Vertical GaN nanowires are grown in a self-induced way on a sputtered Ti film by plasma-assisted molecular beam epitaxy. Both in situ electron diffraction and ex situ ellipsometry show that Ti is converted to TiN upon exposure of the surface to the N plasma. In addition, the ellipsometric data demonstrate this TiN film to be metallic. The diffraction data evidence that the GaN nanowires have a strict epitaxial relationship to this film. Photoluminescence spectroscopy of the GaN nanowires shows excitonic transitions virtually identical in spectral position, line width, and decay time to those of state-of-the-art GaN nanowires grown on Si. Therefore, the crystalline quality of the GaN nanowires grown on metallic TiN and on Si is equivalent. The freedom to employ metallic substrates for the epitaxial growth of semiconductor nanowires in high structural quality may enable novel applications that benefit from the associated high thermal and electrical conductivity as well as optical reflectivity.
The realization of semiconductor structures with stable excitons at room temperature is crucial for the development of excitonics and polaritonics. Quantum confinement has commonly been employed for enhancing excitonic effects in semiconductor heterostructures. Dielectric confinement, which gives rises to much stronger enhancement, has proven to be more difficult to achieve because of the rapid nonradiative surface/interface recombination in hybrid dielectric-semiconductor structures. Here, we demonstrate intense excitonic emission from bare GaN nanowires with diameters down to 6 nm. The large dielectric mismatch between the nanowires and vacuum greatly enhances the Coulomb interaction, with the thinnest nanowires showing the strongest dielectric confinement and the highest radiative efficiency at room temperature. In situ monitoring of the fabrication of these structures allows one to accurately control the degree of dielectric enhancement. These ultrathin nanowires may constitute the basis for the fabrication of advanced low-dimensional structures with an unprecedented degree of confinement.
We investigate the nature of excitons bound to I 1 basal-plane stacking faults [(I 1 , X)] in GaN nanowire ensembles by continuous-wave and time-resolved photoluminescence spectroscopy. Based on the linear increase of the radiative lifetime of these excitons with temperature, they are demonstrated to exhibit a two-dimensional density of states, i. e., a basal-plane stacking fault acts as a quantum well. From the slope of the linear increase, we determine the oscillator strength of the (I 1 , X) and show that the value obtained reflects the presence of large internal electrostatic fields across the stacking fault. While the recombination of donor-bound and free excitons in the GaN nanowire ensemble is dominated by nonradiative phenonema already at 10 K, we observe that the (I 1 , X) recombines purely radiatively up to 60 K. This finding provides important insight into the nonradiative recombination processes in GaN nanowires. First, the radiative lifetime of about 6 ns measured at 60 K sets an upper limit for the surface recombination velocity of 450 cm s −1 considering the nanowires mean diameter of 105 nm. Second, the density of nonradiative centers responsible for the fast decay of donor-bound and free excitons cannot be higher than 2 × 10 16 cm −3 . As a consequence, the nonradiative decay of donor-bound excitons in these GaN nanowire ensembles has to occur indirectly via the free exciton state.
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.
Light emitting diodes (LEDs) have been fabricated using ensembles of free-standing (In, Ga)N/GaN nanowires (NWs) grown on Si substrates in the self-induced growth mode by molecular beam epitaxy. Electron-beam-induced current analysis, cathodoluminescence as well as biased μ-photoluminescence spectroscopy, transmission electron microscopy, and electrical measurements indicate that the electroluminescence of such LEDs is governed by the differences in the individual current densities of the single-NW LEDs operated in parallel, i.e. by the inhomogeneity of the current path in the ensemble LED. In addition, the optoelectronic characterization leads to the conclusion that these NWs exhibit N-polarity and that the (In, Ga)N quantum well states in the NWs are subject to a non-vanishing quantum confined Stark effect.
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