potential applications. However, the controllable growth methods of their crystal facets and the corresponding synthetic chemistry have not yet been resolved. In this paper, we report a ligand substitution strategy for the facet-tunable growth of perovskite structure KMF3 (M = Mg, Mn, Co, Ni and Zn) fluorides under mild hydrothermal conditions. The competition of the strong ligand of NH3 and weak ligand of F in the octahedral crystal fields of M2+ results in different facet evolution routes for KMF3 samples with the M-site of empty-, partially- or fully-filled 3d orbitals. Although X-ray diffraction results indicated that all five KMF3 compounds are crystalized into the same space group (Pm[3 with combining overline]m, no. 221), the crystal shape of KMF3 with M = Mg, Mn, Co and Ni evolved from cubic shape to edge-truncated chamfer box shape, while KZnF3 evolved from cubic shape to corner-truncated cubic shape under the same set of synthetic conditions. The cubic shape habitat morphology of KMF3 crystals is enclosed by {100} facets, chamfer box {100} and {110} facets, and corner-truncated cube {100} and {111} facets. The crystal shape formation mechanism was analysed based on ligand field theory and the Bravais–Friedel–Donnay–Harker (BFDH) theory. We expect that the shape controllable synthetic method can benefit the growth of other halide material crystals, and the shape tunable crystals can find more important applications.

Graphical abstract: Hydrothermal growth of facet-tunable fluoride perovskite crystals KMF3 (M = Mg, Mn, Co, Ni and Zn)

Supplementary files

Article information

Article type
Paper
Submitted
03 Jun 2020
Accepted
17 Aug 2020
First published
18 Aug 2020

CrystEngComm, 2020,22, 6216-6227

Hydrothermal growth of facet-tunable fluoride perovskite crystals KMF3 (M = Mg, Mn, Co, Ni and Zn)

L. Yuan, L. Ge, X. Sun, J. Zhang, J. Yu, C. Zhang and H. Li, CrystEngComm, 2020, 22, 6216 DOI: 10.1039/D0CE00807A

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