RESUMEN
Semiconductor photocatalyst particles convert solar energy to fuels like H2. The particles are often assumed to provide crystalline-facet-dependent electron-hole separation. A common strategy is to deposit a hydrogen evolution reaction (HER) electrocatalyst on electron-selective facets and an oxygen evolution reaction (OER) electrocatalyst on hole-selective facets. A precise understanding of how charge-carrier-selective contacts emerge and how they are rationally designed, however, is missing. Using a combination of ex situ and in situ conducting atomic force microscopy (AFM) experiments and new ionomer/catalyst-semiconductor test structures, we show how heterogeneity in charge-carrier selectivity can be measured at the nanoscale. We discover that the presence of the water/electrolyte interface is critical to induce hole selectivity between the CoOx water-oxidation catalyst and the BiVO4 light absorber. pH-dependent measurements suggest that negative surface charge on the semiconductor is central to inducing hole selectivity. The work also demonstrates a new approach to control local pH and introduce water using thin-film ionomers compatible with conductive AFM measurements.
RESUMEN
Understanding and characterizing the intrinsic properties of charge carrier transport across the interfaces in van der Waals heterostructures is critical to their applications in modern electronics, thermoelectrics, and optoelectronics. However, there are very few published cross-plane resistivity measurements of thin samples because these inherently 2-probe measurements must be corrected for contact and lead resistances. Here, we present a method to extract contact resistances and metal lead resistances by fitting the width dependence of the contact end voltages of top and bottom electrodes of different contact widths to a model based on current crowding. These contributions are then subtracted from the total 2-probe cross-plane resistance to obtain the cross-plane resistance of the material itself without needing multiple devices and/or etching steps. This approach was used to measure cross-plane resistivities of a (PbSe)1(VSe2)1 heterostructure containing alternating layers of PbSe and VSe2 with random in-plane rotational disorder. Several samples measured exhibited a 4 order of magnitude difference between cross-plane and in-plane resistivities over the 6-300 K temperature range. We also reported the observation of charge density wave transition in the cross-plane transport of the (PbSe)1(VSe2)1 heterostructure. The device fabrication process is fully liftoff compatible, and the method developed enables the straightforward measurement of the resistivity anisotropy of most thin film materials with nm thicknesses.