Issue 8, 2016

Tuneable mechanical and dynamical properties in the ferroelectric perovskite solid solution [NH3NH2]1−x[NH3OH]xZn(HCOO)3

Abstract

We report how mechanical and dynamical properties in formate-based perovskites can be manipulated by the preparation of an A-site solid-solution. In the series [NH3NH2]1−x[NH3OH]xZn(HCOO)3 with xmax = 0.48, the substitution of [NH3NH2]+ by [NH3OH]+ is accompanied by a series of complex changes in crystal chemistry which are analysed using PXRD, SCXRD, 1H solid state NMR, DSC and nanoindentation. NMR shows increased motion of [NH3NH2]+ in [NH3NH2]0.52[NH3OH]0.48Zn(HCOO)3, which results in a shift of the ferroelectric-to-paraelectric phase transition temperature from Tc = 352 K (x = 0) to Tc = 324 K (x = 0.48). Additionally, the loss of hydrogen bonds directly influences the mechanical response of the framework; the elastic moduli and hardnesses decrease by around 25% from E110 = 24.6 GPa and H110 = 1.25 GPa for x = 0, to E110 = 19.0 GPa and H110 = 0.97 GPa for x = 0.48. Our results give an in-depth insight into the crystal chemistry of ABX3 formate perovskites and highlight the important role of hydrogen bonding and dynamics.

Graphical abstract: Tuneable mechanical and dynamical properties in the ferroelectric perovskite solid solution [NH3NH2]1−x[NH3OH]xZn(HCOO)3

Supplementary files

Article information

Article type
Edge Article
Submitted
18 mar. 2016
Accepted
11 apr. 2016
First published
12 apr. 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 5108-5112

Tuneable mechanical and dynamical properties in the ferroelectric perovskite solid solution [NH3NH2]1−x[NH3OH]xZn(HCOO)3

G. Kieslich, S. Kumagai, A. C. Forse, S. Sun, S. Henke, M. Yamashita, C. P. Grey and A. K. Cheetham, Chem. Sci., 2016, 7, 5108 DOI: 10.1039/C6SC01247G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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