James M. Rondinelli

K3B6O10Cl: A New Structure Analogous to Perovskite with a Large Second Harmonic Generation Response and Deep UV Absorption Edge

Introduction of the Cl(-) anion in the borate systems generates a new perovskite-like phase, K(3)B(6)O(10)Cl, which exhibits a large second harmonic response, about four times that of KH(2)PO(4) (KDP), and is transparent from the deep UV (180 nm) to middle-IR region. K(3)B(6)O(10)Cl crystallizes in the noncentrosymmetric and rhombohedral space group R3m. The structure consists of the A-site hexaborate [B(6)O(10)] groups and the BX(3) Cl-centered octahedral [ClK(6)] groups linked together through vertices to form the perovskite framework represented by ABX(3).

Designing a Deep-Ultraviolet Nonlinear Optical Material with a Large Second Harmonic Generation Response

The generation of intense coherent deep-UV light from nonlinear optical materials is crucial to applications ranging from semiconductor photolithography and laser micromachining to photochemical synthesis. However, few materials with large second harmonic generation (SHG) and a short UV-cutoff edge are effective down to 200 nm. A notable exception is KBe2BO3F2, which is obtained from a solid-state reaction of highly toxic beryllium oxide powders. We designed and synthesized a benign polar material, Ba4B11O20F, that satisfies these requirements and exhibits the largest SHG response in known borates containing neither lone-pair-active anions nor second-order Jahn-Teller-active transition metals. We developed a microscopic model to explain the enhancement, which is unexpected on the basis of conventional anionic group theory arguments. Crystal engineering of atomic displacements along the polar axis, which are difficult to attribute to or identify within unique anionic moieties, and greater cation polarizabilities are critical to the design of next-generation SHG materials.

Carrier-mediated magnetoelectricity in complex oxide heterostructures

Increasing demands for high-density, stable nanoscale memory elements, as well as fundamental discoveries in the field of spintronics, have led to renewed interest in exploring the coupling between magnetism and electric fields. Although conventional magnetoelectric routes often result in weak responses, there is considerable current research activity focused on identifying new mechanisms for magnetoelectric coupling. Here we demonstrate a linear magnetoelectric effect that arises from a carrier-mediated mechanism, and is a universal feature of the interface between a dielectric and a spin-polarized metal. Using first-principles density functional calculations, we illustrate this effect at the SrRuO3/SrTiO3 interface and describe its origin. To formally quantify the magnetic response of such an interface to an applied electric field, we introduce and define the concept of spin capacitance. In addition to its magnetoelectric and spin capacitive behaviour, the interface displays a spatial coexistence of magnetism and dielectric polarization, suggesting a route to a new type of interfacial multiferroic.

Cs3Zn6B9O21: a chemically benign member of the KBBF family exhibiting the largest second harmonic generation response.

Nonlinear optical (NLO) crystals are essential materials for generation of coherent UV light in solid state lasers. KBBF is the only material that can achieve coherent light below 200 nm by direct second harmonic generation (SHG). However, its strong layer habits and the high toxicity of the beryllium oxide powders required for synthesis limit its application. By substituting Be with Zn and connecting adjacent [Zn2BO3O2]∞ layers by B3O6 groups, a new UV nonlinear optical material, Cs3Zn6B9O21, was synthesized. It overcomes the processing limitations of KBBF and exhibits the largest SHG response in the KBBF family.

Whither the oxide interface

Interfaces formed by transition-metal oxide materials offer a tremendous opportunity for fundamental as well as applied research. Yet, as exciting as these opportunities are, several challenges remain.

Structure and Properties of Functional Oxide Thin Films: Insights From Electronic‐Structure Calculations

The confluence of state-of-the-art electronic-structure computations and modern synthetic materials growth techniques is proving indispensable in the search for and discovery of new functionalities in oxide thin films and heterostructures. Here, we review the recent contributions of electronic-structure calculations to predicting, understanding, and discovering new materials physics in thin-film perovskite oxides. We show that such calculations can accurately predict both structure and properties in advance of film synthesis, thereby guiding the search for materials combinations with specific targeted functionalities. In addition, because they can isolate and decouple the effects of various parameters which unavoidably occur simultaneously in an experiment-such as epitaxial strain, interfacial chemistry and defect profiles-they are able to provide new fundamental knowledge about the underlying physics. We conclude by outlining the limitations of current computational techniques, as well as some important open questions that we hope will motivate further methodological developments in the field.

Octahedral Rotation‐Induced Ferroelectricity in Cation Ordered Perovskites

Electronic structure calculations based on density functional theory have uncovered a novel mechanism for inducing ferroelectric polarizations in cation ordered perovskites. We outline a materials selection strategy for designing this behavior. The guidelines are based on the octahedral rotations found in the two constituent oxides and the way the perovskite building blocks are interwoven to form the superlattice.

Quantifying octahedral rotations in strained perovskite oxide films

We have measured the oxygen positions in

Turning ABO3 Antiferroelectrics into Ferroelectrics: Design Rules for Practical Rotation-Driven Ferroelectricity in Double Perovskites and A3B2O7 Ruddlesden-Popper Compounds

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Colloquium : Emergent properties in plane view: Strong correlations at oxide interfaces

films to elucidate the coupling between epitaxial strain and oxygen octahedral rotations. The oxygen positions are determined by comparing the measured and calculated intensities of half-order Bragg peaks, arising from the octahedral rotations. Combining ab initio density-functional calculations with these experimental results, we show how strain systematically modifies both bond angles and lengths in this functional perovskite oxide.