Water splitting with silicon p-i-n superlattices suspended in solution.

Photoelectrochemical (PEC) water splitting to produce hydrogen fuel was first reported 50 years ago1, yet artificial photosynthesis has not become a widespread technology. Although planar Si solar cells have become a ubiquitous electrical energy source economically competitive with fossil fuels, analogous PEC devices have not been realized, and standard Si p-type/n-type (p-n) junctions cannot be used for water splitting because the bandgap precludes the generation of the needed photovoltage. An alternative paradigm, the particle suspension reactor (PSR), forgoes the rigid design in favour of individual PEC particles suspended in solution, a potentially low-cost option compared with planar systems2,3. Here we report Si-based PSRs by synthesizing high-photovoltage multijunction Si nanowires (SiNWs) that are co-functionalized to catalytically split water. By encoding a p-type-intrinsic-n-type (p-i-n) superlattice within single SiNWs, tunable photovoltages exceeding 10 V were observed under 1 sun illumination. Spatioselective photoelectrodeposition of oxygen and hydrogen evolution co-catalysts enabled water splitting at infrared wavelengths up to approximately 1,050 nm, with the efficiency and spectral dependence of hydrogen generation dictated by the photonic characteristics of the sub-wavelength-diameter SiNWs. Although initial energy conversion efficiencies are low, multijunction SiNWs bring the photonic advantages of a tunable, mesoscale geometry and the material advantages of Si-including the small bandgap and economies of scale-to the PSR design, providing a new approach for water-splitting reactors.

Ratcheting quasi-ballistic electrons in silicon geometric diodes at room temperature.

Ratcheting effects play an important role in systems ranging from mechanical socket wrenches to biological motor proteins. The underlying principle is to convert a fluctuating, unbiased force into unidirectional motion. Here, we report the ratcheting of electrons at room temperature using a semiconductor nanowire with precisely engineered asymmetry. Modulation of the nanowire diameter creates a cylindrical sawtooth geometry with broken inversion symmetry on a nanometer-length scale. In a two-terminal device, this structure responded as a three-dimensional geometric diode that funnels electrons preferentially in one direction through specular reflection of quasi-ballistic electrons at the nanowire surface. The ratcheting effect causes charge rectification at frequencies exceeding 40 gigahertz, demonstrating the potential for applications such as high-speed data processing and long-wavelength energy harvesting.

The influence of nanoscale roughness and substrate chemistry on the frictional properties of single and few layer graphene.

Nanoscale carbon lubricants such as graphene, have garnered increased interest as protective surface coatings for devices, but its tribological properties have been shown to depend on its interactions with the underlying substrate surface and its degree of surface conformity. This conformity is especially of interest as real interfaces exhibit roughness on the order of ∼10 nm that can dramatically impact the contact area between the graphene film and the substrate. To examine the combined effects of surface interaction strength and roughness on the frictional properties of graphene, a combination of Atomic Force Microscopy (AFM) and Raman microspectroscopy has been used to explore substrate interactions and the frictional properties of single and few-layer graphene as a coating on silica nanoparticle films, which yield surfaces that mimic the nanoscaled asperities found in realistic devices. The interactions between the graphene and the substrate have been controlled by comparing their binding to hydrophilic (silanol terminated) and hydrophobic (octadecyltrichlorosilane modified) silica surfaces. AFM measurements revealed that graphene only partially conforms to the rough surfaces, with decreasing conformity, as the number of layers increase. Under higher mechanical loading the graphene conformity could be reversibly increased, allowing for a local estimation of the out-of-plane bending modulus of the film. The frictional properties were also found to depend on the number of layers, with the largest friction observed on single layers, ultimately decreasing to that of bulk graphite. This trend however, was found to disappear, depending on the tip-sample contact area and interfacial shear strain of the graphene associated with its adhesion to the substrate.