Epitaxial thin films of pyrochlore iridate Bi2+xIr2-yO7-δ: structure, defects and transport properties.

While pyrochlore iridate thin films are theoretically predicted to possess a variety of emergent topological properties, experimental verification of these predictions can be obstructed by the challenge in thin film growth. Here we report on the pulsed laser deposition and characterization of thin films of a representative pyrochlore compound Bi2Ir2O7. The films were epitaxially grown on yttria-stabilized zirconia substrates and have lattice constants that are a few percent larger than that of the bulk single crystals. The film composition shows a strong dependence on the oxygen partial pressure. Density-functional-theory calculations indicate the existence of BiIr antisite defects, qualitatively consistent with the high Bi: Ir ratio found in the films. Both Ir and Bi have oxidation states that are lower than their nominal values, suggesting the existence of oxygen deficiency. The iridate thin films show a variety of intriguing transport characteristics, including multiple charge carriers, logarithmic dependence of resistance on temperature, antilocalization corrections to conductance due to spin-orbit interactions, and linear positive magnetoresistance.

Colossal Terahertz Magnetoresistance at Room Temperature in Epitaxial La0.7Sr0.3MnO3 Nanocomposites and Single-Phase Thin Films.

Colossal magnetoresistance (CMR) is demonstrated at terahertz (THz) frequencies by using terahertz time-domain magnetospectroscopy to examine vertically aligned nanocomposites (VANs) and planar thin films of La0.7Sr0.3MnO3. At the Curie temperature (room temperature), the THz conductivity of the VAN was dramatically enhanced by over 2 orders of magnitude under the application of a magnetic field with a non-Drude THz conductivity that increased with frequency. The direct current (dc) CMR of the VAN is controlled by extrinsic magnetotransport mechanisms such as spin-polarized tunneling between nanograins. In contrast, we find that THz CMR is dominated by intrinsic, intragrain transport: the mean free path was smaller than the nanocolumn size, and the planar thin-film exhibited similar THz CMR to the VAN. Surprisingly, the observed colossal THz magnetoresistance suggests that the magnetoresistance can be large for alternating current motion on nanometer length scales, even when the magnetoresistance is negligible on the macroscopic length scales probed by dc transport. This suggests that colossal magnetoresistance at THz frequencies may find use in nanoelectronics and in THz optical components controlled by magnetic fields. The VAN can be scaled in thickness while retaining a high structural quality and offers a larger THz CMR at room temperature than the planar film.

Strain Localization in Thin Films of Bi(Fe,Mn)O3 Due to the Formation of Stepped Mn(4+)-Rich Antiphase Boundaries.

The atomic structure and chemistry of thin films of Bi(Fe,Mn)O3 (BFMO) films with a target composition of Bi2FeMnO6 on SrTiO3 are studied using scanning transmission electron microscopy imaging and electron energy loss spectroscopy. It is shown that Mn(4+)-rich antiphase boundaries are locally nucleated right at the film substrate and then form stepped structures that are approximately pyramidal in three dimensions. These have the effect of confining the material below the pyramids in a highly strained state with an out-of-plane lattice parameter close to 4.1 Å. Outside the area enclosed by the antiphase boundaries, the out-of-plane lattice parameter is much closer to bulk values for BFMO. This suggests that to improve the crystallographic perfection of the films whilst retaining the strain state through as much of the film as possible, ways need to be found to prevent nucleation of the antiphase boundaries. Since the antiphase boundaries seem to form from the interaction of Mn with the Ti in the substrate, one route to perform this would be to grow a thin buffer layer of pure BiFeO3 on the SrTiO3 substrate to minimise any Mn-Ti interactions.

Synthetic magnetoelectric coupling in a nanocomposite multiferroic.

Given the paucity of single phase multiferroic materials (with large ferromagnetic moment), composite systems seem an attractive solution to realize magnetoelectric coupling between ferromagnetic and ferroelectric order parameters. Despite having antiferromagnetic order, BiFeO3 (BFO) has nevertheless been a key material due to excellent ferroelectric properties at room temperature. We studied a superlattice composed of 8 repetitions of 6 unit cells of La0.7Sr0.3MnO3 (LSMO) grown on 5 unit cells of BFO. Significant net uncompensated magnetization in BFO, an insulating superlattice, is demonstrated using polarized neutron reflectometry. Remarkably, the magnetization enables magnetic field to change the dielectric properties of the superlattice, which we cite as an example of synthetic magnetoelectric coupling. Importantly, controlled creation of magnetic moment in BFO is a much needed path toward design and implementation of integrated oxide devices for next generation magnetoelectric data storage platforms.

Using ultrashort optical pulses to couple ferroelectric and ferromagnetic order in an oxide heterostructure.

A new approach to all-optical detection and control of the coupling between electric and magnetic order on ultrafast timescales is achieved using time-resolved second-harmonic generation (SHG) to study a ferroelectric (FE)/ferromagnet (FM) oxide heterostructure. We use femtosecond optical pulses to modify the spin alignment in a Ba(0.1)Sr(0.9)TiO3 (BSTO)/La(0.7)Ca(0.3)MnO3 (LCMO) heterostructure and selectively probe the ferroelectric response using SHG. In this heterostructure, the pump pulses photoexcite non-equilibrium quasiparticles in LCMO, which rapidly interact with phonons before undergoing spin-lattice relaxation on a timescale of tens of picoseconds. This reduces the spin-spin correlations in LCMO, applying stress on BSTO through magnetostriction. This then modifies the FE polarization through the piezoelectric effect, on a timescale much faster than laser-induced heat diffusion from LCMO to BSTO. We have thus demonstrated an ultrafast indirect magnetoelectric effect in a FE/FM heterostructure mediated through elastic coupling, with a timescale primarily governed by spin-lattice relaxation in the FM layer.

Induced magnetization in La0.7Sr0.3MnO3/BiFeO3 superlattices.

Using polarized neutron reflectometry, we observe an induced magnetization of 75 ± 25 kA/m at 10 K in a La(0.7)Sr(0.3)MnO(3) (LSMO)/BiFeO(3) superlattice extending from the interface through several atomic layers of the BiFeO(3) (BFO). The induced magnetization in BFO is explained by density functional theory, where the size of band gap of BFO plays an important role. Considering a classical exchange field between the LSMO and BFO layers, we further show that magnetization is expected to extend throughout the BFO, which provides a theoretical explanation for the results of the neutron scattering experiment.

Method for controlling energy density for reliable pulsed laser deposition of thin films.

We have established a methodology to stabilize the laser energy density on a target surface in pulsed laser deposition of thin films. To control the focused laser spot on a target, we have imaged a defined aperture in the beamline (so called image-focus) instead of focusing the beam on a target based on a simple "lens-focus." To control the laser energy density on a target, we have introduced a continuously variable attenuator between the output of the laser and the imaged aperture to manipulate the energy to a desired level by running the laser in a "constant voltage" mode to eliminate changes in the lasers' beam dimensions. This methodology leads to much better controllability/reproducibility for reliable pulsed laser deposition of high performance electronic thin films.

Nucleation and growth of epitaxial metal-oxide films based on polymer-assisted deposition.

Polymer-assisted deposition (PAD) is one of the chemical solution deposition methods which have been successfully used to grow films, form coatings, and synthesize nanostructured materials. In comparison with other conventional solution-based deposition techniques, PAD differs in its use of water-soluble polymers in the solution that prevent the metal ions from unwanted chemical reactions and keep the solution stable. Furthermore, filtration to remove non-coordinated cations and anions in the PAD process ensures well controlled nucleation, which enables the growth of high quality epitaxial films with desired structural and physical properties. The precursor solution is prepared by mixing water-soluble polymer(s) with salt(s). Thermal treatment of the precursor films in a controlled environment leads to the formation of desired materials. Using BaTiO3 grown on SrTiO3 and LaMnO3 on LaAlO3 as model systems, we show the effect of filtration on the nucleation and growth of epitaxial complex metal-oxide films based on the PAD process.

Polymer-assisted-deposition: a chemical solution route for a wide range of materials.

In this tutorial article, the recent development of polymer assisted deposition (PAD) for the growth of a wide range of materials, in particular in thin films, is reviewed. Specifically, we describe the unique chemistry and processes of PAD for the deposition of metals, metal-oxides, metal-nitrides, metal-carbides, and their derived composites. Many examples are given not only to illustrate the powerfulness of PAD for high quality coatings, but also to give readers an opportunity to evaluate this technique for specific applications. The challenging issues related to PAD, based on the authors' experience, are also discussed in this review article.

Highly aligned carbon nanotube forests coated by superconducting NbC.

The formation of carbon nanotube and superconductor composites makes it possible to produce new and/or improved functionalities that the individual material does not possess. Here we show that coating carbon nanotube forests with superconducting niobium carbide (NbC) does not destroy the microstructure of the nanotubes. NbC also shows much improved superconducting properties such as a higher irreversibility and upper critical field. An upper critical field value of ~5 T at 4.2 K is much greater than the 1.7 T reported in the literature for pure bulk NbC. Furthermore, the aligned carbon nanotubes induce anisotropy in the upper critical field, with a higher upper critical field occurring when the magnetic field is parallel to the carbon nanotube growth direction. These results suggest that highly oriented carbon nanotubes embedded in superconducting NbC matrix can function as defects and effectively enhance the superconducting properties of the NbC.

Thermal tunability in terahertz metamaterials fabricated on strontium titanate single-crystal substrates.

We report an experimental demonstration of thermal tuning of resonance frequency in a planar terahertz metamaterial consisting of a gold split-ring resonator array fabricated on a bulk single-crystal strontium titanate (SrTiO3) substrate. Cooling the metamaterial starting from 409 K down to 150 K causes about a 43% shift in resonance frequency, and there is very little variation in resonance strength. The resonance shift is due to the temperature-dependent dielectric constant of the strontium titanate. The experiment opens up avenues for designing tunable terahertz devices by exploiting the temperature-sensitive characteristic of high dielectric constant substrates and complex metal oxide materials.

A chemical solution approach for superconducting and hard epitaxial NbC film.

Epitaxial NbC thin films were grown by a chemical solution technique, polymer assisted deposition. High quality epitaxial NbC film showed a transition temperature of 10 K and a hardness of 19.54 GPa.

Nanoconfined surfactant templated electrodeposition to porous hierarchical nanowires and nanotubes.

Porous metal (Pd and Co) and semiconductor (ZnO) nanowires, porous metal (Pt and Ni) nanotubes, and unique multiple Pt nanowires are prepared from a novel nanoconfined surfactant templated electrodeposition approach. More specifically, the overall diameter of nanowires or nanotubes is defined by the pore channels of membranes. Surfactant assembled structure nanoconfined within the pores of membranes is used to generate the porosity and to control the texture of the nanowires or nanotubes. As compared to solid nanowires and nanotubes, the porous nanowires and nanotubes exhibit unique properties. For example, porous cobalt nanowires show higher coercivity.

Tuning the resonance in high-temperature superconducting terahertz metamaterials.

In this Letter, we present resonance properties in terahertz metamaterials consisting of a split-ring resonator array made from high-temperature superconducting films. By varying the temperature, we observe efficient metamaterial resonance switching and frequency tuning. The results are well reproduced by numerical simulations of metamaterial resonance using the experimentally measured complex conductivity of the superconducting film. We develop a theoretical model that explains the tuning features, which takes into account the resistive resonance damping and additional split-ring inductance contributed from both the real and imaginary parts of the temperature-dependent complex conductivity. The theoretical model further predicts more efficient resonance tuning in metamaterials consisting of a thinner superconducting split-ring resonator array, which are also verified in subsequent experiments.

Ultrafast structural phase transition driven by photoinduced melting of charge and orbital order.

We use femtosecond x-ray diffraction to probe directly the structural dynamics of a charge ordered and orbitally ordered thin film of La0.42Ca0.58MnO3 initiated by an ultrafast optical pulse. At low excitation fluences we observe the displacive excitation of a coherent optical A(g) phonon. Under high excitation conditions we observe a complete phase transition within 1 ps via the disappearance of a superlattice reflection. The initial step of the phase transition occurs on a time scale significantly faster than the 200 fs time resolution of our experiment.

Strong and ductile colossal carbon tubes with walls of rectangular macropores.

We report a new type of carbon material-porous colossal carbon tubes. Compared with carbon nanotubes, colossal carbon tubes have a much bigger size, with a diameter of between 40 and 100 mum and a length in the range of centimeters. Significantly, the walls of the colossal tubes are composed of macroscopic rectangular columnar pores and exhibit an ultralow density comparable to that of carbon nanofoams. The porous walls of colossal tubes also show a highly ordered lamellar structure similar to that of graphite. Furthermore, colossal tubes possess excellent mechanical and electrical properties.

Polymer assisted deposition.

Polymer assisted deposition (PAD) is a chemical solution route to high quality thin films of metal oxides. This technique employs metal ions coordinated to polymers as the film precursor. The use of polymer bound metals has several advantages. The polymer controls the viscosity and binds metal ions, resulting in a homogeneous distribution of metal precursors in the solution and the formation of uniform metal oxide films. The nature of the metal oxide deposition is dominated by bottom-up growth, leading to ready formation of crack-free epitaxial metal oxides and the ability to coat nanofeatured substrates in a conformal fashion.

Materials science challenges for high-temperature superconducting wire.

Twenty years ago in a series of amazing discoveries it was found that a large family of ceramic cuprate materials exhibited superconductivity at temperatures above, and in some cases well above, that of liquid nitrogen. Imaginations were energized by the thought of applications for zero-resistance conductors cooled with an inexpensive and readily available cryogen. Early optimism, however, was soon tempered by the hard realities of these new materials: brittle ceramics are not easily formed into long flexible conductors; high current levels require near-perfect crystallinity; and--the downside of high transition temperature--performance drops rapidly in a magnetic field. Despite these formidable obstacles, thousands of kilometres of high-temperature superconducting wire have now been manufactured for demonstrations of transmission cables, motors and other electrical power components. The question is whether the advantages of superconducting wire, such as efficiency and compactness, can outweigh the disadvantage: cost. The remaining task for materials scientists is to return to the fundamentals and squeeze as much performance as possible from these wonderful and difficult materials.