Nanoscale ferroelectrics are expected to exhibit various exotic domain configurations, such as the full flux-closure pattern that is well known in ferromagnetic materials. Here we observe not only the atomic morphology of the flux-closure quadrant but also a periodic array of flux closures in ferroelectric PbTiO3 films, mediated by tensile strain on a GdScO3 substrate. Using aberration-corrected scanning transmission electron microscopy, we directly visualize an alternating array of clockwise and counterclockwise flux closures, whose periodicity depends on the PbTiO3 film thickness. In the vicinity of the core, the strain is sufficient to rupture the lattice, with strain gradients up to 10(9) per meter. Engineering strain at the nanoscale may facilitate the development of nanoscale ferroelectric devices.
The direct synthesis of hydrogen peroxide (H2O2) from H2 and O2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H2O2. This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. We show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriate second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H2O2 production that do not contain gold.
We explore ferroelectric properties of cleaved 2-D flakes of copper indium thiophosphate, CuInP2S6 (CITP), and probe size effects along with limits of ferroelectric phase stability, by ambient and ultra high vacuum scanning probe microscopy. CITP belongs to the only material family known to display ferroelectric polarization in a van der Waals, layered crystal at room temperature and above. Our measurements directly reveal stable, ferroelectric polarization as evidenced by domain structures, switchable polarization, and hysteresis loops. We found that at room temperature the domain structure of flakes thicker than 100 nm is similar to the cleaved bulk surfaces, whereas below 50 nm polarization disappears. We ascribe this behavior to a well-known instability of polarization due to depolarization field. Furthermore, polarization switching at high bias is also associated with ionic mobility, as evidenced both by macroscopic measurements and by formation of surface damage under the tip at a bias of 4 V-likely due to copper reduction. Mobile Cu ions may therefore also contribute to internal screening mechanisms. The existence of stable polarization in a van-der-Waals crystal naturally points toward new strategies for ultimate scaling of polar materials, quasi-2D, and single-layer materials with advanced and nonlinear dielectric properties that are presently not found in any members of the growing "graphene family".
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