arXiv subjects

Craig J. Fennie

Publications and source records attributed to Craig J. Fennie.

At least 37 records · Page 2Linked to original sources

arXiv2012

The Magnetoelectric Effect in Transition Metal Oxides: Insights and the Rational Design of New Materials from First Principles

The search for materials displaying a large magnetoelectric effect has occupied researchers for many decades. The rewards could include not only advanced electronics technologies, but also fundamental insights concerning the dielectric and magnetic properties of condensed matter. In this article, we focus on the magnetoelectric effect in transition metal oxides and review the manner in which first-principles calculations have helped guide the search for (and increasingly, predicted) new materials and shed light on the microscopic mechanisms responsible for magnetoelectric phenomena.

cond-mat.mtrl-sci↗

arXiv2012

Electrical properties of improper ferroelectrics from first principles

We study the interplay of structural and polar distortions in hexagonal YMnO3 and short-period PbTiO3/SrTiO3 superlattices by means of first-principles calculations at constrained electric displacement field D. We find that in YMnO3 the tilts of the oxygen polyhedra produce a robustly polar ground state, which persists at any choice of the electrical boundary conditions. Conversely, in PTO/STO the antiferrodistortive instabilities alone do not break inversion symmetry, and open-circuit bundary conditions restore a non-polar state. We suggest that this qualitative difference naturally provides a route to rationalizing the concept of "improper ferroelectricity" from the point of view of first-principles theory. We discuss the implications of our arguments for the design of novel multiferroic materials with enhanced functionalities, and for the symmetry analysis of the phase transitions.

cond-mat.mtrl-sci↗

arXiv2012

Octahedral rotation-induced ferroelectricity in cation ordered perovskites

Increasing demands for electric field-tunable electric, magnetic, and orbital (EMO) materials has renewed interests in ferroelectricity and its coupling to EMO properties in complex perovskite oxides. The historic design strategy to achieve a spontaneous polarization involves the incorporation of second-order Jahn-Teller (SOJT) active cations. The challenge, however, is that this mechanism is limited to specific chemistries and the polar distortions that arise are largely decoupled from EMO properties, limiting their use as field-tunable multifunctional technology materials. Here we report the crystal-chemistry criteria which circumvents those restrictions and enables the rational design of new materials displaying octahedral rotation-induced ferroelectricity - an innovative route to realize electric polarization without the need for SOJT cations - from non-polar building blocks. The strategy exploits the centric octahedral rotation patterns, which strongly couple to EMO properties, and cation ordering commonly observed in non-polar $AB$O$_3$ perovskites. By uniting switchable electric polarizations to the connectivity of the transition-metal oxygen octahedra, electric-field control over materials properties is possible.

cond-mat.mtrl-sci↗

arXiv2012

Polar octahedral rotations: a path to new multifunctional materials

Perovskite ABO$_3$ oxides display an amazing variety of phenomena that can be altered by subtle changes in the chemistry and internal structure, making them a favorite class of materials to explore the rational design of novel properties. Here we highlight a recent advance in which rotations of the BO$_6$ octahedra give rise to a novel form of ferroelectricity -- hybrid improper ferroelectricity. Octahedral rotations also strongly influence other structural, magnetic, orbital, and electronic degrees of freedom in perovskites and related materials. Octahedral rotation-driven ferroelectricity consequently has the potential to robustly control emergent phenomena with an applied electric field. The concept of `functional' octahedral rotations is introduced and the challenges for materials chemistry and the possibilities for new rotation-driven phenomena in multifunctional materials are explored.

cond-mat.mtrl-sci↗

arXiv2012

Interface control of emergent ferroic order in Ruddlesden-Popper Sr$_{n+1}$Ti$_n$O$_{3n+1}$

We have discovered from first-principles an unusual polar state in the low n Sr$_{n+1}$Ti$_n$O$_{3n+1}$ Ruddlesden-Popper (RP) layered perovskites in which ferroelectricity is nearly degenerate with antiferroelectricity, a relatively rare form of ferroic order. We show that epitaxial strain plays a key role in tuning the "perpendicular coherence length" of the ferroelectric mode, and does not induce ferroelectricity in these low dimensional RP materials as is well known to occur in SrTiO$_3$. These systems present an opportunity to manipulate the coherence length of a ferroic distortion in a controlled way, without disorder or a free surface.

cond-mat.mtrl-sci↗

arXiv2011

RbFe2+Fe3+F6: Synthesis, Structure, and Characterization of a New Charge-Ordered Magnetically Frustrated Pyrochlore-Related Mixed-Metal Fluoride

A new charge-ordered magnetically frustrated mixed-metal fluoride with a pyrochlore-related structure has been synthesized and characterized. The material, RbFe2F6 (RbFe2+Fe3+F6) was synthesized through mild hydrothermal conditions. The material exhibits a three-dimensional pyrochlore-related structure consisting of corner-shared Fe2+F6 and Fe3+F6 octahedra. In addition to single crystal diffraction data, neutron powder diffraction and magnetometry measurements were carried out. Magnetic data clearly reveal strong antiferromagnetic interactions (a Curie-Weiss temperature of -270 K) but sufficient frustration to prevent ordering until 16 K. No structural phase transformation is detected from the variable temperature neutron diffraction data. Infrared, UV -vis, thermogravimetric, and differential thermal analysis measurements were also performed. First-principles density functional theory (DFT) electronic structure calculations were also done. Crystal data: RbFe2F6, orthorhombic, space group Pnma (No. 62), a = 7.0177(6) Å, b = 7.4499(6) Å, c = 10.1765(8) Å, V = 532.04(8) Å3, Z = 4.

cond-mat.mtrl-sci↗

arXiv2011

Band Gap and Edge Engineering via Ferroic Distortion and Anisotropic Strain: The Case of SrTiO$_{3}$

The effects of ferroic distortion and biaxial strain on the band gap and band edges of SrTiO$_{3}$ (STO) are calculated using density functional theory and many-body perturbation theory. Anisotropic strains are shown to reduce the gap by breaking degeneracies at the band edges. Ferroic distortions are shown to widen the gap by allowing new band edge orbital mixings. Compressive biaxial strains raise band edge energies, while tensile strains lower them. To reduce the STO gap, one must lower the symmetry from cubic while suppressing ferroic distortions. Our calculations indicate that for engineered orientation of the growth direction along [111], the STO gap can be controllably and considerably reduced at room temperature.

cond-mat.mtrl-sci↗

arXiv2010

Hybrid Improper Ferroelectricity: A Mechanism for Controllable Magnetization-Polarization Coupling

First-principles calculations are presented for the layered perovskite Ca$_3$Mn$_2$O$_7$. The results reveal a rich set of coupled structural, magnetic and polar domains in which oxygen octahedron rotations induce ferroelectricity, magnetoelectricity and weak-ferromagnetism. The key point is that the rotation distortion is a combination of two non-polar modes with different symmetries. We use the term "hybrid" improper ferroelectricity to describe this phenomenon and discuss how control over magnetism is achieved through these functional antiferrodistortive octahedron rotations.

cond-mat.mtrl-sci↗

arXiv2008

Absence of Critical Thickness in an Ultrathin Improper Ferroelectric Film

We study the ferroelectric stability and surface structural properties of an oxygen-terminated hexagonal YMnO$_3$ ultra-thin film using density functional theory. Under an open circuit boundary condition, the ferroelectric state with the spontaneous polarization normal to the (0001) surface, is found to be metastable in a single domain state despite the presence of a depolarizing field. We establish a connection between the result and the role of improper ferroelectric transition. Our results imply that improper ferroelectric ultrathin films can have rather unique properties that are distinctive from those of very thin films of ordinary ferroelectrics.

cond-mat.mtrl-sci↗

arXiv2008

Response to "Comment on Ferroelectrically induced weak ferromagnetism by design," by R. de Sousa and J. E. Moore, arXiv:0806.2142

A recent Comment [arXiv:0806.2142] has argued that "there is a simple duality between A-site and B-site" R3c ABO$_3$ materials and that our Letter [PRL 100, 167203 (2208)] "breaks this duality by ignoring a non-polar distortion that is directly measured in crystallography." Here we point out that this is not correct. The Comment contains three elementary crystallographic errors. In this response we address each error in some detail.

cond-mat.mtrl-sci↗

arXiv2008

Electric-field switchable magnetization via the Dzyaloshinskii-Moriya interaction: FeTiO_3 versus BiFeO_3

In this article we review and discuss a mechanism for coupling between electric polarization and magnetization that can ultimately lead to electric-field switchable magnetization. The basic idea is that a ferroelectric distortion in an antiferromagnetic material can "switch on" the Dzyaloshinskii-Moriya interaction which leads to a canting of the antiferromagnetic sublattice magnetizations, and thus to a net magnetization. This magnetization M is coupled to the polarization P via a trilinear free energy contribution of the form P(M x L), where L is the antiferromagnetic order parameter. In particular, we discuss why such an invariant is present in R3c FeTiO_3 but not in the isostructural multiferroic BiFeO_3. Finally, we construct symmetry groups that in general allow for this kind of ferroelectrically-induced weak ferromagnetism.

cond-mat.mtrl-sci↗

arXiv2007

Ferroelectrically induced weak-ferromagnetism in a single-phase multiferroic by design

We present a strategy to design structures for which a polar lattice distortion induces weak ferromagnetism. We identify a large class of multiferroic oxides as potential realizations and use density-functional theory to screen several promising candidates. By elucidating the interplay between the polarization and the Dzyaloshinskii-Moriya vector, we show how the direction of the magnetization can be switched between 180$^{\circ}$ symmetry equivalent states with an applied electric field.

cond-mat.mtrl-sci↗

arXiv2007

Lattice instabilities in cubic pyrochlore Bi$_2$Ti$_2$O$_7$

The oxide pyrochlore Bi$_2$Ti$_2$O$_7$ is in some ways analogous to perovskite PbTiO$_3$, in that Bi$_2$Ti$_2$O$_7$ has two cations, Bi$^{3+}$ and Ti$^{4+}$ in oxidation states that are normally associated with a propensity to off-center. However, unlike PbTiO$_3$, Bi$_2$Ti$_2$O$_7$ is experimentally observed to remain cubic down to 2 K, while the only observed ionic displacements are local and incoherent. Here we report first-principles calculations of the zone-center phonons of the ordered cubic pyrochlore which reveal several lattice instabilities. An analysis of the structural energetics suggest that the ordered cubic pyrochlore is unstable with respect to distortion towards a ferroelectric ground state with a large polarization. Our results suggest a key role of a frustrated soft polar mode in the dielectric properties of bismuth pyrochlores.

cond-mat.mtrl-sci↗

arXiv2007

Spin-Filtering Multiferroic-Semiconductor Heterojunctions

We report on the structural and electronic properties of the interface between the multiferoic oxide YMnO$_3$ and wide band-gap semiconductor GaN studied with the Hubbard-corrected local spin density approximation (LSDA+U) to density-functional theory (DFT). We find that the band offsets at the interface between antiferromagnetically ordered YMnO$_3$ and GaN are different for spin-up and spin-down states. This behavior is due to the spin splitting of the valence band induced by the interface. The energy barrier depends on the relative orientation of the electric polarization with respect to the polarization direction of the GaN substrate suggesting an opportunity to create magnetic tunnel junctions in this materials system.

cond-mat.mtrl-sci↗

arXiv2006

Magnetic and electric phase control in epitaxial EuTiO$_3$ from first principles

We propose a design strategy - based on the coupling of spins, optical phonons, and strain - for systems in which magnetic (electric) phase control can be achieved by an applied electric (magnetic) field. Using first-principles density-functional theory calculations, we present a realization of this strategy for the magnetic perovskite EuTiO$_3$.

cond-mat.mtrl-sci↗

arXiv2006

Ferroelectricity in the Dion-Jacobson CsBiNb$_2$O$_7$ from first principles

We have studied ferroelectricity in Dion-Jacobson CsBiNb$_2$O$_7$ from first principles. Using group-theoretical analysis and first-principles density functional calculations of the total energy and phonons, we perform a systematic study of the energy surface around a paraelectric prototypic phase. Our results suggest that CsBiNb$_2$O$_7$ is a ferroelectric with a polarization of P$_s$=40$μ$C cm$^{-2}$. We propose further experiments to clarify this point.

cond-mat.mtrl-sci↗

arXiv2006

Magnetic-induced phonon anisotropy in ZnCr$_2$O$_4$ from first principles

We have studied the influence of magnetic order on the optical phonons of the geometrically frustrated spinel ZnCr$_2$O$_4$ from first-principles. By mapping the first-principles phonon calculations onto a Heisenberg-like model, we developed a method to calculate exchange derivatives and subsequently the spin-phonon couping parameter from first-principles. All calculations were performed within LSDA+U.

cond-mat.mtrl-sci↗

arXiv2005

The ferroelectric transition in YMnO$_3$ from first principles

We have studied the structural phase transition of multiferroic YMnO$_3$ from first principles. Using group-theoretical analysis and first-principles density functional calculations of the total energy and phonons, we perform a systematic study of the energy surface around the prototypic phase. We find a single instability at the zone-boundary which couples strongly to the polarization. This coupling is the mechanism that allows multiferroicity in this class of materials. Our results imply that YMnO$_3$ is an improper ferroelectric. We suggest further experiments to clarify this point.

cond-mat.mtrl-sci↗