Redox‐Based Resistive Switching Memories – Nanoionic Mechanisms, Prospects, and Challenges

The great variability in the electrical properties of multinary oxide materials, ranging from insulating, through semiconducting to metallic behaviour, has given rise to the idea of modulating the electronic properties on a nanometre scale for high-density electronic memory devices. A particularly promising aspect seems to be the ability of perovskites to provide bistable switching of the conductance between non-metallic and metallic behaviour by the application of an appropriate electric field. Here we demonstrate that the switching behaviour is an intrinsic feature of naturally occurring dislocations in single crystals of a prototypical ternary oxide, SrTiO(3). The phenomenon is shown to originate from local modulations of the oxygen content and to be related to the self-doping capability of the early transition metal oxides. Our results show that extended defects, such as dislocations, can act as bistable nanowires and hold technological promise for terabit memory devices.

Switching the electrical resistance of individual dislocations in single-crystalline SrTiO3

An imaging technique able to resolve and identify all individual atoms in non-periodic solids would be a very useful tool for materials analysis. Annular dark-field (ADF) imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation allows such an analysis, as shown by Ondrej Krivanek and co-workers. The technique was used to examine a monolayer of boron nitride, in which it revealed individual atomic substitutions involving carbon and oxygen impurity atoms. Careful analysis of the data enables the construction of a detailed map of the atomic structure, with all the atoms of the four species resolved and identified. An imaging technique that could identify all the individual atoms, including defects, in a material would be a useful tool. Here an electron-microscopy approach to the problem, based on annular dark-field imaging, is described. A monolayer of boron nitride was studied, and three types of atomic substitution were identified. Careful analysis of the data enabled the construction of a detailed map of the atomic structure. Direct imaging and chemical identification of all the atoms in a material with unknown three-dimensional structure would constitute a very powerful general analysis tool. Transmission electron microscopy should in principle be able to fulfil this role, as many scientists including Feynman realized early on1. It images matter with electrons that scatter strongly from individual atoms and whose wavelengths are about 50 times smaller than an atom. Recently the technique has advanced greatly owing to the introduction of aberration-corrected optics2,3,4,5,6,7,8. However, neither electron microscopy nor any other experimental technique has yet been able to resolve and identify all the atoms in a non-periodic material consisting of several atomic species. Here we show that annular dark-field imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation can resolve and identify the chemical type of every atom in monolayer hexagonal boron nitride that contains substitutional defects. Three types of atomic substitutions were found and identified: carbon substituting for boron, carbon substituting for nitrogen, and oxygen substituting for nitrogen. The substitutions caused in-plane distortions in the boron nitride monolayer of about 0.1 A magnitude, which were directly resolved, and verified by density functional theory calculations. The results demonstrate that atom-by-atom structural and chemical analysis of all radiation-damage-resistant atoms present in, and on top of, ultra-thin sheets has now become possible.

Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy

We present a transmission electron microscopy investigation of graphene membranes, crystalline foils with a thickness of only 1 atom. By using aberration-correction in combination with a monochromator, 1-A resolution is achieved at an acceleration voltage of only 80 kV. The low voltage is crucial for the stability of these membranes. As a result, every individual carbon atom in the field of view is detected and resolved. We observe a highly crystalline lattice along with occasional point defects. The formation and annealing of Stone-Wales defects is observed in situ. Multiple five- and seven-membered rings appear exclusively in combinations that avoid dislocations and disclinations, in contrast to previous observations on highly curved (tube- or fullerene-like) graphene surfaces.

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Direct Imaging of Lattice Atoms and Topological Defects in Graphene Membranes

Domains in ferroelectrics were considered to be well understood by the middle of the last century: They were generally rectilinear, and their walls were Ising-like. Their simplicity stood in stark contrast to the more complex Bloch walls or N\'eel walls in magnets. Only within the past decade and with the introduction of atomic-resolution studies via transmission electron microscopy, electron holography, and atomic force microscopy with polarization sensitivity has their real complexity been revealed. Additional phenomena appear in recent studies, especially of magnetoelectric materials, where functional properties inside domain walls are being directly measured. In this paper these studies are reviewed, focusing attention on ferroelectrics and multiferroics but making comparisons where possible with magnetic domains and domain walls. An important part of this review will concern device applications, with the spotlight on a new paradigm of ferroic devices where the domain walls, rather than the domains, are the active element. Here magnetic wall microelectronics is already in full swing, owing largely to the work of Cowburn and of Parkin and their colleagues. These devices exploit the high domain wall mobilities in magnets and their resulting high velocities, which can be supersonic, as shown by Kreines' and co-workers 30 years ago. By comparison, nanoelectronic devices employing ferroelectric domain walls often have slower domain wall speeds, but may exploit their smaller size as well as their different functional properties. These include domain wall conductivity (metallic or even superconducting in bulk insulating or semiconducting oxides) and the fact that domain walls can be ferromagnetic while the surrounding domains are not.

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Domain wall nanoelectronics

Using an imaging mode based on the adjustment of a negative value of the spherical-aberration coefficient of the objective lens of a transmission electron microscope, we successfully imaged all types of atomic columns in the dielectric SrTiO3 and the superconductor YBa2Cu3O7. In particular, we were able to view the oxygen atoms which, due to their low scattering power, were not previously accessible, and this allowed us to detect local nonstoichiometries or the degree of oxygen-vacancy ordering. This technique offers interesting opportunities for research into oxides, minerals, and ceramics. In particular, this holds for the huge group of perovskite-derived electroceramic materials in which the local oxygen content sensitively controls the electronic properties.

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Atomic-resolution imaging of oxygen in perovskite ceramics.

High-resolution imaging with an aberration-corrected transmission electron microscope.

A novel imaging mode for high-resolution transmission electron microscopy is described. It is based on the adjustment of a negative value of the spherical aberration C S of the objective lens of a transmission electron microscope equipped with a multipole aberration corrector system. Negative spherical aberration applied together with an overfocus yields high-resolution images with bright-atom contrast. Compared to all kinds of images taken in conventional transmission electron microscopes, where the then unavoidable positive spherical aberration is combined with an underfocus, the contrast is dramatically increased. This effect can only be understood on the basis of a full nonlinear imaging theory. Calculations show that the nonlinear contrast contributions diminish the image contrast relative to the linear image for a positive-C S setting whereas they reinforce the image contrast relative to the linear image for a negative-C S setting. The application of the new mode to the imaging of oxygen in SrTiO3 and YBa2Cu3O7 demonstrates the benefit to materials science investigations. It allows us to image directly, without further image processing, strongly scattering heavy-atom columns together with weakly scattering light-atom columns.

High-Resolution Transmission Electron Microscopy Using Negative Spherical Aberration

Aberration-corrected transmission electron microscopy allows us to image the structure of matter at genuine atomic resolution. A prominent role for the imaging of crystalline samples is played by the negative spherical aberration imaging (NCSI) technique. The physical background of this technique is reviewed. The especially high contrast observed under these conditions owes its origin to an enhancing combination of amplitude contrast due to electron diffraction channelling and phase contrast. A number of examples of the application of NCSI are reviewed in order to illustrate the applicability and the state-of-the-art of this technique.

Negative spherical aberration ultrahigh-resolution imaging in corrected transmission electron microscopy.

The optimum imaging of an object structure at the sub-angstrom length scale requires precise adjustment of the lens aberrations of a high-resolution instrument up to the fifth order. A least-squares optimization of defocus aberration C1, third-order spherical aberration C3, and fifth-order spherical aberration C5 yields two sets of aberration coefficients for strong phase contrast up to the information limit: one for variable C1 and C3, at fixed C5, another for variable C1, C3, and C5. An additional correction to the defocus aberration, dependent on object thickness, is described, which becomes important for the use of image simulation programs in predicting optimum high-resolution contrast from thin objects at the sub-angstrom scale. For instruments with a sub-angstrom information limit the ultimate structure resolution, the power to resolve adjacent atom columns in a crystalline object, depends on both the instrumental pointspread and an object pointspread due to finite width of the atomic column potentials. A simulation study on a simple double-column model yields a range for structure resolutions, dependent on the atomic scattering power, from 0.070 nm down to 0.059 nm, for a hypothetical 300-kV instrument with an information limit of 0.050 nm.

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Markus Lentzen

Papers

Atomic-resolution imaging of oxygen in perovskite ceramics.

High-resolution imaging with an aberration-corrected transmission electron microscope.

High-Resolution Transmission Electron Microscopy Using Negative Spherical Aberration

Negative spherical aberration ultrahigh-resolution imaging in corrected transmission electron microscopy.

Contrast transfer and resolution limits for sub-angstrom high-resolution transmission electron microscopy.