Songrui Zhao

Visible light-driven efficient overall water splitting using p -type metal-nitride nanowire arrays

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 ∼12.3% is achieved for overall neutral (pH∼7.0) 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 ∼1.8% 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.

Tuning the surface Fermi level on p-type gallium nitride nanowires for efficient overall water splitting

Solar water splitting is one of the key steps in artificial photosynthesis for future carbon-neutral, 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 ~51% and ~4.0 mol hydrogen h(-1) g(-1), respectively. The nanowires remain virtually unchanged after over 50,000 μmol gas (hydrogen and oxygen) is produced, which is more than 10,000 times the amount of photocatalyst itself (~4.6 μmol). The essential role of Fermi-level tuning in balancing redox reactions and in enhancing the efficiency and stability is also elucidated.

Ultralow-threshold electrically injected AlGaN nanowire ultraviolet lasers on Si operating at low temperature

Ultraviolet laser radiation has been adopted in a wide range of applications as diverse as water purification, flexible displays, data storage, sterilization, diagnosis and bioagent detection. Success in developing semiconductor-based, compact ultraviolet laser sources, however, has been extremely limited. Here, we report that defect-free disordered AlGaN core-shell nanowire arrays, formed directly on a Si substrate, can be used to achieve highly stable, electrically pumped lasers across the entire ultraviolet AII (UV-AII) band (∼320-340 nm) at low temperatures. The laser threshold is in the range of tens of amps per centimetre squared, which is nearly three orders of magnitude lower than those of previously reported quantum-well lasers. This work also reports the first demonstration of electrically injected AlGaN-based ultraviolet lasers monolithically grown on a Si substrate, and offers a new avenue for achieving semiconductor lasers in the ultraviolet B (UV-B) (280-320 nm) and ultraviolet C (UV-C) (<280 nm) bands.

One-step overall water splitting under visible light using multiband InGaN/GaN nanowire heterostructures.

The conversion of solar energy into hydrogen via water splitting process is one of the key sustainable technologies for future clean, storable, and renewable source of energy. Therefore, development of visible light-responsive and efficient photocatalyst material has been of immense interest, but with limited success. Here, we show that overall water splitting under visible-light irradiation can be achieved using a single photocatalyst material. Multiband InGaN/GaN nanowire heterostructures, decorated with rhodium (Rh)/chromium-oxide (Cr2O3) core-shell nanoparticles can lead to stable hydrogen production from pure (pH ∼ 7.0) water splitting under ultraviolet, blue and green-light irradiation (up to ∼560 nm), the longest wavelength ever reported. At ∼440-450 nm wavelengths, the internal quantum efficiency is estimated to be ∼13%, the highest value reported in the visible spectrum. The turnover number under visible light well exceeds 73 in 12 h. Detailed analysis further confirms the stable photocatalytic activity of the nanowire heterostructures. This work establishes the use of metal-nitrides as viable photocatalyst for solar-powered artificial photosynthesis for the production of hydrogen and other solar fuels.

Highly Stable Photoelectrochemical Water Splitting and Hydrogen Generation Using a Double-Band InGaN/GaN Core/Shell Nanowire Photoanode

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.

Aluminum nitride nanowire light emitting diodes: Breaking the fundamental bottleneck of deep ultraviolet light sources

Despite broad interest in aluminum gallium nitride (AlGaN) optoelectronic devices for deep ultraviolet (DUV) applications, the performance of conventional Al(Ga)N planar devices drastically decays when approaching the AlN end, including low internal quantum efficiencies (IQEs) and high device operation voltages. Here we show that these challenges can be addressed by utilizing nitrogen (N) polar Al(Ga)N nanowires grown directly on Si substrate. By carefully tuning the synthesis conditions, a record IQE of 80% can be realized with N-polar AlN nanowires, which is nearly ten times higher compared to high quality planar AlN. The first 210 nm emitting AlN nanowire light emitting diodes (LEDs) were achieved, with a turn on voltage of about 6 V, which is significantly lower than the commonly observed 20 – 40 V. This can be ascribed to both efficient Mg doping by controlling the nanowire growth rate and N-polarity induced internal electrical field that favors hole injection. In the end, high performance N-polar AlGaN nanowire LEDs with emission wavelengths covering the UV-B/C bands were also demonstrated.

Tuning the surface charge properties of epitaxial InN nanowires

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.

High efficiency photoelectrochemical water splitting and hydrogen generation using GaN nanowire photoelectrode

We have studied the photoelectrochemical properties of both undoped and Si-doped GaN nanowire arrays in 1 mol l(-1) solutions of hydrogen bromide and potassium bromide, which were used separately as electrolytes. It is observed that variations of the photocurrent with bias voltage depend strongly on the n-type doping in GaN nanowires in both electrolytes, which are analyzed in the context of GaN surface band bending and its variation with the incorporation of Si-doping. Maximum incident-photon-to-current-conversion efficiencies of ~15% and 18% are measured for undoped and Si-doped GaN nanowires under ~350 nm light illumination, respectively. Stable hydrogen generation is also observed at a zero bias potential versus the counter-electrode.

Highly efficient, spectrally pure 340 nm ultraviolet emission from AlxGa1−xN nanowire based light emitting diodes

High crystal quality, vertically aligned AlxGa1-xN nanowire based double heterojunction light emitting diodes (LEDs) are grown on Si substrate by molecular beam epitaxy. Such AlxGa1-xN nanowires exhibit unique core-shell structures, which can significantly suppress surface nonradiative recombination. We successfully demonstrate highly efficient AlxGa1-xN nanowire array based LEDs operating at ∼340 nm. Such nanowire devices exhibit superior electrical and optical performance, including an internal quantum efficiency of ∼59% at room temperature, a relatively small series resistance, highly stable emission characteristics, and the absence of efficiency droop under pulsed biasing conditions.

Surface Emitting, High Efficiency Near-Vacuum Ultraviolet Light Source with Aluminum Nitride Nanowires Monolithically Grown on Silicon

To date, it has remained challenging to realize electrically injected light sources in the vacuum ultraviolet wavelength range (∼200 nm or shorter), which are important for a broad range of applications, including sensing, surface treatment, and photochemical analysis. In this Letter, we have demonstrated such a light source with molecular beam epitaxially grown aluminum nitride (AlN) nanowires on low cost, large area Si substrate. Detailed angle dependent electroluminescence studies suggest that, albeit the light is TM polarized, the dominant light emission direction is from the nanowire top surface, that is, along the c axis, due to the strong light scattering effect. Such an efficient surface emitting device was not previously possible using conventional c-plane AlN planar structures. The AlN nanowire LEDs exhibit an extremely large electrical efficiency (>85%), which is nearly ten times higher than the previously reported AlN planar devices. Our detailed studies further suggest that the performance of AlN nanowire LEDs is predominantly limited by electron overflow. This study provides important insight on the fundamental emission characteristics of AlN nanowire LEDs and also offers a viable path to realize an efficient surface emitting near-vacuum ultraviolet light source through direct electrical injection.