Control of octahedral connectivity in perovskite oxide heterostructures: An emerging route to multifunctional materials discovery

Rondinelli, James M.; May, Steven J.; Freeland, J. W.

doi:10.1557/mrs.2012.49

Cited by 410 publications

(388 citation statements)

References 104 publications

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“…Although there are 15 distinct ways in which the octahedra can cooperatively rotate while retaining connectivity (as identified by Glazer), 46 the vast majority exhibit either an orthorhombic or rhombohedral tilt pattern (given by a − a − c + or a − a − a − in Glazer notation, respectively). A high degree of control over the electronic structure can be achieved by using epitaxial strain (or chemical substation, as captured by τ ) to control these rotations, owing primarily to the strong coupling between the lattice and electronic degrees of freedom in perovskites ( Figure 9a); [47][48][49][50] as mentioned previously, buckling of the B-O-B bond away from a linear 180 • configuration (i.e., increasing the magnitude of the octahedral rotations) decreases the overlap between the O p and metal B d orbitals, thereby increasing the band gap in insulating compounds or inducing bandwidth-driven metal-insulator transitions. [51][52][53][54][55][56] As we have shown, the distinct alternating tetrahedral and octahedral layers in brownmillerites allow for many more structural degrees of freedom than perovskites.…”

Section: Comparison To Perovskite Oxidesmentioning

confidence: 99%

Crystal structure and electronic properties of bulk and thin film brownmillerite oxides

Young¹,

Rondinelli²

2015

Phys. Rev. B

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The equilibrium structure and functional properties exhibited by brownmillerite oxides, a family of perovskite-derived structures with alternating layers of BO6 octahedra and BO4 tetrahedra, viz., ordered arrangements of oxygen vacancies, is dependent on a variety of competing crystal-chemistry factors. We use electronic structure calculations to disentangle the complex interactions in two ferrates, Sr2Fe2O5 and Ca2Fe2O5, relating the stability of the equilibrium (strain-free) and thin film structures to both previously identified and newly herein proposed descriptors. We show that cation size and intralayer separation of the tetrahedral chains provide key contributions to the preferred ground state. We show the bulk ground state structure is retained in the ferrates over a range of strain values; however, a change in the orientation of the tetrahedral chains, i.e., a perpendicular orientation of the vacancies relative to the substrate, is stabilized in the compressive region. The structure stability under strain is largely governed by maximizing the intraplane separation of the 'dipoles' generated from rotations of the FeO4 tetrahedra. Lastly, we find that the electronic band gap is strongly influenced by strain, manifesting as an unanticipated asymmetric-vacancy alignment dependent response. This atomistic understanding establishes a practical route for the design of functional electronic materials in thin film geometries.

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Section: Comparison To Perovskite Oxidesmentioning

confidence: 99%

Crystal structure and electronic properties of bulk and thin film brownmillerite oxides

Young¹,

Rondinelli²

2015

Phys. Rev. B

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“…[5][6][7][8][9][10][11][12][13][14][15][16] Symmetry mismatch occurs when the interface is formed from two non-isostructural materials such as an orthorhombic film on a cubic substrate, or even materials consisting of different coordination environments.…”

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confidence: 99%

Symmetry‐Driven Atomic Rearrangement at a Brownmillerite–Perovskite Interface

Meyer

Jeen

Gao

et al. 2015

Adv Elect Materials

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The design of new materials has transformed considerably over the past decade from an emphasis on tailoring bulk properties to those isolated at the interface between two materials.Undoubtedly, many would argue that the interface is the key to new, multifunctional materials and devices. Examples include the discovery of a 2-dimensional electron gas (2DEG) and thermopower enhancement in LaTiO 3 /SrTiO 3 (STO) heterostructures [1][2][3] , electric-field control of spin polarization between ferroelectric and ferromagnetic film layers [4] and colossal ionic conductivity at the yttria-stabilized ZrO 2 (YSZ)/STO interface [5] . The strong property modification in heterostructures such as these suggests that the structural, electronic, lattice and orbital degrees of freedom at the interface can be tuned from the individual constituents.Many of the interfacial properties that have drawn significant attention have been linked to structural effects induced by lattice or symmetry mismatch. [5][6][7][8][9][10][11][12][13][14][15][16] Symmetry mismatch occurs when the interface is formed from two non-isostructural materials such as an orthorhombic film on a cubic substrate, or even materials consisting of different coordination environments.While it is possible for non-isostructural bilayers to contain a negligible average lattice mismatch, low symmetry materials grown on higher symmetry substrates will likely exhibit an unavoidable non-uniform strain due to different lattice parameters along the in-plane

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“…The concept of interfacial octahedral coupling resides in the idea that the substrate tends to transmit its octahedral pattern to the film. This concept has motivated an intense research on its use for the engineering of novel tilt patterns with specific functionalities (Rondinelli and Spaldin, 2011;Rondinelli et al, 2012;Moon et al, 2014). Excitingly, recent advances in electron microscopy have provided direct access to oxygen positions (Jia et al, 2009;Borisevich et al, 2010a), and though direct experimental evidences are still very scarce, indeed they support the idea of octahedral coupling across the interfaces.…”

Section: Octahedral Tilt Discontinuitiesmentioning

confidence: 99%

“…This behavior stems from the confluence of strongly competing charge, spin, orbital and lattice degrees of freedom, the coupling between them, and a surprisingly versatile mechanical response of octahedral frameworks to external perturbations. A radically new concept that holds strong promise for the predictive manipulation of the framework topology is the translation of the octahedral pattern of the substrate to the film (Rondinelli et al, 2012). Nevertheless, detailed knowledge on the boundaries between elastic, electronic, octahedral tilting, and plastic deformation regimes , as well as on the ability to control polar discontinuities (Dagotto, 2009;Boschker et al, 2012), is still needed to avoid interactions that could interfere with octahedral couplings.…”

Section: Future Prospectsmentioning

confidence: 99%

Interfaces and Nanostructures of Functional Oxide Octahedral Framework Structures

Sandiumenge¹,

Bagués²,

Santiso³

2014

Front. Mater.

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In the past decade, the rich physics exhibited by solid interfaces combining octahedral framework structures of transition-metal oxides has fascinated the materials science community. However, their behavior still eludes the current understanding of classical semiconductor and metal epitaxy. The reason for that is rooted in the surprising versatility of linked coordination units to adapt to a dissimilar substrate and the strong sensitivity of strongly correlated electron oxides to external perturbations. The confluence of atomic control in oxide thin film epitaxy, state of the art high spatial resolution characterization techniques, and electronic-structure computations, has allowed in recent years to obtain first insights on the microscopic mechanisms governing the epitaxy of these complex materials.

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Control of octahedral connectivity in perovskite oxide heterostructures: An emerging route to multifunctional materials discovery

Abstract: Abstract

Cited by 410 publications

References 104 publications

Crystal structure and electronic properties of bulk and thin film brownmillerite oxides

Crystal structure and electronic properties of bulk and thin film brownmillerite oxides

Symmetry‐Driven Atomic Rearrangement at a Brownmillerite–Perovskite Interface

Interfaces and Nanostructures of Functional Oxide Octahedral Framework Structures

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