p-Type Doping of GaN Nanowires Characterized by Photoelectrochemical Measurements.

GaN nanowires (NWs) doped with Mg as a p-type impurity were grown on Si(111) substrates by plasma-assisted molecular beam epitaxy. In a systematic series of experiments, the amount of Mg supplied during NW growth was varied. The incorporation of Mg into the NWs was confirmed by the observation of donor-acceptor pairs and acceptor-bound excitons in low-temperature photoluminescence spectroscopy. Quantitative information about the Mg concentrations was deduced from Raman scattering by local vibrational modes related to Mg. In order to study the type and density of charge carriers present in the NWs, we employed two photoelectrochemical techniques, open-circuit potential and Mott-Schottky measurements. Both methods showed the expected transition from n-type to p-type conductivity with increasing Mg doping level, and the latter characterization technique allowed us to quantify the charge carrier concentration. Beyond the quantitative information obtained for Mg doping of GaN NWs, our systematic and comprehensive investigation demonstrates the benefit of photoelectrochemical methods for the analysis of doping in semiconductor NWs in general.

Broad Band Light Absorption and High Photocurrent of (In,Ga)N Nanowire Photoanodes Resulting from a Radial Stark Effect.

The photoelectrochemical properties of (In,Ga)N nanowire photoanodes are investigated using H2O2 as a hole scavenger to prevent photocorrosion. Under simulated solar illumination, In0.16Ga0.84N nanowires grown by plasma-assisted molecular beam epitaxy show a high photocurrent of 2.7 mA/cm2 at 1.2 V vs reversible hydrogen electrode. This value is almost the theoretical maximum expected from the corresponding band gap (2.8 eV) for homogeneous bulk material without taking into account surface effects. These nanowires exhibit a higher incident photon-to-current conversion efficiency over a broader wavelength range and a higher photocurrent than a compact layer with higher In content of 28%. These results are explained by the combination of built-in electric fields at the nanowire sidewall surfaces and compositional fluctuations in (In,Ga)N, which gives rise to a radial Stark effect. This effect enables spatially indirect transitions at energies much lower than the band gap. The resulting broad band light absorption leads to high photocurrents. This benefit of the radial Stark effect in (In,Ga)N nanowires for solar harvesting applications opens up the perspective to break the theoretical limit for photocurrents.

Radial Stark Effect in (In,Ga)N Nanowires.

We study the luminescence of unintentionally doped and Si-doped InxGa1-xN nanowires with a low In content (x < 0.2) grown by molecular beam epitaxy on Si substrates. The emission band observed at 300 K from the unintentionally doped samples is centered at much lower energies (800 meV) than expected from the In content measured by X-ray diffractometry and energy dispersive X-ray spectroscopy. This discrepancy arises from the pinning of the Fermi level at the sidewalls of the nanowires, which gives rise to strong radial built-in electric fields. The combination of the built-in electric fields with the compositional fluctuations inherent to (In,Ga)N alloys induces a competition between spatially direct and indirect recombination channels. At elevated temperatures, electrons at the core of the nanowire recombine with holes close to the surface, and the emission from unintentionally doped nanowires exhibits a Stark shift of several hundreds of meV. The competition between spatially direct and indirect transitions is analyzed as a function of temperature for samples with various Si concentrations. We propose that the radial Stark effect is responsible for the broadband absorption of (In,Ga)N nanowires across the entire visible range, which makes these nanostructures a promising platform for solar energy applications.

Photoelectrochemical properties of (In,Ga)N nanowires for water splitting investigated by in situ electrochemical mass spectroscopy.

We investigated the photoelectrochemical properties of both n- and p-type (In,Ga)N nanowires (NWs) for water splitting by in situ electrochemical mass spectroscopy (EMS). All NWs were prepared by plasma-assisted molecular beam epitaxy. Under illumination, the n-(In,Ga)N NWs exhibited an anodic photocurrent, however, no O2 but only N2 evolution was detected by EMS, indicating that the photocurrent was related to photocorrosion rather than water oxidation. In contrast, the p-(In,Ga)N NWs showed a cathodic photocurrent under illumination which was correlated with the evolution of H2. After photodeposition of Pt on such NWs, the photocurrent density was significantly enhanced to 5 mA/cm(2) at a potential of -0.5 V/NHE under visible light irradiation of ∼40 mW/cm(2). Also, incident photon-to-current conversion efficiencies of around 40% were obtained at -0.45 V/NHE across the entire visible spectral region. The stability of the NW photocathodes for at least 60 min was verified by EMS. These results suggest that p-(In,Ga)N NWs are a promising basis for solar hydrogen production.