Solar water splitting for hydrogen generation can be a potential source of renewable energy for the future. Here we show that efficient and stable stoichiometric dissociation of water into hydrogen and oxygen can be achieved under visible light by eradicating the potential barrier on nonpolar surfaces of indium gallium nitride nanowires through controlled p-type dopant incorporation. An apparent quantum efficiency of B12.3% is achieved for overall neutral (pHB7.0) water splitting under visible light illumination (400-475 nm). Moreover, using a double-band p-type gallium nitride/indium gallium nitride nanowire heterostructure, we show a solar-to-hydrogen conversion efficiency of B1.8% under concentrated sunlight. The dominant effect of near-surface band structure in transforming the photocatalytic performance is elucidated. The stability and efficiency of this recyclable, wafer-level nanoscale metal-nitride photocatalyst in neutral water demonstrates their potential use for large-scale solar-fuel conversion.

Solar water splitting is one of the key steps in artificial photosynthesis for future carbonneutral, storable and sustainable source of energy. Here we show that one of the major obstacles for achieving efficient and stable overall water splitting over the emerging nanostructured photocatalyst is directly related to the uncontrolled surface charge properties. By tuning the Fermi level on the nonpolar surfaces of gallium nitride nanowire arrays, we demonstrate that the quantum efficiency can be enhanced by more than two orders of magnitude. The internal quantum efficiency and activity on p-type gallium nitride nanowires can reach B51% and B4.0 mol hydrogen h À 1 g À 1 , respectively. The nanowires remain virtually unchanged after over 50,000 mmol gas (hydrogen and oxygen) is produced, which is more than 10,000 times the amount of photocatalyst itself (B4.6 mmol). The essential role of Fermi-level tuning in balancing redox reactions and in enhancing the efficiency and stability is also elucidated.

We report on the first demonstration of stable photoelectrochemical water splitting and hydrogen generation on a double-band photoanode in acidic solution (hydrogen bromide), which is achieved by InGaN/GaN core/shell nanowire arrays grown on Si substrate using catalyst-free molecular beam epitaxy. The nanowires are doped n-type using Si to reduce the surface depletion region and increase current conduction. Relatively high incident-photon-to-current-conversion efficiency (up to ~27%) is measured under ultraviolet and visible light irradiation. Under simulated sunlight illumination, steady evolution of molecular hydrogen is further demonstrated.

We have investigated the correlated surface electronic and optical properties of [0001]-oriented epitaxial InN nanowires grown directly on silicon. By dramatically improving the epitaxial growth process, we have achieved, for the first time, intrinsic InN both within the bulk and at nonpolar InN surfaces. The near-surface Fermi-level was measured to be ∼0.55 eV above the valence band maximum for undoped InN nanowires, suggesting the absence of surface electron accumulation and Fermi-level pinning. This result is in direct contrast to the problematic degenerate two-dimensional electron gas universally observed on grown surfaces of n-type degenerate InN. We have further demonstrated that the surface charge properties of InN nanowires, including the formation of two-dimensional electron gas and the optical emission characteristics can be precisely tuned through controlled n-type doping. At relatively high doping levels in this study, the near-surface Fermi-level was found to be pinned at ∼0.95-1.3 eV above the valence band maximum. Through these trends, well captured by the effective mass and ab initio materials modeling, we have unambiguously identified the definitive role of surface doping in tuning the surface charge properties of InN.

No abstract