Progress in nanotechnology requires new approaches to materials synthesis that make it possible to control material functionality down to the smallest scales. An objective of materials research is to achieve enhanced control over the physical properties of materials such as ferromagnets, ferroelectrics and superconductors. In this context, complex oxides and inorganic perovskites are attractive because slight adjustments of their atomic structures can produce large physical responses and result in multiple functionalities. In addition, these materials often contain ferroelastic domains. The intrinsic symmetry breaking that takes place at the domain walls can induce properties absent from the domains themselves, such as magnetic or ferroelectric order and other functionalities, as well as coupling between them. Moreover, large domain wall densities create intense strain gradients, which can also affect the material's properties. Here we show that, owing to large local stresses, domain walls can promote the formation of unusual phases. In this sense, the domain walls can function as nanoscale chemical reactors. We synthesize a two-dimensional ferromagnetic phase at the domain walls of the orthorhombic perovskite terbium manganite (TbMnO3), which was grown in thin layers under epitaxial strain on strontium titanate (SrTiO3) substrates. This phase is yet to be created by standard chemical routes. The density of the two-dimensional sheets can be tuned by changing the film thickness or the substrate lattice parameter (that is, the epitaxial strain), and the distance between sheets can be made as small as 5 nanometres in ultrathin films, such that the new phase at domain walls represents up to 25 per cent of the film volume. The general concept of using domain walls of epitaxial oxides to promote the formation of unusual phases may be applicable to other materials systems, thus giving access to new classes of nanoscale materials for applications in nanoelectronics and spintronics.

Periodic ferroelectric-ferroelastic 90° domain patterns with an unprecedented small domain periodicity of 27nm were observed in thin PbTiO3 films grown on DyScO3 substrates. These patterns contain the narrowest possible a domains (6nm wide) that allow to preserve the lateral coherence in the films, producing highly ordered patterns visible by x-ray diffraction.

TbMnO(3) films have been grown under compressive strain on (001)-oriented SrTiO(3) crystals. They have an orthorhombic structure and display the (001) orientation. With increasing thickness, the structure evolves from a more symmetric (tetragonal) to a less symmetric (bulk-like orthorhombic) structure, while keeping constant the in-plane compression, thereby leaving the out-of-plane lattice spacing unchanged. The domain microstructure of the films is also revealed, showing an increasing number of orthorhombic domains as the thickness is decreased: we directly observe ferroelastic domains as narrow as 4 nm. The high density of domain walls may explain the induced ferromagnetism observed in the films, while both the decreased anisotropy and the small size of the domains could account for the absence of a ferroelectric spin spiral phase.

No abstract

During application, electrocatalysts are exposed to harsh electrochemical conditions, which can induce degradation. This work addresses the degradation of AuPd bimetallic catalysts used for the electrocatalytic production of hydrogen peroxide (H2O2) by oxygen reduction reaction (ORR). Potential dependent changes in the AuPd surface composition occur because the two metals have different dissolution onset potentials, resulting in catalyst dealloying. Using the scanning flow cell (SFC) with an inductively coupled plasma mass spectrometer (ICPMS), the simultaneous Pd and/or Au dissolution can be observed. Thereafter, three accelerated degradation protocols (ADPs), simulating different dissolution regimes, are employed to study the catalyst structure degradation on the nanoscale with identical location (IL-) TEM. When only Pd or both Au and Pd dissolve, the composition changes rapidly and the surface becomes enriched with Au as observed by cyclic voltammetry and elemental mapping. Such changes are mirrored by the evolution of electrocatalytic performances towards the H2O2 production. Our experimental findings are finally summarized in a dissolution/structure/selectivity mechanism providing a clear picture of the degradation of bimetallic catalyst used for H2O2 synthesis.