Proton-transfer Ferroelectricity / Multiferroicity in Rutile Oxyhydroxides

Abstract

Oxyhydroxide minerals like FeOOH have been a research focus in geology for studying the Earth interior, and also in chemistry for studying oxygen electrocatalysis activity. In this paper we provide first-principles evidence of a new class of ferroelectrics or multiferroics among them:GaOOH,InOOH,CrOOH,FeOOH, which are earth-abundant minerals and have been experimentally verified to possess distorted rutile structures, are ferroelectric with considerable polarizations(up to 24 muC/cm2) and piezoelectric coefficients. Their atomic-thick layer may possess vertical polarization robust against depolarizing field due to the formation of O-H O bonds that can hardly be symmetrized. Moreover,CrOOH (guyanaite) is revealed to be a combination of high-Tc in-plane type-I multiferroics and vertical type-II multiferroics, which is strain-tunable and may render a desirable coupling between magnetism and ferroelectricity. Supported by experimental evidence on reversible conversion between metal oxyhydroxides and dioxides and their nice lattice match that renders convenient epitaxial growth, heterostructure composed of oxyhydroxides and prevalent metal dioxides (e.g. TiO2, SnO2 and CrO2) may be constructed for various applications like ferroelectric field-effect transistors and multiferroic tunneling junctions