Juliane Hanzig

Single crystal strontium titanate surface and bulk modifications due to vacuum annealing

Vacuum annealing is a widely used method to increase the electric conductivity of SrTiO3 single crystals. The induced oxygen vacancies act as intrinsic donors and lead to n-type conductivity. Apart from the changed electronic structure, however, also crystal structure modifications arise from this treatment. Hence, electronic properties are determined by the interplay between point defects and line defects. The present paper provides a survey of the real structure of commercially available SrTiO3 single crystals and the changes induced by reducing vacuum heat-treatment. Therefore, all investigations were performed ex situ, i.e., after the annealing process. Used characterization methods include atomic force microscopy, transmission electron microscopy, spectroscopic ellipsometry, infrared spectroscopy, and photoluminescence spectroscopy. Besides the expected variation of bulk properties, especially surface modifications have been detected. The intrinsic number of near-surface dislocations in the samples w...

How to measure the pyroelectric coefficient

The precise quantification of the pyroelectric coefficient p is indispensable for the characterization of pyroelectric materials and the development of pyroelectric-based devices, such as radiation sensors or energy harvesters. A summary of the variety of techniques to measure p is given in the present review. It provides a classification after the thermal excitation and an outline of capabilities and drawbacks of the individual techniques. The main selection criteria are: the possibility to separate different contributions to the pyroelectric coefficient, to exclude thermally stimulated currents, the capability to measure p locally, and the requirement for metallic electrodes. This overview should enable the reader to choose the technique best suited for specific samples.

Dielectric to pyroelectric phase transition induced by defect migration

Subjecting strontium titanate single crystals to an electric field in the order of 106 V m−1 is accompanied by a distortion of the cubic crystal structure, so that inversion symmetry vanishes and a polar phase is established. Since the polar nature of the migration-induced field-stabilized polar (MFP) phase is still unclear, the present work investigates and confirms the pyroelectric structure. We present measurements of thermally stimulated and pyroelectric currents that reveal a pyroelectric coefficient pMFP in the order of 30 μC K−1m−2. Therefore, a dielectric to pyroelectric phase transition in an originally centrosymmetric crystal structure with an inherent dipole moment is found, which is induced by defect migration. From symmetry considerations, we derive space group for the MFP phase of SrTiO3. The entire electroformation cycle yields additional information about the directed movement and defect chemistry of oxygen vacancies.

The anisotropy of oxygen vacancy migration in SrTiO3.

Oxygen migration in perovskites is well known to occur via vacancies along the TiO6 octahedron edges. Ionic conduction depends further on the orientation of the crystal in the electric field. To study the anisotropy in cubic SrTiO3 single crystals, temperature-dependent electroformation measurements ranging from 11 °C to 50 °C have been conducted for representative crystallographic directions within the crystal system. Electroformation of pure SrTiO3 follows an Arrhenius behavior, implying an ionic migration process of intrinsic oxygen defects. Activation energies E A for oxygen vacancy migration have been determined to 0.70 eV for [Formula: see text] and [Formula: see text] directions in contrast to 0.77 eV for [Formula: see text]. Mobility of oxygen vacancies is enhanced in [Formula: see text] compared to [Formula: see text] and [Formula: see text] by up to half an order of magnitude. A migration model based on atomistic migration paths and their multiplicities accounts for these experimental variations in mobility.

Large piezoelectricity in electric-field modified single crystals of SrTiO3

Defect engineering is an effective and powerful tool to control the existing material properties and produce completely new ones, which are symmetry-forbidden in a defect-free crystal. For example, the application of a static electric field to a single crystal of SrTiO3 forms a strained near-surface layer through the migration of oxygen vacancies out of the area beneath the positively charged electrode. While it was previously shown that this near-surface phase holds pyroelectric properties, which are symmetry-forbidden in centrosymmetric bulk SrTiO3, this paper reports that the same phase is strongly piezoelectric. We demonstrate the piezoelectricity of this phase through stroboscopic time-resolved X-ray diffraction under alternating electric field and show that the effective piezoelectric coefficient d33 ranges between 60 and 100 pC/N. The possible atomistic origins of the piezoelectric activity are discussed as a coupling between the electrostrictive effect and spontaneous polarization of this near-sur...

Crystallization dynamics and interface stability of strontium titanate thin films on silicon

Nonstoichiometric SrTiO3 thin films were fabricated by different thin-film deposition methods. The impact on the oxide/silcon interface stability as well as the crystallization onset temperature is investigated.

Picometer polar atomic displacements in strontium titanate determined by resonant X-ray diffraction

Physical properties of crystalline materials often manifest themselves as atomic displacements either away from symmetry positions or driven by external fields. Especially the origin of multiferroic or magnetoelectric effects may be hard to ascertain as the related displacements can reach the detection limit. Here we present a resonant X-ray crystal structure analysis technique that shows enhanced sensitivity to minute atomic displacements. It is applied to a recently found crystalline modification of strontium titanate that forms in single crystals under electric field due to oxygen vacancy migration. The phase has demonstrated unexpected properties, including piezoelectricity and pyroelectricity, which can only exist in non-centrosymmetric crystals. Apart from that, the atomic structure has remained elusive and could not be obtained by standard methods. Using resonant X-ray diffraction, we determine atomic displacements with sub-picometer precision and show that the modified structure of strontium titanate corresponds to that of well-known ferroelectrics such as lead titanate.It is a challenge to measure changes in the crystal structures in picometer scale and the associated phase. Here the authors demonstrate the lattice expansion and polar distortions of oxygen deficient SrTiO3 using a resonance X-ray scattering technique.

Anomalous ferroelectricity in P(VDF70-TrFE30)

ABSTRACT The ferroelectric phase transition of copolymers of vinylidene fluoride (VDF) with trifluoroethylene (TrFE) is well known and related to conformational changes in the polymer chain. Contrary to the expected paraelectric behaviour in the high temperature phase a pyroelectric investigation of the phase transition in the range from 0°C to 130°C combined with X-ray diffraction indicate the copolymer as ferroelectric when prepared and polarised in the high-temperature phase. Based on this finding the orthorhombic space-group Fmm2 is proposed for the polar high-temperature phase. Above the Curie temperature the material exhibits pyroelectricity with inverted sign, whose origin is interpreted as flexoelectricity.

Fundamental principles of battery design

Abstract With an increasing diversity of electrical energy sources, in particular with respect to the pool of renewable energies, and a growing complexity of electrical energy usage, the need for storage solutions to counterbalance the discrepancy of demand and offer is inevitable. In principle, a battery seems to be a simple device since it just requires three basic components – two electrodes and an electrolyte – in contact with each other. However, only the control of the interplay of these components as well as their dynamics, in particular the chemical reactions, can yield a high-performance system. Moreover, specific aspects such as production costs, weight, material composition and morphology, material criticality, and production conditions, among many others, need to be fulfilled at the same time. They present some of the countless challenges, which make battery design a long-lasting, effortful task. This chapter gives an introduction to the fundamental concepts of batteries. The principles are exemplified for the basic Daniell cell followed by a review of Nernst equation, electrified interface reactions, and ionic transport. The focus is addressed to crystalline materials. A comprehensive discussion of crystal chemical and crystal physical peculiarities reflects favourable and unfavourable local structural aspects from a crystallographic view as well as considerations with respect to electronic structure and bonding. A brief classification of battery types concludes the chapter.

Optical spectroscopy as a tool for battery research

Abstract The following compendium reviews the development and establishment of optical spectroscopy as an analytical method for battery material components and electrochemical reactions. The interaction of light with matter is a sensitive and non-destructive way to characterize any sample state, i.e. solids, liquids or gases. Special attention is devoted to infrared and ultraviolet spectroscopy, covering a wavelength range from 12 μm to 200 nm, as well as Raman scattering spectroscopy, in order to excite different vibrational/rotational lattice modes and transitions of valence electrons. This allows an insight into structural properties, chemical composition, oxidation states or kinetic processes. The development of spectroelectrochemical in situ cells allows the investigation of various battery components, e.g. working and counter electrode, separator, electrolyte as well as interfaces between these components. These powerful tools allow the evaluation of the functionality, stability and safety aspects of an electrochemical storage cell.