Electric field induced pyroelectricity in strontium titanate

Pyroelectric materials have a broad spectrum for practical application. Apart from the established infrared sensor technology, recently the pyroelectric effect has been employed unconventionally in waste heat recovery, X-ray generation or water disinfection. This coupling phenomenon is the temperature dependence of a ferroelectric's spontaneous polarisation. A crystal structure that allows pyroelectricity cannot have an inversion centre, if it had a polar axis would not exist. Hence the well-known perovskite strontium titanate, crystallizing in the space group Pm-3m, is known to be dielectric. Nonetheless, under an external electric field of 1MV/m charged defects like oxygen vacancies redistribute in a strontium titanate single crystal, leading to a distortion of the unit cell and sub­seq­uent­ly to the formation of a defect structure called the migration-induced field-stabilized polar (MFP) phase [1]. Raman scattering shows that the MFP phase of strontium titanate may ex­hibit broken centro­symmetry, suggesting the existence of a polar axis. Here, we investigate the pyroelectric properties of strontium titanate single crystals at room temp­era­ture during these electroformation cycles with a modified Sharp-Garn method [2]. Our frequency and field dependent measurements indicate the pyroelectricity of the MFP phase. Additionally the measurement method elucidates the kinetics of the oxygen vacancy migration as well as electric properties during electro­formation. Inducing pyroelectricity in a centro-symmetric crystal structure opens the scope for a new class of pyroelectric materials.

Defect separation in strontium titanate: Formation of a polar phase

Stoichiometric perovskite-type strontium titanate acts as an insulator because of its wide electronic band gap and has therefore great potential as high-k dielectric and storage material in memory applications. Degradation phenomena of insulating properties of transition metal oxides occur during long time voltage application. From the defect chemistry point of view the question arises how mobile species react on an external electric field and which impact the redistribution has on the stability of the crystal structure. Here, we discuss near-surface reversible structural changes in SrTiO3 single crystals caused by oxygen vacancy redistribution in an external electric field. We present in-situ X-ray diffraction during and after electroformation. Several reflections are monitored and show a tetragonal elongation of the cubic unit cell. Raman investigations were carried out to verify that the expansion involves a transition from the centrosymmetric to a less symmetric structure. Regarding a whole formation cycle, two different time scales occur: a slow one during the increase of the lattice constant and a fast one after switching off the electric field. Based on the experimental data we suggest a model containing the formation of a polar SrTiO3 unit cell stabilized by the electric field, which is referred to as migration-induced field-stabilized polar phase [1] at room temperature. As expected by a non-centrosymmetric crystal structure, pyroelectric properties will be presented in conjunction with temperature modulated electroformation cycles. Furthermore, we show that intrinsic defect separation establishes a non-equilibrium accompanied by an electromotive force. A comprehensive thermodynamic deduction in terms of theoretical energy and entropy calculations indicates an exergonic electrochemical reaction after the electric field is switched off. Based on that driving force the experimental and theoretical proof of concept of a solid-state SrTiO3 battery is reported.

Composition profiles across MIMs for resistive switching studied by EDS and EELS

Resistive switching in MIM (metal-insulator-metal) stacks is an effect that enables a promising data storage technology which is able to overcome the size limitations of conventional non-volatile memories. The resistive switching effect was already demonstrated for several binary as well as ternary transition metal oxides (TiO2, NiO, SrTiO3, Nb2O5) [1,2]. The current models of the switching mechanisms suggest the important role of defects like oxygen vacancies [3]. Here, we report on the local structural and electronic properties of transition metal oxides embedded in MIM stacks that were obtained by using transmission electron microscopy and electron spectroscopy. We focus on the development of the stoichiometry across the MIM stack for amorphous and partial crystalline niobium oxides. Therefore, electron energy loss spectra (EELS) as well as the energy dispersive X-ray spectra (EDS) were collected on the atomic scale utilizing a nanometer probe in the scanning transmission electron microscope (STEM). The differences in the oxygen content among the electrodes and the concentration profiles at the metal/oxide interfaces in particular were investigated in dependence on the preparation method and on the electrode material. Besides, focusing on the electron loss near edge structure (ELNES) of the oxygen K edge we employed simulations using FEFF9 to describe the modifications of the electronic structure with variations in the oxygen content.