We investigate in detail the self-assembled nucleation and growth of vertically oriented GaN nanowires by molecular beam epitaxy on crystalline TiN films. We demonstrate that this type of substrate allows for the growth of long and thin GaN nanowires that do not suffer from coalescence, a problem common to the growth on Si and other substrates. Only beyond a certain nanowire length that depends on the nanowire density and exceeds here 1.5 μm, coalescence takes place by bundling, i.e. the same process as on Si. By analyzing the nearest neighbor distance distribution, we identify the diffusion-induced repulsion of neighboring nanowires as the main mechanism limiting nanowire density during nucleation on TiN. Since on Si the final density is determined by shadowing of the impinging molecular beams by existing nanowires, it is the difference in adatom surface diffusion that enables the formation of nanowire ensembles with reduced density on TiN. These nanowire ensembles combine properties that make them a promising basis for the growth of core–shell heterostructures.
1 December 2021 in ACS Applied Materials & Interfaces
Methylammonium lead tribromide (MAPbBr3) perovskite single crystals demonstrate to be excellent direct X-ray and gamma-ray detectors with outstanding sensitivity and low limit of detection. Despite this, thorough studies on the photophysical effects of exposure to high doses of ionizing radiation on this material are still lacking. In this work, we present our findings regarding the effects of controlled X-ray irradiation on the optoelectronic properties of MAPbBr3 single crystals. Irradiation is carried out in air with an imaging X-ray tube, simulating real-life application in a medical facility. By means of surface photovoltage spectroscopy, we find that X-ray exposure quenches free excitons in the material and introduces new bound excitonic species. Despite this drastic effect, the crystals recover after 1 week of storage in dark and low humidity conditions. By means of X-ray photoelectron spectroscopy, we find that the origin of the new bound excitonic species is the formation of bromine vacancies, leading to local changes in the dielectric response of the material. The recovery effect is attributed to vacancy filling by atmospheric oxygen and water.
We report room temperature Hall mobility measurements, low temperature magnetoresistance analysis and low-frequency noise characterization of inkjet-printed graphene films on fused quartz and SiO2/Si substrates. We found that thermal annealing in vacuum at 450 °C is a necessary step in order to stabilize the Hall voltage across the devices, allowing their electrical characterization. The printed films present a minimum sheet resistance of 23.3 Ω sq−1 after annealing, and are n-type doped, with carrier concentrations in the low 1020 cm−3 range. The charge carrier mobility is found to increase with increasing film thickness, reaching a maximum value of 33 cm2 V−1 s−1 for a 480 nm-thick film printed on SiO2/Si. Low-frequency noise characterization shows a 1/f noise behavior and a Hooge parameter in the range of 0.1–1. These results represent the first in-depth electrical and noise characterization of transport in inkjet-printed graphene films, able to provide physical insights on the mechanisms at play.
We report on plasma-assisted molecular beam epitaxial growth of almost randomly oriented, uniformly tilted, and vertically aligned self-assembled GaN nanowires (NWs), respectively, on different types of polycrystalline Ti foils. The NW orientation with respect to the substrate normal, which is affected by an in situ treatment of the foil surface before NW growth, depends on the crystallinity of the native oxide. Direct growth on the as-received foils results in the formation of ensembles of nearly randomly oriented NWs due to the strong roughening of the surface induced by chemical reactions between the impinging elements and Ti. Surface nitridation preceding the NW growth is found to reduce this roughening by transformation of the uppermost layers into TiN and TiO x N y species. These compounds are more stable against chemical reactions and facilitate the growth of uniformly oriented GaN NW ensembles on the surface of the individual grains of the polycrystalline Ti foils. If an amorphous oxide layer is present at the foil surface, vertically oriented NWs are obtained all across the substrate because this layer blocks the transfering of the epitaxial information from the underlying grains. The control of NW orientation and the understanding behind the achievement of vertically oriented NWs obtained in this study represent an important step towards the realization of GaN NW-based bendable devices on polycrystalline metal foils.
We investigate the occurrence of interfacial reactions during the self-assembled formation of GaN nanowires on Ti/Al2O3(0001) substrates in plasma-assisted molecular beam epitaxy. The conditions typical for the synthesis of ensembles of long nanowires (>1 μm) are found to promote several chemical reactions. In particular, the high substrate temperature leads to the interdiffusion of Al and O at the Ti/Al2O3 interface resulting in the formation of Al x Ti y O1-x-y and Ti x O1-x compounds. Furthermore, O is found to incorporate into the nanowires degrading their luminescence by heavy n-type doping. At the same time, impinging Ga and N species react with the substrate giving rise to the simultaneous formation of single-crystalline TiN and Ga x Ti y O1-x-y compounds. The latter compounds tend to form hillocks at the substrate surface, on top of which nanowires elongate with large tilt angles with respect to the substrate normal. We develop here a specific process in order to mitigate the detrimental effects of these interfacial reactions, while maintaining the low areal density and absence of coalescence which is the strong asset of growing nanowires on Ti/Al2O3. We find that the combination of a thick Ti film with an intentional low temperature nitridation step preceding nanowire growth and a limited growth temperature results in ensembles of uncoalesced and well-oriented nanowires with luminescence properties comparable to those of standard GaN nanowires prepared on Si. All these properties, together with the inherent benefits of integrating semiconductors on metals, make the present materials combination a promising platform for the further development of group-III nitride nanowire-based devices.
Defects are inherent in transition metal dichalcogenides and significantly affect their chemical and physical properties. In this study, surface defect electrochemical nanopatterning is proposed as a promising method to tune in a controlled manner the electronic and functional properties of defective MoS₂ thin films. Using parallel electrochemical nanolithography, MoS₂ thin films are patterned, creating sulphur vacancy‐rich active zones alternated with defect‐free regions over a centimetre scale area, with sub‐micrometre spatial resolution. The patterned films display tailored optical and electronic properties due to the formation of sulphur vacancy‐rich areas. Moreover, the effectiveness of defect nanopatterning in tuning functional properties is demonstrated by studying the electrocatalytic activity for the hydrogen evolution reaction.