Tuneable mechanical and dynamical properties in the ferroelectric perovskite solid solution [NH3 NH2 ]1-x [NH3 OH] x Zn(HCOO)3

Chemical Science
Gregor KieslichAnthony K Cheetham

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] x Zn(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.

References

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Jun 1, 2015·Chemical Science·Gregor KieslichAnthony K Cheetham

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Citations

Mar 15, 2019·Chemical Communications : Chem Comm·Michael G EhrenreichGregor Kieslich
Aug 5, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Stefan BurgerGregor Kieslich
Jun 2, 2017·Chemical Science·Keith T ButlerGregor Kieslich
May 13, 2017·Chemistry : a European Journal·Yao YuSong Gao
Dec 15, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Hanna L B BoströmAndrew L Goodwin
Nov 25, 2016·Scientific Reports·E TenutaO Rubel
Sep 28, 2017·Chemical Communications : Chem Comm·Xiaoxuan DiXiaojuan Liang
Jul 4, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Shu LiuSong Gao
Jun 25, 2016·Physical Chemistry Chemical Physics : PCCP·Mantas ŠimėnasEvaldas E Tornau
Jul 15, 2016·Journal of the American Chemical Society·Nicole L EvansAndrew L Goodwin
Dec 9, 2017·The Journal of Physical Chemistry Letters·Katrine L SvaneKeith T Butler

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Methods Mentioned

BETA
X-ray
nuclear
NMR

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