Suppressed Magnetization at the Surfaces and Interfaces of Ferromagnetic Metallic Manganites

What happens to ferromagnetism at the surfaces and interfaces of manganites? With the competition between charge, spin, and orbital degrees of freedom, it is not surprising that the surface behavior may be profoundly different than that of the bulk. Using a powerful combination of two surface probes, tunneling and polarized x-ray interactions, this paper reviews our work on the nature of the electronic and magnetic states at manganite surfaces and interfaces. The general observation is that ferromagnetism is not the lowest energy state at the surface or interface, which results in a suppression or even loss of ferromagnetic order at the surface. Two cases will be discussed ranging from the surface of the quasi-2D bilayer manganite (La$_{2-2x}$Sr$_{1+2x}$Mn$_2$O$_7$) to the 3D Perovskite (La$_{2/3}$Sr$_{1/3}$MnO$_3$)/SrTiO$_3$ interface. For the bilayer manganite, that is, ferromagnetic and conducting in the bulk, these probes present clear evidence for an intrinsic insulating non-ferromagnetic surface layer atop adjacent subsurface layers that display the full bulk magnetization. This abrupt intrinsic magnetic interface is attributed to the weak inter-bilayer coupling native to these quasi-two-dimensional materials. This is in marked contrast to the non-layered manganite system (La$_{2/3}$Sr$_{1/3}$MnO$_3$/SrTiO$_3$), whose magnetization near the interface is less than half the bulk value at low temperatures and decreases with increasing temperature at a faster rate than the bulk.Comment: 15 pages, 13 figure

Extrinsic Magnetotransport Phenomena in Ferromagnetic Oxides

This review is focused on extrinsic magnetotransport effects in ferromagnetic oxides. It consists of two parts; the second part is devoted to an overview of experimental data and theoretical models for extrinsic magnetotransport phenomena. Here a critical discussion of domain-wall scattering is given. Results on surfacial and interfacial magnetism in oxides are presented. Spin-polarized tunnelling in ferromagnetic junctions is reviewed and grain-boundary magnetoresistance is interpreted within a model of spin-polarized tunnelling through natural oxide barriers. The situation in ferromagnetic oxides is compared with data and models for conventional ferromagnets. The first part of the review summarizes basic material properties, especially data on the spin-polarization and evidence for half-metallicity. Furthermore, intrinsic conduction mechanisms are discussed. An outlook on the further development of oxide spin-electronics concludes this review.Comment: 133 pages, 47 figures, submitted to Rep. Prog. Phy

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss

Spin blockade effects in chromium oxide intergrain magnetoresistance

CrO2 thin films with crystallites of a significant size permit investigation of the thin intergrain conduction between a limited numbers of crystals. Phoemission techniques reveal that the CrO2 films are covered by a 1–2-nm-thick Cr2O3 insulating barrier. The electronic band gap of the surface electrons is 3.4 eV at low temperatures, decreases sharply down to 2.8 eV at ambient. Electric transport though a few junctions in series shows a remarkable zero-bias anomaly, interpreted in terms of blockade effects. We show that the magnetoresistance is governed by low-bias blockade in these junctions. © 2002 American Institute of Physics. [DOI: 10.1063/1.1452240