We review recent experimental work falling under the broad classification of colossal magnetoresistance (CMR), which is magnetoresistance associated with a ferromagnetic-toparamagnetic phase transition. The prototypical CMR compound is derived from the parent compound, perovskite LaMnO 3. When hole doped at a concentration of 20–40% holes/Mn ion, for instance by Ca or Sr substitution for La, the material displays a transition from a high-temperature paramagnetic insulator to a low-temperature ferromagnetic metal. Near the phase transition temperature, which can exceed room temperature in some compositions, large magnetoresistance is observed and its possible application in magnetic recording has revived interest in these materials. In addition, unusual magneto-elastic effects and charge ordering have focused attention on strong electron–phonon coupling. This coupling, which is a type of dynamic extended-system version of the Jahn–Teller effect, in conjunction with the double-exchange interaction, is also viewed as essential for a microscopic description of CMR in the manganite perovskites. Large magnetoresistance is also seen in other systems, namely Tl 2Mn2O7 and some Cr chalcogenide spinels, compounds which differ greatly from the manganite perovskites. We describe the relevant points of contrast between the various CMR materials.

REVIEW ARTICLE: Colossal magnetoresistance

Ferroelectric oxide materials have offered a tantalizing potential for applications since the discovery of ferroelectric perovskites more than 50 years ago. Their switchable electric polarization is ideal for use in devices for memory storage and integrated microelectronics, but progress has long been hampered by difficulties in materials processing. Recent breakthroughs in the synthesis of complex oxides have brought the field to an entirely new level, in which complex artificial oxide structures can be realized with an atomic-level precision comparable to that well known for semiconductor heterostructures. Not only can the necessary high-quality ferroelectric films now be grown for new device capabilities, but ferroelectrics can be combined with other functional oxides, such as high-temperature superconductors and magnetic oxides, to create multifunctional materials and devices. Moreover, the shrinking of the relevant lengths to the nanoscale produces new physical phenomena. Real-space characterization and manipulation of the structure and properties at atomic scales involves new kinds of local probes and a key role for first-principles theory.

http://science.sciencemag.org/content/sci/303/5657/488.full.pdf

Ferroelectricity at the Nanoscale: Local Polarization in Oxide Thin Films and Heterostructures

The manganese oxides of general formula RE1−xMxMnO3 (RE = rare earth, M = Ca, Sr, Ba, Pb) have remarkable interrelated structural, magnetic and transport properties induced by the mixed valence (3+–4+) of the Mn ions. In particular, they exhibit very large negative magnetoresistance, called colossal magnetoresistance (CMR), in the vicinity of metal–insulator transition for certain compositions. In this review paper, we summarize the most important features of the physics of the CMR manganites. The growth techniques for manganese oxide thin films, which are the basic material for potential applications, are reviewed and their structure and morphology examined in relation to growth parameters. The effects of epitaxial strains on the physical properties are discussed. Early works on superlattices and devices are presented.

http://iopscience.iop.org/article/10.1088/0022-3727/36/8/201/pdf

CMR manganites: physics, thin films and devices

▪ Abstract Scanning force microscopy (SFM) is becoming a powerful technique with great potential both for imaging and for control of domain structures in ferroelectric materials at the nanometer scale. Application of SFM to visualization of domain structures in ferroelectric thin films is described. Imaging methods of ferroelectric domains are based on the detection of surface charges in the noncontact mode of SFM and on the measurement of the piezoelectric response of a ferroelectric film to an external field applied by the tip in the SFM contact mode. This latter mode can be used for nondestructive evaluation of local ferroelectric and piezoelectric properties and for manipulation of domains of less than 50 nm in diameter. The effect of the film thickness and crystallinity on the imaging resolution is discussed. Scanning force microscopy is shown to be a technique well suited for nanoscale investigation of switching processes and electrical degradation effects in ferroelectric thin films.

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Imaging and control of domain structures in ferroelectric thin films via scanning force microscopy

The surface chemistry of cerium oxide

An investigation designed to display the intrinsic properties of perovskite manganites was accomplished by comparing the behavior of bulk samples with that of thin films. Epitaxial 1500 \AA{} films of perovskite ${\mathrm{La}}_{0.67}$${\mathrm{Ca}}_{0.33}$Mn${\mathrm{O}}_{3}$ and ${\mathrm{La}}_{0.67}$${\mathrm{Sr}}_{0.33}$Mn${\mathrm{O}}_{3}$ were grown by solid source chemical vapor deposition on LaAl${\mathrm{O}}_{3}$ and post annealed in oxygen at 950 \ifmmode^\circ\else\textdegree\fi{}C. Crystals were prepared by laser heated pedestal growth. The magnetic and electrical transport properties of the polycrystalline pellets, crystals, and annealed films are essentially the same. Below $\frac{{T}_{C}}{2}$ the intrinsic magnetization decreases as ${T}^{2}$ (as can be expected for itinerant electron ferromagnets) while the intrinsic resistivity increases proportional to ${T}^{2}$. The constant and ${T}^{2}$ coefficients of the resistivity are largely independent of magnetic field and alkaline earth element (Ca, Sr, or Ba). Hall effect measurements indicate that holes are mobile carriers in the metallic state. We identify three distinct types of negative magnetoresistance. The largest effect, observed near the Curie temperature, is 25% for the Sr and 250% [$\frac{\ensuremath{\Delta}R}{R(H)}$] for the Ca compound. There is also magnetoresistance associated with the net magnetization of polycrystalline samples which is not seen in films. Finally a small magnetoresistance linear in $H$ is observed even at low temperatures. The high temperature (above ${T}_{C}$) resistivity of ${\mathrm{La}}_{0.67}$${\mathrm{Ca}}_{0.33}$Mn${\mathrm{O}}_{3}$ is consistent with small polaron hopping conductivity with a slight transition at 750 K, while ${\mathrm{La}}_{0.67}$${\mathrm{Sr}}_{0.33}$Mn${\mathrm{O}}_{3}$ does not exhibit activated conductivity until about 500 K, well above ${T}_{C}$. The limiting low and high temperature resistivities place a limit on the maximum possible magnetoresistance of these materials and may explain why the "colossal" magnetoresistance reported in the literature correlates with the suppression of ${T}_{C}$.

Intrinsic electrical transport and magnetic properties of La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 MOCVD thin films and bulk material.

Nanometer size polarized domains were written in a PbZr1−xTixO3 (PZT) thin film using an atomic force microscope (AFM) and the relationship between the polarized domain and the grain of the film was investigated. The polarized domain was formed by applying a pulse voltage to the ferroelectric PZT thin film through a conductive AFM tip. The polarized domain structure was observed by imaging the piezoelectric‐induced surface vibration by an AFM with an ac voltage applied between the tip and the bottom electrode of a sample. The polarized domains with a diameter of 50 nm were written within a single grain.

Formation and observation of 50 nm polarized domains in PbZr1−xTixO3 thin film using scanning probe microscope

Resistivity measurements on a La0.67Ca0.33MnO3 film are reported for a series of argon anneals at successively higher temperatures. Tc, the ferromagnetic ordering temperature, increases uniformly with increasing annealing temperature and annealing time. Hence, Tc can be tuned by appropriate annealing. In order to fully anneal these samples, i.e., achieve bulk properties, it proves sufficient to anneal them in argon. Further annealing in oxygen produces only minor changes in the resistivity. Data from Tc up to 1200 K show activated conduction with ρ=BTeEa/kT, the temperature dependence predicted by the Emin–Holstein theory of adiabatic polaron hopping. Their model fits both data from the partially annealed and fully annealed samples better than the variable range hopping or semiconductor models which have been used by previous workers. The activation energy Ea and resistivity coefficient B decrease with increasing maximum anneal temperature. These changes, together with the increase in Tc, are consistent w...

Anneal‐tunable Curie temperature and transport of La0.67Ca0.33MnO3

Bulk, single crystal, and metal-organic chemical-vapor deposition thin-film samples of ${\mathrm{Gd}}_{0.67}$ ${\mathrm{Ca}}_{0.33}$ ${\mathrm{MnO}}_{3}$ were prepared and examined for their electrical, magnetic, and structural properties. ${\mathrm{Gd}}_{0.67}$ ${\mathrm{Ca}}_{0.33}$ ${\mathrm{MnO}}_{3}$ is ferrimagnetic with a transition temperature between 50 and 80 K and a compensation temperature of about 15 K. A molecular field model with a ferromagnetic manganese sublattice antiparallel to the gadolinium sublattice qualitatively explains the magnetism data. A large high-field susceptibility is observed at 5 K, suggesting a sublattice rotation. The resistivity and the magnetoresistance show no anomaly near the ferrimagnetic transition. There is no noticeable change in the structure, as seen from the x-ray-absorption fine structure between 40 and 69 K, indicating that there is no structural discontinuity across the paramagnetic insulator to ferromagnetic insulator phase boundary. The resistivity of ${\mathrm{Gd}}_{0.67}$ ${\mathrm{Ca}}_{0.33}$ ${\mathrm{MnO}}_{3}$ is consistent with small polaron hopping at high temperatures (up to 1100 K), and possibly by a different mechanism at low temperatures.

Local structure, transport, and rare-earth magnetismin the ferrimagnetic perovskite Gd 0.67 Ca 0.33 MnO 3 s

YBa2Cu3O7 films 2000–7500 A thick were deposited onto [100] LaAlO3 substrates using a novel single source metalorganic chemical vapor deposition technique. We have so far observed critical currents as high as 4×106 A/cm2 at 77 K, transition temperatures (Tc at R=0) as high as 91 K, and the 10 GHz microwave surface resistance Rs as low as 40 μΩ at 4.2 K and 400 μΩ at 77 K.

R. Hiskes

Papers

Intrinsic electrical transport and magnetic properties of La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 MOCVD thin films and bulk material.

Formation and observation of 50 nm polarized domains in PbZr1−xTixO3 thin film using scanning probe microscope

Anneal‐tunable Curie temperature and transport of La0.67Ca0.33MnO3

Local structure, transport, and rare-earth magnetismin the ferrimagnetic perovskite Gd 0.67 Ca 0.33 MnO 3 s

Single source metalorganic chemical vapor deposition of low microwave surface resistance YBa2Cu3O7