Engineering interfacial polarization switching in van der Waals multilayers.

In conventional ferroelectric materials, polarization is an intrinsic property limited by bulk crystallographic structure and symmetry. Recently, it has been demonstrated that polar order can also be accessed using inherently non-polar van der Waals materials through layer-by-layer assembly into heterostructures, wherein interfacial interactions can generate spontaneous, switchable polarization. Here we show that deliberate interlayer rotations in multilayer van der Waals heterostructures modulate both the spatial ordering and switching dynamics of polar domains. The engendered tunability is unparalleled in conventional bulk ferroelectrics or polar bilayers. By means of operando transmission electron microscopy we show how alterations of the relative rotations of three WSe2 layers produce structural polytypes with distinct arrangements of polar domains with either a global or localized switching response. Furthermore, the presence of uniaxial strain generates structural anisotropy that yields a range of switching behaviours, coercivities and even tunable biased responses. We also provide evidence of mechanical coupling between the two interfaces of the trilayer, a key consideration for the control of switching dynamics in polar multilayer structures more broadly.

Anomalous Interfacial Electron-Transfer Kinetics in Twisted Trilayer Graphene Caused by Layer-Specific Localization.

Interfacial electron-transfer (ET) reactions underpin the interconversion of electrical and chemical energy. It is known that the electronic state of electrodes strongly influences ET rates because of differences in the electronic density of states (DOS) across metals, semimetals, and semiconductors. Here, by controlling interlayer twists in well-defined trilayer graphene moirés, we show that ET rates are strikingly dependent on electronic localization in each atomic layer and not the overall DOS. The large degree of tunability inherent to moiré electrodes leads to local ET kinetics that range over 3 orders of magnitude across different constructions of only three atomic layers, even exceeding rates at bulk metals. Our results demonstrate that beyond the ensemble DOS, electronic localization is critical in facilitating interfacial ET, with implications for understanding the origin of high interfacial reactivity typically exhibited by defects at electrode-electrolyte interfaces.