M. A. Zurbuchen

Crossover from incoherent to coherent phonon scattering in epitaxial oxide superlattices

Elementary particles such as electrons or photons are frequent subjects of wave-nature-driven investigations, unlike collective excitations such as phonons. The demonstration of wave-particle crossover, in terms of macroscopic properties, is crucial to the understanding and application of the wave behaviour of matter. We present an unambiguous demonstration of the theoretically predicted crossover from diffuse (particle-like) to specular (wave-like) phonon scattering in epitaxial oxide superlattices, manifested by a minimum in lattice thermal conductivity as a function of interface density. We do so by synthesizing superlattices of electrically insulating perovskite oxides and systematically varying the interface density, with unit-cell precision, using two different epitaxial-growth techniques. These observations open up opportunities for studies on the wave nature of phonons, particularly phonon interference effects, using oxide superlattices as model systems, with extensive applications in thermoelectrics and thermal management.

Epitaxial growth of non-c-oriented SrBi2Nb2O9 on (111) SrTiO3

Epitaxial SrBi2Nb2O9 thin films have been grown with a (103) orientation on (111) SrTiO3 substrates by pulsed-laser deposition. Four-circle x-ray diffraction and transmission electron microscopy reveal nearly phase-pure epitaxial films. Epitaxial (111) SrRuO3 electrodes enabled the electrical properties of these (103)-oriented SrBi2Nb2O9 films to be measured. The low-field relative permittivity was 185, the remanent polarization was 15.7 μC/cm2, and the dielectric loss was 2.5% for a 0.5-μm-thick film.

Growth of (103) fiber-textured SrBi2Nb2O9 films on Pt-coated silicon

(103) fiber-textured SrBi2Nb2O9 thin films have been grown on Pt-coated Si substrates using a SrRuO3 buffer layer. High-resolution transmission electron microscopy reveals that the fiber texture arises from the local epitaxial growth of (111) SrRuO3 grains on (111) Pt grains and in turn (103) SrBi2Nb2O9 grains on (111) SrRuO3 grains. The films exhibit remanent polarization values of 9 μC/cm2. The uniform grain orientation (fiber texture) should minimize grain-to-grain variations in the remanent polarization, which is important to continued scaling of ferroelectric memory device structures.

Multiferroic composite ferroelectric-ferromagnetic films

Multiferroic behavior was confirmed for epitaxial composite ferroelectric-ferromagnetic heterostructures, using a ferromagnetic crystal as both substrate and straining medium. Heterostructures having 2-2 connectivity (plane-on-plane) were fabricated by chemical solution deposition of Pb(Zr0.3,Ti0.7)O3 (PZT) thin films on La1.2Sr1.8Mn2O7 (LSMO) single crystal substrates. Magnetostriction (0.13%) of the substrate at its transition temperature (∼105K) induces an abrupt 7.3% increase in switchable polarization of the PZT. This confirmation of elastic coupling induced by the onset of ferromagnetism is a first step toward fabricating such structures for study of the interrelationship of their magnetic and electrical field-dependent behaviors.

Ferroelectric domain structures in SrBi2Nb2O9 epitaxial thin films: Electron microscopy and phase-field simulations

Ferroelectric domain structures of (001)SrBi2Nb2O9 epitaxial films, investigated using both transmission electron microscopy and phase-field simulations, are reported. Experiment and numerical simulation both reveal that the domain structures consist of irregularly shaped domains with curved domain walls. It is shown that the elastic contribution to domain structures can be neglected in SrBi2Nb2O9 due to its small ferroelastic distortion, less than 0.0018%. Two-beam dark-field imaging using reflections unique to domains of each of the two 90° polarization axes reveal the domain structure. Phase-field simulation is based on the elastic and electrostatic solutions obtained for thin films under different mechanical and electric boundary conditions. The effects of ferroelastic distortion and dielectric constant on ferroelectric domains are systematically analyzed. It is demonstrated that electrostatic interactions which favor straight domain walls are not sufficient to overcome the domain wall energy which favors curved domains in SrBi2Nb2O9.Ferroelectric domain structures of (001)SrBi2Nb2O9 epitaxial films, investigated using both transmission electron microscopy and phase-field simulations, are reported. Experiment and numerical simulation both reveal that the domain structures consist of irregularly shaped domains with curved domain walls. It is shown that the elastic contribution to domain structures can be neglected in SrBi2Nb2O9 due to its small ferroelastic distortion, less than 0.0018%. Two-beam dark-field imaging using reflections unique to domains of each of the two 90° polarization axes reveal the domain structure. Phase-field simulation is based on the elastic and electrostatic solutions obtained for thin films under different mechanical and electric boundary conditions. The effects of ferroelastic distortion and dielectric constant on ferroelectric domains are systematically analyzed. It is demonstrated that electrostatic interactions which favor straight domain walls are not sufficient to overcome the domain wall energy which fa...

Epitaxial growth and magnetic properties of the first five members of the layered Srn+1RunO3n+1 oxide series

Epitaxial thin films of the n=1–5 members of the layered Srn+1RunO3n+1 oxide series were produced by reactive molecular-beam epitaxy. X-ray diffraction and high-resolution transmission electron microscopy confirm that these films are epitaxially oriented and nearly phase pure (>98%). The Sr2RuO4 (n=1) and Sr3Ru2O7 (n=2) samples show no ferromagnetic transition in the range from 5to300K, while the Sr4Ru3O10 (n=3), Sr5Ru4O13 (n=4), and Sr6Ru5O16 (n=5) samples show ferromagnetic transitions at 85, 95, and 130K, respectively.

Depth-graded multilayers for application in transmission geometry as linear zone plates

Fresnel zone plates for x-ray focusing optics are typically made using lithographic techniques. To achieve optimum efficiency for hard x rays, a depth of several microns is required, which limits the minimum zone width and hence minimum focal spot size achievable using lithography. We are exploring the fabrication of zone plates by an alternative technique that surmounts these limitations: the growth of a multilayer film to be used in transmission (Laue) diffraction geometry, in which the thickness of consecutive layers gradually increases according to the Fresnel zone formula; the film is sectioned after growth to the required depth. For a planar multilayer, this produces a linear zone plate that can focus x rays in one dimension. Here we report the growth and characterization of a depth-graded multilayer suitable for use as a zone plate for hard x-ray focusing. The multilayer has a total of 470 alternating layers of WSi2 and Si with thicknesses increasing monotonically from 15 to 60 nm, for a total thic...

Morphology, structure, and nucleation of out-of-phase boundaries (OPBs) in epitaxial films of layered oxides

Out-of-phase boundaries (OPBs) are translation boundary defects characterized by a misregistry of a fraction of a unit cell dimension in neighboring regions of a crystal. Although rarely observed in the bulk, they are common in epitaxial films of complex crystals due to the physical constraint of the underlying substrate and a low degree of structural rearrangement during growth. OPBs can strongly affect properties, but no extensive studies of them are available. The morphology, structure, and nucleation mechanisms of OPBs in epitaxial films of layered complex oxides are presented with a review of published studies and new work. Morphological trends in two families of layered oxide phases are described. The atomic structure at OPBs is presented. OPBs may be introduced into a film during growth via the primary mechanisms that occur at film nucleation (steric, nucleation layer, a-bmisfit, and inclined-cmisfit) or after growth via the secondary nucleation mechanism (crystallographic shear in response to loss of a volatile component). Mechanism descriptions are accompanied by experimental examples. Alternative methods to the direct imaging of OPBs are also presented.

Epitaxial growth of SrBi2Nb2O9 on (110) SrTiO3 and the establishment of a lower bound on the spontaneous polarization of SrBi2Nb2O9

Epitaxial SrBi2Nb2O9 thin films have been grown on (110) SrTiO3 substrates by pulsed laser deposition. Four-circle x-ray diffraction and transmission electron microscopy reveal nearly phase pure epitaxial films with the c axis of the films at 45° with respect to the substrate normal. Electrical characterization is presented for films grown on epitaxial SrRuO3 electrodes. The low-field relative permittivity was 235, the remanent polarization was 11.4 μC/cm2, and the dielectric loss was 3.0% for 0.3-μm-thick films. From the remanent polarization and an understanding of the epitaxial geometry, a lower bound of 22.8 μC/cm2 was determined for the spontaneous polarization of SrBi2Nb2O9.

Crossover in thermal transport properties of natural, perovskite-structured superlattices

Atomic-level simulations are used to analyze the thermal-transport properties of a naturally layered material: the Ruddlesden–Popper phase, formed by interleaving perovskite layers of strontium titanate with strontium oxide rocksalt layers. The thermal conductivity parallel to the plane of structural layering is found to be systematically greater than that perpendicular to the layering. With decreasing number of perovskite blocks in the structure, a transition is seen from the thermal-transport properties of a bulk solid containing interfaces to that of an anisotropic monolithic material. The exact transition point should be temperature dependent and might enable tuning of the thermal conductance properties of the material.