Observations of Co4+ in a higher spin state and the increase in the Seebeck coefficient of thermoelectric Ca3Co4O9.

Ca3Co4O9 has a unique structure that leads to exceptionally high thermoelectric transport. Here we report the achievement of a 27% increase in the room-temperature in-plane Seebeck coefficient of Ca3Co4O9 thin films. We combine aberration-corrected Z-contrast imaging, atomic-column resolved electron energy-loss spectroscopy, and density-functional calculations to show that the increase is caused by stacking faults with Co4+-ions in a higher spin state compared to that of bulk Ca3Co4O9. The higher Seebeck coefficient makes the Ca3Co4O9 system suitable for many high temperature waste-heat-recovery applications.

Effect of substrate on the atomic structure and physical properties of thermoelectric Ca3Co4O9 thin films.

The incommensurately layered cobalt oxide Ca(3)Co(4)O(9) exhibits an unusually high Seebeck coefficient as a polycrystalline bulk material, making it ideally suited for many high temperature thermoelectric applications. In this paper, we investigate properties of Ca(3)Co(4)O(9) thin films grown on cubic perovskite SrTiO(3), LaAlO(3), and (La(0.3)Sr(0.7))(Al(0.65)Ta(0.35))O(3) substrates and on hexagonal Al(2)O(3) (sapphire) substrates using the pulsed laser deposition technique. X-ray diffraction and transmission electron microscopy analysis indicate strain-free growth of films, irrespective of the substrate. However, depending on the lattice and symmetry mismatch, defect-free growth of the hexagonal CoO(2) layer is stabilized only after a critical thickness and, in general, we observe the formation of a stable Ca(2)CoO(3) buffer layer near the substrate-film interface. Beyond this critical thickness, a large concentration of CoO(2) stacking faults is observed, possibly due to weak interlayer interaction in this layered material. We propose that these stacking faults have a significant impact on the Seebeck coefficient and we report higher values in thinner Ca(3)Co(4)O(9) films due to additional phonon scattering sites, necessary for improved thermoelectric properties.

Aberration-corrected Z-contrast imaging of SrTiO3 dislocation cores.

Many fundamental problems in materials science, physics, and particular nanotechnology rely on the direct determination and characterization of atomic arrangements and electronic environments of individual interfaces or defects. In this paper, we will show how aberration-corrected Z-contrast imaging in combination with electron energy-loss spectroscopy can be used to directly measure the local atomic and electronic structures of dislocation cores in low-angle SrTiO3 [001] tilt grain boundaries. In particular, we will study two types of dislocation cores in a 3 degrees tilt grain boundary, a pure edge dislocation, and a dissociated dislocation core. While it is energetically favorable for an edge dislocation to dissociate into two partial dislocations in such a low-angle grain boundary, we can find pure edge dislocations that show a higher O vacancy concentration than the dissociated cores. We suggest that the increased oxygen vacancy concentration might help stabilizing the pure edge dislocations in 3 degrees tilt grain boundaries of SrTiO3.

Direct measurement of the low-temperature spin-state transition in LaCoO3.

LaCoO3 exhibits an anomaly in its magnetic susceptibility around 80 K associated with a thermally excited transition of the Co3+-ion spin. We show that electron energy-loss spectroscopy is sensitive to this Co3+-ion spin-state transition, and that the O K edge prepeak provides a direct measure of the Co3+ spin state in LaCoO3 as a function of temperature. Our experimental results are confirmed by first-principles calculations, and we conclude that the thermally excited spin-state transition occurs from a low to an intermediate spin state, which can be distinguished from the high-spin state.

Polaron melting and ordering as key mechanisms for colossal resistance effects in manganites.

Polarons, the combined motion of electrons in a cloth of their lattice distortions, are a key transport feature in doped manganites. To develop a profound understanding of the colossal resistance effects induced by external fields, the study of polaron correlations and the resulting collective polaron behavior, i.e., polaron ordering and transition from polaronic transport to metallic transport is essential. We show that static long-range ordering of Jahn-Teller polarons forms a polaron solid which represents a new type of charge and orbital ordered state. The related noncentrosymmetric lattice distortions establish a connection between colossal resistance effects and multiferroic properties, i.e., the coexistence of ferroelectric and antiferromagnetic ordering. Colossal resistance effects due to an electrically induced polaron solid-liquid transition are directly observed in a transmission electron microscope with local electric stimulus applied in situ using a piezo-controlled tip. Our results shed light onto the colossal resistance effects in magnetic field and have a strong impact on the development of correlated electron-device applications such as resistive random access memory (RRAM).

Enhanced current transport at grain boundaries in high-T(c) superconductors.

Large-scale applications of high-transition-temperature (high-T(c)) superconductors, such as their use in superconducting cables, are impeded by the fact that polycrystalline materials (the only practical option) support significantly lower current densities than single crystals. The superconducting critical current density (J(c)) across a grain boundary drops exponentially if the misorientation angle exceeds 2 degrees -7 degrees. Grain texturing reduces the average misorientation angle, but problems persist. Adding impurities (such as Ca in YBa2Cu3O7-delta; YBCO) leads to increased J(c) (refs 9, 10), which is generally attributed to excess holes introduced by Ca2+ substituting for Y3+ (ref. 11). However, a comprehensive physical model for the role of grain boundaries and Ca doping has remained elusive. Here we report calculations, imaging and spectroscopy at the atomic scale that demonstrate that in poly-crystalline YBCO, highly strained grain-boundary regions contain excess O vacancies, which reduce the local hole concentration. The Ca impurities indeed substitute for Y, but in grain-boundary regions under compression and tension they also replace Ba and Cu, relieving strain and suppressing O-vacancy formation. Our results demonstrate that the ionic radii are more important than their electronic valences for enhancing J(c).

Atomic resolution STEM analysis of defects and interfaces in ceramic materials.

Atomic resolution scanning transmission electron microscopy (STEM) analysis, in particular the combination of Z-contrast imaging and electron energy-loss spectroscopy (EELS) has been successfully used to measure the atomic and electronic structure of materials with sub-nanometer spatial resolution. Furthermore, the combination of this incoherent imaging technique with EELS allows us to correlate certain structural features, such as defects or interfaces directly with the measured changes in the local electronic fine-structure. In this review, we will discuss the experimental procedures for achieving high-resolution Z-contrast imaging and EELS. We will describe the alignment and experimental setup for high-resolution STEM analysis and also describe some of our recent results where the combined use of atomic-resolution Z-contrast imaging and column-by-column EELS has helped solve important materials science problems.

Inversion of two-band superconductivity at the critical electron doping of (Mg, Al)B2.

Electron energy-loss spectroscopy (EELS) was combined with heat capacity measurements to probe changes of electronic structure and superconductivity in Mg(1-x)Al(x)B(2). A simultaneous decrease of EELS intensity from sigma-band hole states and the magnitude of the sigma gap was observed with increasing x, thus verifying that band filling results in the loss of strong superconductivity. These quantities extrapolated to zero at x approximately 0.33 as inferred from the unit cell volume. However, superconductivity was not quenched completely, but persisted with T(c) < 7 K up to about x approximately 55. Only the pi band had detectable density of states for 0.33 < or =x < or = 0.55, implying an inversion of the two-band hierarchy of MgB(2) in that regime. Since pi-band superconductivity is active in other materials such as intercalated graphite, implications for new materials with high T(c) are discussed.

Application of atomic scale STEM techniques to the study of interfaces and defects in materials.

Incoherent imaging and analysis techniques in the scanning transmission electron microscope (STEM) provide the potential to map changes in structure, composition and bonding that occur at materials interfaces and defects on the fundamental atomic scale. Such comprehensive characterization capabilities permit a detailed analysis of the structure-property relationships of interfaces and defects to be performed. In this paper, we discuss the resolution limits of such techniques in the JEOL 2010F STEM/TEM operating both under standard conditions and at elevated temperatures. Examples of the use of such techniques to quantify the atomic scale defect chemistry at interfaces and defects in perovskite oxides, the growth and structure of II-VI and III-V quantum dots and the electronic structure of threading dislocations in GaN will also be presented.

Observation of oxygen vacancy ordering and segregation in perovskite oxides.

Oxygen vacancies are known to dominate the overall electrical behavior of perovskite oxides, which are used in many applications. Although theories have been developed to explain the effect of these vacancies and the defect chemistry of perovskites, there has yet to be incontrovertible evidence of the fundamental origins of the structure-property relationship. However, recently developed technologies in scanning transmission electron microscopy, such as Z-contrast imaging and EELS combined with in-situ heating experiments, provide a new opportunity to address vacancy characteristics and defect chemistry on the basic atomic level. In this paper we discuss the practical aspects of these techniques and demonstrate their application to the characterization of defect chemistry and vacancies in ordered micro-domains, at domain boundaries and at grain boundaries.