http://sces.phys.utk.edu/mostcited/mc1_1114.pdf

Colossal Magnetoresistant Materials: The Key Role of Phase Separation

In this chapter, we will restrict our attention to the ferrites and a few other closely related materials. The great interest in ferrites stems from their unique combination of a spontaneous magnetization and a high electrical resistivity. The observed magnetization results from the difference in the magnetizations of two non-equivalent sub-lattices of the magnetic ions in the crystal structure. Materials of this type should strictly be designated as “ferrimagnetic” and in some respects are more closely related to anti-ferromagnetic substances than they are to ferromagnetics in which the magnetization results from the parallel alignment of all the magnetic moments present. We shall not adhere to this special nomenclature except to emphasize effects, which are due to the existence of the sub-lattices.

Ferromagnetic materials

This review covers important advances in recent years in the physics of thin-film ferroelectric oxides, the strongest emphasis being on those aspects particular to ferroelectrics in thin-film form. The authors introduce the current state of development in the application of ferroelectric thin films for electronic devices and discuss the physics relevant for the performance and failure of these devices. Following this the review covers the enormous progress that has been made in the first-principles computational approach to understanding ferroelectrics. The authors then discuss in detail the important role that strain plays in determining the properties of epitaxial thin ferroelectric films. Finally, this review ends with a look at the emerging possibilities for nanoscale ferroelectrics, with particular emphasis on ferroelectrics in nonconventional nanoscale geometries.

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Physics of thin-film ferroelectric oxides

Predictions and measurements of the effect of biaxial strain on the properties of epitaxial ferroelectric thin films and superlattices are reviewed. Results for single-layer ferroelectric films of biaxially strained SrTiO3, BaTiO3, and PbTiO3 as well as PbTiO3/SrTiO3 and BaTiO3/SrTiO3 superlattices are described. Theoretical ap- proaches, including first principles, thermodynamic analysis, and phase-field models, are applied to these biaxially strained materials, the assumptions and limitations of each technique are explained, and the predictions are compared. Measurements of the effect of biax- ial strain on the paraelectric-to-ferroelectric transition temperature (TC) are shown, demonstrating the ability of percent-level strains to shift TC by hundreds of degrees in agreement with the predic- tions that predated such experiments. Along the way, important ex- perimental techniques for characterizing the properties of strained ferroelectric thin films and superlattices, as well as appropriate sub- strates on which to grow them, are mentioned.

/pdf/strain-tuning-of-ferroelectric-thin-films-i3r81086fk.pdf

Strain Tuning of Ferroelectric Thin Films

Giant and isotropic magnetoresistance as huge as −53% was observed in magnetic manganese oxide La0.72Ca0.25MnOz films with an intrinsic antiferromagnetic spin structure. We ascribe this magnetoresistance to spin‐dependent electron scattering due to spin canting of the manganese oxide.

31p-S-4 Giant Magnetoresistance in Magnetic Manganese Oxide with Intrinsic Antiferromagnetic Spin Structure

A survey of recent experimental results is given, presenting the growth of oxide epitaxial thin films in P−T−x conditions, which are far from those necessary for the existence of corresponding phases in a bulk state. The unstable in bulk BaCu3O4, NdMn7O12, RNiO3, and unusual polymorphous forms of BaRuO3, RMnO3, TiO2, and Mn3O4 are some examples. The stabilizing effect is observed only if epitaxial growth is induced. A rich variety of the effect observations are demonstrated to be of a thermodynamic origin, rather than of a kinetic one. Epitaxial stabilization is shown to be the result of the low energy of coherent interfaces formed due to epitaxy.

Epitaxial Stabilization of Oxides in Thin Films

Perovskite manganites derived from LaMnO3 have recently become the subject of intensive study following the discovery of ‘colossal’ magnetoresistance (a magnetically induced change in electrical resistance of up to several orders of magnitude) in several members of this family of compounds1. The manganites exhibit a broad range of electronic and magnetic phases, ranging from low-resistance ferromagnetic metals to high-resistance insulators, which are extremely sensitive to variation of composition2, temperature and pressure3. A recent study showed that such sensitivity also extends to oxygen isotope exchange4: replacing 16O with 18O in La0.8Ca0.2MnO3 produces an unusually large change in the magnetic properties (a 21-kelvin decrease in the Curie temperature). The magnitude of this isotope shift is evidence for the essential role played by electron–phonon coupling5 in determining the transport properties of these materials. Here we show that this sensitivity to oxygen isotope exchange can be even more extreme. In its normal state, the compound La0.175Pr0.525Ca0.3MnO3 undergoes an insulator-to-metal transition as it is cooled below ∼95 K. But we find that, after substituting 18O for 16O, the compound remains an insulator down to 4.2 K, so providing a vivid demonstration of the importance of lattice vibrations in these materials.

Metal–insulator transition induced by oxygen isotope exchange in the magnetoresistive perovskite manganites

We have succeeded in the preparation of thin films of rare-earth nickelates RNiO3 (R=Pr, Nd, Sm, and Gd) under reduced oxygen pressure <0.02 bar by metalorganic chemical-vapor deposition owing to their epitaxial stabilization on perovskite substrates. The film–substrate lattice mismatch is critical for the epitaxial stabilization of RNiO3 phases. Increase of the lattice mismatch or film thickness results in the deposition of rare-earth oxides and NiO instead of RNiO3. The epitaxial films of nickelates were strained and consisted of 90° domains with the orthorhombic Pnma structure. The transport properties of the strained films on LaAlO3 were similar to those of the bulk material of the same composition under applied pressure of 9 kbar but they were different from the properties of the bulk material under ambient pressure. The result implies that transport properties of RNiO3 films with sharp metal-to-insulator transition can be effectively tuned by the control of the lattice strain.

Perovskite rare-earth nickelates in the thin-film epitaxial state

For the first time the magnetocaloric properties of La0.9Ag0.1MnO3, La0.8Ag0.2MnO3, La0.85Ag0.15MnO3, La0.8Ag0.15MnO3 and La0.8Ag0.1MnO3 manganites have been investigated by direct and indirect measurement techniques. All samples showed almost the same relative cooling power (RCP). Temperatures of maxima of the magnetocaloric effect (MCE) are between a few degrees below freezing and the room temperature region. The compounds showed RCP values of about 100 J kg−1 at a field change of 2.6 T, which is about half the RCP of gadolinium. Because of considerable MCE and the Curie temperatures ranging from 269 to 303 K, these materials could be used as magnetic refrigerants for magnetic refrigeration in the sub-room and room temperature range.

O. Yu. Gorbenko

Papers

Epitaxial Stabilization of Oxides in Thin Films

Metal–insulator transition induced by oxygen isotope exchange in the magnetoresistive perovskite manganites

Perovskite rare-earth nickelates in the thin-film epitaxial state

Magnetocaloric effect in La1−xAgyMnO3 (y ⩽ x): direct and indirect measurements

The structure and properties of Mn3O4 thin films grown by MOCVD