Mechanisms for collective inversion-symmetry breaking in dabconium perovskite ferroelectrics

Dabconium hybrid perovskites include a number of recently-discovered ferroelectric phases with large spontaneous polarisations. The origin of ferroelectric response has been rationalised in general terms in the context of hydrogen bonding, covalency, and strain coupling. Here we use a combination of simple theory, Monte Carlo simulations, and density functional theory calculations to assess the ability of these microscopic ingredients-together with the always-present through-space dipolar coupling-to account for the emergence of polarisation in these particular systems whilst not in other hybrid perovskites. Our key result is that the combination of A-site polarity, preferred orientation along 111 directions, and ferroelastic strain coupling drives precisely the ferroelectric transition observed experimentally. We rationalise the absence of polarisation in many hybrid perovskites, and arrive at a set of design rules for generating FE examples beyond the dabconium family alone.

Automated summary

In this study, a combination of simple theory, Monte Carlo simulations, and density functional theory calculations was used to analyze the origin and characteristics of ferroelectric phases in Dabconium hybrid perovskites. It was found that the combination of A-site polarity, preferred orientation, and ferroelastic strain coupling are key factors driving the ferroelectric transition observed experimentally, providing design rules for generating FE examples beyond the dabconium family.