Structure and dynamics of the fast lithium ion conductor "li 7La3Zr2O12"

The solid lithium-ion electrolyte "Li7La3Zr 2O12" (LLZO) with a garnet-type structure has been prepared in the cubic and tetragonal modification following conventional ceramic syntheses routes. Without aluminium doping tetragonal LLZO was obtained, which shows a two orders of magnitude lower room temperature conductivity than the cubic modification. Small concentrations of Al in the order of 1 wt% were sufficient to stabilize the cubic phase, which is known as a fast lithium-ion conductor. The structure and ion dynamics of Al-doped cubic LLZO were studied by impedance spectroscopy, dc conductivity measurements, 6Li and 7Li NMR, XRD, neutron powder diffraction, and TEM precession electron diffraction. From the results we conclude that aluminium is incorporated in the garnet lattice on the tetrahedral 24d Li site, thus stabilizing the cubic LLZO modification. Simulations based on diffraction data show that even at the low temperature of 4 K the Li ions are blurred over various crystallographic sites. This strong Li ion disorder in cubic Al-stabilized LLZO contributes to the high conductivity observed. The Li jump rates and the activation energy probed by NMR are in very good agreement with the transport parameters obtained from electrical conductivity measurements. The activation energy Ea characterizing long-range ion transport in the Al-stabilized cubic LLZO amounts to 0.34 eV. Total electric conductivities determined by ac impedance and a four point dc technique also agree very well and range from 1 × 10-4 Scm-1 to 4 × 10-4 Scm-1 depending on the Al content of the samples. The room temperature conductivity of Al-free tetragonal LLZO is about two orders of magnitude lower (2 × 10 -6 Scm-1, Ea = 0.49 eV activation energy). The electronic partial conductivity of cubic LLZO was measured using the Hebb-Wagner polarization technique. The electronic transference number te- is of the order of 10-7. Thus, cubic LLZO is an almost exclusive lithium ion conductor at ambient temperature. © the Owner Societies 2011

Local atomic arrangements and lattice distortions in layered Ge-Sb-Te crystal structures

Insights into the local atomic arrangements of layered Ge-Sb-Te compounds are of particular importance from a fundamental point of view and for data storage applications. In this view, a detailed knowledge of the atomic structure in such alloys is central to understanding the functional properties both in the more commonly utilized amorphous–crystalline transition and in recently proposed interfacial phase change memory based on the transition between two crystalline structures. Aberration-corrected scanning transmission electron microscopy allows direct imaging of local arrangement in the crystalline lattice with atomic resolution. However, due to the non-trivial influence of thermal diffuse scattering on the high-angle scattering signal, a detailed examination of the image contrast requires comparison with theoretical image simulations. This work reveals the local atomic structure of trigonal Ge-Sb-Te thin films by using a combination of direct imaging of the atomic columns and theoretical image simulation approaches. The results show that the thin films are prone to the formation of stacking disorder with individual building blocks of the Ge2Sb2Te5, Ge1Sb2Te4 and Ge3Sb2Te6 crystal structures intercalated within randomly oriented grains. The comparison with image simulations based on various theoretical models reveals intermixed cation layers with pronounced local lattice distortions, exceeding those reported in literature

Conversion of p–n conduction type by spinodal decomposition in Zn-Sb-Bi phase-change alloys

Phase-change films with multiple resistance levels are promising for increasing the storage density in phase-change memory technology. Diffusion-dominated Zn2Sb3 films undergo transitions across three states, from high through intermediate to low resistance, upon annealing. The properties of the Zn2Sb3 material can be further optimized by doping with Bi. Based on scanning transmission electron microscopy combined with electrical transport measurements, at a particular Bi concentration, the conduction of Zn-Sb-Bi compounds changes from p- to n-type, originating from spinodal decomposition. Simultaneously, the change in the temperature coefficient of resistivity shows a metal-to-insulator transition. Further analysis of microstructure characteristics reveals that the distribution of the Bi-Sb phase may be the origin of the driving force for the p–n conduction and metal-to-insulator transitions and therefore may provide us with another way to improve multilevel data storage. Moreover, the Bi doping promotes the thermoelectric properties of the studied alloys, leading to higher values of the power factor compared to known reported structures. The present study sheds valuable light on the spinodal decomposition process caused by Bi doping, which can also occur in a wide variety of chalcogenide-based phase-change materials. In addition, the study provides a new strategy for realizing novel p–n heterostructures for multilevel data storage and thermoelectric applications

Coupled magnetic and structural transitions in La0.7Sr0.3MnO3 films on SrTiO3

The magnetic properties of three epitaxial La0.7Sr0.3MnO3 films of thickness 5, 15 and 40 nm grown on SrTiO3 (001) substrates were investigated. The structural transition of the SrTiO3 substrate induces a magnetic transition in the manganite films due to magnetoelastic coupling. Below the temperature of the structural transition additional steps in the magnetization reversal characteristics appear characterized by clearly defined coercive fields. These additional coercive fields depend on the cooling history of the sample and are related to the formation of structural domains in the La0.7Sr0.3MnO3 films induced by the substrate

Influence of substrate dimensionality on the growth mode of epitaxial 3D-bonded GeTe thin films: From 3D to 2D growth

The pseudo-binary line of Sb2Te3-GeTe contains alloys featuring different crystalline characteristics from two-dimensionally (2D-) bonded Sb2Te3 to three-dimensionally (3D-) bonded GeTe. Here, the growth scenario of 3D-bonded GeTe is investigated by depositing epitaxial GeTe thin films on Si(111) and Sb2Te3-buffered Si(111) substrates using pulsed laser deposition (PLD). GeTe thin films were grown in trigonal structure within a temperature window for epitaxial growth of 210–270 °C on unbuffered Si(111) substrates. An unconventional growth onset was characterized by the formation of a thin amorphous GeTe layer. Nonetheless, the as-grown film is found to be crystalline. Furthermore, by employing a 2D-bonded Sb2Te3 thin film as a seeding layer on Si(111), a 2D growth of GeTe is harnessed. The epitaxial window can substantially be extended especially towards lower temperatures down to 145 °C. Additionally, the surface quality is significantly improved. The inspection of the local structure of the epitaxial films reveals the presence of a superposition of twinned domains, which is assumed to be an intrinsic feature of such thin films. This work might open a way for an improvement of an epitaxy of a 3D-bonded material on a highly-mismatched substrate (e.g. Si (111)) by employing a 2D-bonded seeding layer (e.g. Sb2Te3)

Conductive Tracks in Carbon Implanted Titania Nanotubes: Atomic-Scale Insights from Experimentally Based Ab Initio Molecular Dynamics Modeling

Ion implantation of titania nanotubes is a highly versatile approach for tailoring structural and electrical properties. While recently self-organized nanoscale compositional patterning has been reported, the atomistic foundations and impact on electronic structure are not established at this point. To study these aspects, ab initio molecular dynamic simulations based on atomic compositions in C implanted titania nanotubes according to elastic recoil detection analysis are employed. Consistent with experimental data, carbon accumulates in chainlike precipitates, which are favorable for enhancing conductivity, as revealed by density-functional theory electronic ground states calculations are demonstrated

Formation of BaTiO 3 thin films from (110) TiO 2 rutile single crystals and BaCO 3 by solid state reactions

Abstract The formation of BaTiO 3 thin films from (110) TiO 2 rutile single crystals and BaCO 3 was investigated experimentally by solid -solid and gassolid reactions in vacuum. X-ray diffraction revealed the formation of an intermediate Ba 2 TiO 4 phase before BaTiO 3 is formed. According to our calculations the formation of Ba 2 TiO 4 is associated with a maximum decrease in the Gibbs energy at a CO 2 pressure lower than 10 À 4 mbar. Reactions at 600 -900 -C showed different processes to occur in the solid -solid and gas -solid reactions. The observations are interpreted in terms of the different mass transport mechanisms involved. The results shed new light on the phase sequence during BaTiO 3 formation; in particular a dissociation of BaCO 3 prior to its participation in the reaction has become rather unlikely.

Structural Transitions in Ge2Sb2Te5 Phase Change Memory Thin Films Induced by Nanosecond UV Optical Pulses

Ge-Sb-Te-based phase change memory alloys have recently attracted a lot of attention due to their promising applications in the fields of photonics, non-volatile data storage, and neuromorphic computing. Of particular interest is the understanding of the structural changes and underlying mechanisms induced by short optical pulses. This work reports on structural changes induced by single nanosecond UV laser pulses in amorphous and epitaxial Ge2Sb2Te5 (GST) thin films. The phase changes within the thin films are studied by a combined approach using X-ray diffraction and transmission electron microscopy. The results reveal different phase transitions such as crystalline-to-amorphous phase changes, interface assisted crystallization of the cubic GST phase and structural transformations within crystalline phases. In particular, it is found that crystalline interfaces serve as crystallization templates for epitaxial formation of metastable cubic GST phase upon phase transitions. By varying the laser fluence, GST thin films consisting of multiple phases and different amorphous to crystalline volume ratios can be achieved in this approach, offering a possibility of multilevel data storage and realization of memory devices with very low resistance drift. In addition, this work demonstrates amorphization and crystallization of GST thin films by using only one UV laser with one single pulse duration and one wavelength. Overall, the presented results offer new perspectives on switching pathways in Ge-Sb-Te-based materials and show the potential of epitaxial Ge-Sb-Te thin films for applications in advanced phase change memory concepts