Study of disorder in pulsed laser deposited double perovskite oxides by first-principle structure prediction

Double perovskite oxides,with generalized formula A_(2)BB'O_(6),attract wide interest due to their multiferroic and charge transfer properties.They offer a wide range of potential applications such as spintronics and electrically tunable devices.However,great practical limitations are encountered,since a spontaneous order of the B-site cations is notoriously hard to achieve.In this joint experimental-theoretical work,we focused on the characterization of double perovskites La2TiFeO6 and La_(2)VCuO_(6) films grown by pulsed laser deposition and interpretation of the observed B-site disorder and partial charge transfer between the B-site ions.A random structure sampling method was used to show that several phases compete due to their corresponding configurational entropy.In order to capture a representative picture of the most relevant competing microstates in realistic experimental conditions,this search included the potential formation of non-stoichiometric phases as well,which could also be directly related to the observed partial charge transfer.We optimized the information encapsulated in the potential energy landscape,captured via structure sampling,by evaluating both enthalpic and entropic terms.These terms were employed as a metric for the competition of different phases.This approach,applied herein specifically to La_(2)TiFeO_(6),highlights the presence of highly entropic phases above the ground state which can explain the disorder observed frequently in the broader class of double perovskite oxides.

From Slater to Mott physics by epitaxially engineering electronic correlations in oxide interfaces

Using spin-assisted ab initio random structure searches,we explore an exhaustive quantum phase diagram of archetypal interfaced Mott insulators,i.e.lanthanum-iron and lanthanum-titanium oxides.In particular,we report that the charge transfer induced by the interfacial electronic reconstruction stabilises a high-spin ferrous Fe2+state.We provide a pathway to control the strength of correlation in this electronic state by tuning the epitaxial strain,yielding a manifold of quantum electronic phases,i.e.Mott-Hubbard,charge transfer and Slater insulating states.Furthermore,we report that the electronic correlations are closely related to the structural oxygen octahedral rotations,whose control is able to stabilise the low-spin state of Fe2+at low pressure previously observed only under the extreme high pressure conditions in the Earth’s lower mantle.Thus,we provide avenues for magnetic switching via THz radiations which have crucial implications for next generation of spintronics technologies.