Polarity discontinuities at the interfaces between different crystalline materials (heterointerfaces) can lead to nontrivial local atomic and electronic structure, owing to the presence of dangling bonds and incomplete atomic coordinations. These discontinuities often arise in naturally layered oxide structures, such as the superconducting copper oxides and ferroelectric titanates, as well as in artificial thin film oxide heterostructures such as manganite tunnel junctions. If polarity discontinuities can be atomically controlled, unusual charge states that are inaccessible in bulk materials could be realized. Here we have examined a model interface between two insulating perovskite oxides--LaAlO3 and SrTiO3--in which we control the termination layer at the interface on an atomic scale. In the simple ionic limit, this interface presents an extra half electron or hole per two-dimensional unit cell, depending on the structure of the interface. The hole-doped interface is found to be insulating, whereas the electron-doped interface is conducting, with extremely high carrier mobility exceeding 10,000 cm2 V(-1) s(-1). At low temperature, dramatic magnetoresistance oscillations periodic with the inverse magnetic field are observed, indicating quantum transport. These results present a broad opportunity to tailor low-dimensional charge states by atomically engineered oxide heteroepitaxy.

A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface

BiFeO3 is perhaps the only material that is both magnetic and a strong ferroelectric at room temperature. As a result, it has had an impact on the field of multiferroics that is comparable to that of yttrium barium copper oxide (YBCO) on superconductors, with hundreds of publications devoted to it in the past few years. In this Review, we try to summarize both the basic physics and unresolved aspects of BiFeO3 (which are still being discovered with several new phase transitions reported in the past few months) and device applications, which center on spintronics and memory devices that can be addressed both electrically and magnetically.

Physics and Applications of Bismuth Ferrite

Dilute ferromagnetic oxides having Curie temperatures far in excess of 300 K and exceptionally large ordered moments per transition-metal cation challenge our understanding of magnetism in solids. These materials are high-k dielectrics with degenerate or thermally activated n-type semiconductivity. Conventional super-exchange or double-exchange interactions cannot produce long-range magnetic order at concentrations of magnetic cations of a few percent. We propose that ferromagnetic exchange here, and in dilute ferromagnetic nitrides, is mediated by shallow donor electrons that form bound magnetic polarons, which overlap to create a spin-split impurity band. The Curie temperature in the mean-field approximation varies as (xdelta)(1/2) where x and delta are the concentrations of magnetic cations and donors, respectively. High Curie temperatures arise only when empty minority-spin or majority-spin d states lie at the Fermi level in the impurity band. The magnetic phase diagram includes regions of semiconducting and metallic ferromagnetism, cluster paramagnetism, spin glass and canted antiferromagnetism.

Donor impurity band exchange in dilute ferromagnetic oxides.

An overview of the state of art in ferroelectric thin films is presented. First, we review applications: microsystems' applications, applications in high frequency electronics, and memories based on ferroelectric materials. The second section deals with materials, structure (domains, in particular), and size effects. Properties of thin films that are important for applications are then addressed: polarization reversal and properties related to the reliability of ferroelectric memories, piezoelectric nonlinearity of ferroelectric films which is relevant to microsystems' applications, and permittivity and loss in ferroelectric films-important in all applications and essential in high frequency devices. In the context of properties we also discuss nanoscale probing of ferroelectrics. Finally, we comment on two important emerging topics: multiferroic materials and ferroelectric one-dimensional nanostructures. (c) 2006 American Institute of Physics.

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Ferroelectric thin films: Review of materials, properties, and applications

The synthesis of carbon nanotubes with predefined structure and functionality plays a central role in the field of nanotechnology1,2, whereas the inhibition of carbon growth is needed to prevent a breakdown of industrial catalysts for hydrogen and synthesis gas production3. The growth of carbon nanotubes and nanofibres has therefore been widely studied4,5,6,7,8,9,10. Recent advances in in situ techniques now open up the possibility of studying gas–solid interactions at the atomic level11,12. Here we present time-resolved, high-resolution in situ transmission electron microscope observations of the formation of carbon nanofibres from methane decomposition over supported nickel nanocrystals. Carbon nanofibres are observed to develop through a reaction-induced reshaping of the nickel nanocrystals. Specifically, the nucleation and growth of graphene layers are found to be assisted by a dynamic formation and restructuring of mono-atomic step edges at the nickel surface. Density-functional theory calculations indicate that the observations are consistent with a growth mechanism involving surface diffusion of carbon and nickel atoms. The finding that metallic step edges act as spatiotemporal dynamic growth sites may be important for understanding other types of catalytic reactions and nanomaterial syntheses.

Atomic-scale imaging of carbon nanofibre growth

We investigated ferromagnetism of a newly discovered ferromagnetic semiconductor Co-doped anatase ${\mathrm{T}\mathrm{i}\mathrm{O}}_{2}$ thin film, using the magnetic circular dichroism (MCD) at the Co ${L}_{2,3}$ absorption edges. The magnetic moment was observed to be $\ensuremath{\sim}0.1{\ensuremath{\mu}}_{B}/\mathrm{C}\mathrm{o}$ in the measurements, but the MCD spectral line shape is nearly identical to that of Co metal, showing that the ferromagnetism is induced by a small amount of clustered Co. With thermal treatments at $\ensuremath{\sim}400\text{ }\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$, the MCD signal increases, and the moment reaches up to $\ensuremath{\sim}1.55{\ensuremath{\mu}}_{B}/\mathrm{C}\mathrm{o}$, which is $\ensuremath{\sim}90%$ of the moment in Co metal. In the latter case, the cluster size was observed to be 20--60 nm.

Ferromagnetism induced by clustered Co in Co-doped anatase TiO2 thin films.

To investigate the critical thickness of ferroelectric BaTiO3 (BTO) films, we fabricated fully strained SrRuO3∕BTO∕SrRuO3 heterostructures on SrTiO3 substrates by pulsed laser deposition with in situ reflection high-energy electron diffraction. We varied the BTO layer thickness from 3to30nm. By fabricating 10×10μm2 capacitors, we could observe polarization versus electric-field hysteresis loops, which demonstrate the existence of ferroelectricity in BTO layers thicker than 5nm. This observation provides an experimental upper bound of 5nm for the critical thickness. The BTO thickness-dependent scaling of the remanent polarization agrees with the predictions of recent first-principle simulations [J. Junquera and P. Ghosez, Nature 422, 506 (2003)].

Critical thickness of ultrathin ferroelectric BaTiO3 films

Multiferroic BiFeO3 epitaxial films with thicknesses ranging from 40to960nm were grown by pulsed laser deposition on SrTiO3 (001) substrates with SrRuO3 bottom electrodes. X-ray characterization shows that the structure evolves from angularly distorted tetragonal with c∕a≈1.04 to more bulklike distorted rhombohedral (c∕a≈1.01) as the strain relaxes with increasing thickness. Despite this significant structural evolution, the ferroelectric polarization along the body diagonal of the distorted pseudocubic unit cells, as calculated from measurements along the normal direction, barely changes.

Effect of epitaxial strain on ferroelectric polarization in multiferroic BiFeO3 films

Multiferroic BiFeO3 epitaxial films with thickness ranging from 40 nm to 960 nm were grown by pulsed laser deposition on SrTiO3 (001) substrates with SrRuO3 bottom electrodes. X-ray characterization shows that the structure evolves from angularly-distorted tetragonal with c/a ~ 1.04 to more bulk-like distorted rhombohedral (c/a ~ 1.01) as the strain relaxes with increasing thickness. Despite this significant structural evolution, the ferroelectric polarization along the body diagonal of the distorted pseudo-cubic unit cells, as calculated from measurements along the normal direction, barely changes.

We demonstrate using four-circle x-ray diffraction that the piezoelectric substrate of Pb(Mg1/3Nb2/3)0.72Ti0.28O3(001) induces uniform reversible in-plane strain to epitaxially-grown oxide films and bilayers. The biaxial in-plane strain depends linearly on the applied electrical voltage. Utilizing the reversible strain, the strain-dependent lattice structure and the Poisson number characterizing the elastic response is determined for 200 nm thick SrTiO3, LaScO3, and BiFeO3 films. The uniformity and reversibility of the strain provides access to the direct quantitative measurement of strain-dependent properties of epitaxial oxide films.

Dae Ho Kim

Papers

Ferromagnetism induced by clustered Co in Co-doped anatase TiO2 thin films.

Critical thickness of ultrathin ferroelectric BaTiO3 films

Effect of epitaxial strain on ferroelectric polarization in multiferroic BiFeO3 films

Effect of epitaxial strain on ferroelectric polarization in multiferroic BiFeO3 films

Applying uniform reversible strain to epitaxial oxide films