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The spinel group is a growing family of materials with general formulation AB2X4 (the X anion typically being a chalcogen like O and S) with many advanced applications for energy. At the time being, the spinel zinc gallate (ZnGa2O4) arguably is the ternary ultra-wide bandgap bipolar oxide semiconductor with the largest bandgap (∼5eV), making this material very promising for implementations in deep UV optoelectronics and ultra-high power electronics. In this work, we further demonstrate that, exploiting the rich cation coordination possibilities of the spinel chemistry, the ZnGa2O4 intrinsic conductivity (and its polarity) can be controlled well over 10 orders of magnitude. p-type and n-type ZnGa2O4 epilayers can be grown by tuning the pressure, oxygen flow and cation precursors ratio during metal-organic chemical vapor deposition. A relatively deep acceptor level can be achieved by promoting antisites (ZnGa) defects, while up to a (n > 1019 cm−3) donor concentration is obtained due to the hybridization of the Zn–O orbitals in the samples grown in Zn-rich conditions. Electrical transport, atomic and optical spectroscopy reveal a free hole conduction (at high temperature) for p-ZnGa2O4 while for n-ZnGa2O4 a (Mott) variable range hopping (VRH) and negative magnetoresistance phenomena take place, originated from “self-impurity” band located at Ev+ ∼3.4 eV. Among arising ultra-wide bandgap semiconductors, spinel ZnGa2O4 exhibit unique self-doping capability thus extending its application at the very frontier of current energy optoelectronics., This study was financially supported by Ministry of Science and Technology, Taiwan (MOST 109-2622-E-009-033, 108-2618-E-009-031, 109-2224-E-009-002, 109-2634-F-009-028, 109-2221-E-009-143-MY3, 108-2628-E-002-010-MY3) and the Higher Education SPROUT Project-Center for Emergent Functional Matter Science of National Yang Ming Chiao Tung University.

International audience; Surface diffusion is known to be of prime importance in the growth of semiconductor nanowires. In this work, we used ZnMgO layers as markers to analyze the growth mechanisms and kinetics during the deposition of ZnMgO/ZnO multilayered shells by molecular beam epitaxy on previously grown ZnO nanowire cores (so called core-shell heterostructures). Specifically, the influence of the O2 flow sent into the plasma cell on the adatom surface mobility was investigated. By carefully measuring the growth rate on the lateral facets as well as on the top of the nanowires, it is concluded that the surface diffusion length of adatoms, within the used MBE growth conditions, is very low. Such poor surface mobility explains why so few works can be found related to the spontaneous growth (without catalyst) of ZnO nanowires by MBE, contrary to other deposition techniques.

The metal–organic chemical vapor deposition growth of various Ga-doped ZnO nanostructures for plasmonics is investigated, with a particular focus on the nanowire facet transformations induced by the addition of trimethylgallium in the gas phase. For nonintentionally doped spontaneous ZnO nanowires, the aspect ratio is strongly decreased due to residual Ga in the reactor, and the shape evolves rapidly toward Christmas-tree-like and hierarchical structures upon intentional Ga doping. Regarding ZnO/ZnO:Ga core–shell structures, a change of the smooth initial M-oriented facets occurs, with the development of {2021} surfaces, and further {1011} and {0001} surfaces. Interestingly, a similar evolution of the lateral roughness is observed in Au-catalyzed doped nanowires. High concentrations of Ga in the grown nanostructures are revealed by photoluminescence and confirmed by Rutherford backscattering spectrometry. First photoacoustic measurements show an optical absorption at 6 μm, evidencing that the degenerate...

Which the actual critical electrical field of the ultra-wide bandgap semiconductor β-Ga2O3 is? Even that it is usual to find in the literature a given value for the critical field of wide and ultra-wide semiconductors such as SiC (3 MV/cm), GaN (3.3 MV/cm), β-Ga2O3 (~8 MV/cm) and diamond (10 MV/cm), this value actually depends on intrinsic and extrinsic factors such as the bandgap energy, material residual impurities or introduced dopants. Indeed, it is well known from 1950's that reducing the residual doping (NB) of the semiconductor layer increases the breakdown voltage capability of a semiconductor media (e.g. as 𝑁𝑁𝐵𝐵 −3⁄4 by using the Fulop's approximation for an abrupt junction). A key limitation is, therefore, the residual donor/acceptor concentration generally found in these materials. Here, we report that doping with amphoteric Zinc a p-type β-Ga2O3 thin films shortens free carrier mean free path (0.37 nm), resulting in the ultra-high critical electrical field of 13.2 MV/cm. Therefore, the critical breakdown field can be, at least, four times larger for the emerging Ga2O3 power semiconductor as compared to SiC and GaN. We further explain these wide-reaching experimental facts by using theoretical approaches based on the impact ionization microscopic theory and thermodynamic calculations., Hagar Mohammed would like to acknowledge Cultural Affairs and Massion Sector, Egyptian Ministry for Higher Education for her fellowship giving possibility work in France. APT acknowledges Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER) under contract ENE2015-74275-JIN. The ICN2 is funded by the CERCA programme/Generalitat de Catalunya and by the Severo Ochoa programme of the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, grant no. SEV-2017-0706).

Coaxially periodic ZnO/ZnMgO core-multishell nanowire (NW) heterostructures were grown via a metal organic chemical vapor deposition method. We investigated their electrical properties via the application of two locally resolved electrical scanning probe microscopy techniques, i.e., scanning capacitance microscopy (SCM) and scanning spreading resistance microscopy (SSRM), following a planarization process. As a result, ZnO and ZnMgO layers can be unambiguously distinguished by both techniques on NWs with diameters

The characterization of nanowires (NWs) often requires the use of scanning electron beam techniques because of their high spatial resolution. However, the impact of the high energetic electron beam on the physical parameters under investigation is rarely taken into account. In this work, a combination of optical and electrical techniques is involved for the measurement of the electron beam dose (EBD) dependence of cathodoluminescence intensity, exciton diffusion length and electrical resistance in ZnO NWs. Large EBD dependences of these key parameters are observed and their reversibility is investigated. The results are discussed in terms of bulk and surface reversible modifications. In particular, the behaviors of surface recombination velocity and surface space charge under electron beam exposure are determined and simulated. This study points out that caution must be taken and experimental protocols must be well defined when measuring physical parameters of NWs using electron beam techniques.

Scanning spreading resistance microscopy (SSRM) was performed on non-intentionally doped (nid) ZnO nanowires (NWs) grown by metal-organic chemical vapor deposition in order to measure their residual carrier concentration. For this purpose, an SSRM calibration profile has been developed on homoepitaxial ZnO:Ga multilayer staircase structures grown by molecular beam epitaxy. The Ga density measured by SIMS varies in the 1.7 × 1017 cm−3 to 3 × 1020 cm−3 range. From measurements on such Ga doped multi-layers, a monotonic decrease in SSRM resistance with increasing Ga density was established, indicating SSRM being a well-adapted technique for two dimensional dopant/carrier profiling on ZnO at nanoscale. Finally, relevant SSRM signal contrasts were detected on nid ZnO NWs, and the residual carrier concentration is estimated in the 1–3 × 1018 cm−3 range, in agreement with the result from four-probe measurements.

ZnO thin films were grown by metalorganic chemical vapor deposition on (0001) Zn- and O-polar surfaces of ZnO substrate. The surface morphology of these films was investigated by micro-Raman scattering and scanning electron microscopy. In the case of Zinc-polar face and using back scattering configuration, two new Raman bands were observed at 398 and 584.5 cm−1. They have been interpreted as quasi phonons TO (qTO) and LO (qLO) respectively. The origin of these modes was attributed to the particular morphology of ZnO films grown on Zn-polar face, which consists in c -axis nano-platelets, randomly tilted from the substrate. qTO and qLO frequencies have been calculated using the model of Loudon. SEM observation is in agreement with our Raman interpretation.

Various one-dimensional (1D) ZnO-based nanostructures, including ZnO nano-wires (NWs) grown using vapour-liquid-solid (VLS) process, ZnO/ZnSe core/shell, nitrogen-doped ZnO and ZnMgO NWs were grown by metalorganic chemical vapour deposition (MOCVD). Transmission electron microscopy (TEM) analysis is presented. For all the samples, a high crystalline quality is observed. Some features are emphasized such as the gold contamination of ZnO wires grown under the metal droplets in the VLS process. It is concluded that MOCVD is a suitable technique for the realization of original ZnO nanodevices.

Possibilities of obtaining laterally ordered arrays of GaAs nanowhiskers on GaAs (110) and GaAs(111)As surfaces during the molecular beam epitaxy are considered. As in the case of the GaAs(111)As substrate, nanowhiskers are formed in the hexagonal phase on the GaAs(110) surface, which is also confirmed by the patterns of the reflection high-energy electron diffraction (obtained during the growth of nanowhiskers) and by the photoluminescence spectra.

The conduction through unintentionally doped ZnO nanowires grown by metalorganic chemical vapor deposition versus temperature (4 to 300 K) and nanowire radius (50 to 175 nm) was investigated. To obtain a reliable picture of the electrical conduction, controlled experimental conditions were used to master the influence of the surrounding environment. Conduction in the nanowires was found to be metallic through the core of the degenerate semiconductor. The origin of the high residual doping level [(1–5) × 1018 cm−3] is discussed in terms of incorporation of impurities during the growth process.

We report on the growth, structural and optical properties of GaN/AlN free standing NWs. The NW lateral growth rate was investigated using thin AlN marker layers. The lateral growth is found to be homogeneous along the NW axis. Its rate can be tuned from ∼1% to ∼10% of the axial growth rate by changing III/V flux ratio. The resulting axial and lateral heterostructures were studied by micro-photoluminescence and micro-cathodoluminescence, which revealed sharp (several meV broad) emission lines. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

International audience; Current–voltage and Kelvin probe force microscopy (KPFM) measurements were performedon single ZnO nanowires. Measurements are shown to be strongly correlated with the contactbehavior, either Ohmic or diode-like. The ZnO nanowires were obtained by metallo-organicchemical vapor deposition (MOCVD) and contacted using electronic-beam lithography.Depending on the contact geometry, good quality Ohmic contacts (linear I–V behavior) ornon-linear (diode-like) contacts were obtained. Current–voltage and KPFM measurements onboth types of contacted ZnO nanowires were performed in order to investigate their behavior.A clear correlation could be established between the I–V curve, the electrical potential profilealong the device and the nanowire geometry. Some arguments supporting this behavior aregiven based on technological issues and on depletion region extension. This work will help tobetter understand the electrical behavior of Ohmic contacts on single ZnO nanowires, forfuture applications in nanoscale field-effect transistors and nano-photodetectors.

ZnO/ZnO:Sb core-shell structured nanowires (NWs) were grown by the metal organic chemical vapor deposition method where the shell was doped with antimony (Sb) in an attempt to achieve ZnO p-type conduction. To directly investigate the Sb doping effect in ZnO, scanning capacitance microscopy (SCM) and scanning spreading resistance microscopy (SSRM) were performed on the NWs' cross-sections mapping their two dimensional (2D) local electrical properties. Although no direct p-type inversion in ZnO was revealed, a lower net electron concentration was pointed out for the Sb-doped ZnO shell layer with respect to the non-intentionally doped ZnO core, indicating an evident compensating effect as a result of the Sb incorporation, which can be ascribed to the formation of Sb-related acceptors. The results demonstrate SCM/SSRM investigation being a direct and effective approach for characterizing radial semiconductor one-dimensional (1D) structures and, particularly, for the doping study on the ZnO nanomaterial towar...

We study theoretically and experimentally nonlinear effects during the ``vapor-liquid-solid'' growth of semiconductor nanowires. Nonlinear growth equation considered contains kinetic coefficients from the surface and sidewall diffusion which can be of either signs. We predict four possible growth scenarios: (I) infinite growth; (II) decomposition; (III) averaging growth to a finite length; and (IV) continuing growth such that nanowires of small initial length decay and longer nanowires grow infinitely. We present the experimental evidence of nontrivial scenarios (II) and (IV) during the Au-assisted molecular-beam epitaxy of GaAs nanowires. Scenario (II) corresponds to the evaporation of GaAs nanowires during the annealing. Scenario (IV) is observed during two-step growth procedure where a low-temperature growth is followed by deposition at $630\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$. We show that the growth via scenario (IV) enables to control the crystal phase and to obtain the stacking-fault-free sections of zinc-blende GaAs NWs having only 15--20 nm in radius.

In this work, we report on the Au-assisted MBE of various InP and related material NWs on InP(111)B substrates. The influence of growth conditions on the InAsP insertion geometry and composition in InP nanowire is evidenced. Ex-situ thermal annealing produces significant changes to the PL spectra of these heterostructures. It is shown that InP/InAsP/InP heterostructures are well suited for fabrication of emitters in the telecommunication wavelength range 1.3-1.55 mum.

Homoepitaxial growths of ZnO were performed by low pressure metal organic chemical vapor deposition (MOCVD) on both bulk hydrothermal and thin film buffer layers of ZnO grown by pulsed laser deposition on c-sapphire substrates. The surface roughness, photoluminescence, and x-ray diffraction (0002) peak omega rocking-curve line widths for the bulk and thin film substrates were similar prior to MOCVD growth. After MOCVD growth, it was found that the surface morphology, crystallographic quality, and optical properties of the ZnO layers were far superior to those typically observed for heteroepitaxial growth of ZnO layers on c-sapphire by MOCVD. The MOCVD layers were comparable for growths on both the bulk substrate and the thin film buffer layer. Furthermore, no significant impact of carrier gas was observed. The quality of the ZnO layer appeared to be correlated with the surface morphology and the crystalline quality of the substrate rather than being dependent on whether the substrate was in bulk or thin f...

This paper reports on the growth, structural and optical properties of GaN free-stranding nanowires synthesized in catalyst-free mode on Si(111) substrate by plasma-assisted molecular beam epitaxy. Cylindrical nanowires with a hexagonal cross-section defined by planes and diameters down to 20 nm were observed. The nanowire length increases as a function of their diameter, following the Gibbs–Thomson expression. The growth rate in the lateral direction was studied using thin AlN marker layers showing that the lateral over axial growth rate ratio can be tuned from ~1% to ~10% by changing the III/V flux ratio, with the lateral growth remaining homogeneous along the NW axis. Nanowire ensembles showed a strong near band edge photoluminescence up to room temperature. Low-temperature micro-photoluminescence from a single wire is peaked at 3.478 eV with broadening of 6–10 meV. This emission is similar to the luminescence of nanowire ensembles, which demonstrates strain homogeneity from wire to wire. The optical properties along the wire axis probed by micro-cathodoluminescence were found to be uniform, with no evidence of a higher defect density in the bottom part of the nanowires next to the Si substrate.

International audience; We report on the efficient room-temperature photoluminescence (PL) quenching of ZnO in the presence of 2,4-dinitrotoluene (DNT) vapor and for concentration as low as 180 ppb. Compared to ZnO thin films, ZnO nanowires exhibit a strong (95%) and fast (41 s) quenching of the PL intensity in the presence of DNT vapor.Assuming that the PL quenching is due to a trapping of the ZnO excitons by adsorbed DNT molecules, Monte-Carlo calculations show that the nanometric dimensions as well as the better crystallographic quality (longer mean free path) of the ZnO nanowires result in an enhanced trapping process at the origin of the improved sensing properties of the nanowires. The results demonstrate the importance of nanostructures in improving the sensitivity of ZnO. The study also reveals the sensing capability of ZnO nanowires and paves the path towards the potential realization of low-cost sub-ppb nitroaromaticderivative sensors.