Chemical Bath Deposition of ZnO/ZnGa2O4 Core-Shell Nanowire Heterostructures Using Partial Chemical Conversion.

The development of innovative heterostructures made of ZnO nanowires is of great interest for enhancing the performances of many devices in the fields of optoelectronics, photovoltaics, and energy harvesting. We report an original fabrication process to form ZnO/ZnGa2O4 core-shell nanowire heterostructures in the framework of the wet chemistry techniques. The process involves the partial chemical conversion of ZnO nanowires grown via chemical bath deposition into ZnO/ZnGa2O4 core-shell nanowire heterostructures with a high interface quality following their immersion in an aqueous solution containing gallium nitrate heated at a low temperature. The double-step process describing the partial chemical conversion relies on successive dissolution and reaction mechanisms. The present finding offers the possibility to fabricate ZnO/ZnGa2O4 core-shell nanowire heterostructures at low temperatures and over a wide variety of substrates with a large surface area, which is attractive for nanostructured solar cells, deep-UV photodetectors, and piezoelectric devices.

Modulating the growth of chemically deposited ZnO nanowires and the formation of nitrogen- and hydrogen-related defects using pH adjustment.

ZnO nanowires (NWs) grown by chemical bath deposition (CBD) have received great interest for nanoscale engineering devices, but their formation in aqueous solution containing many impurities needs to be carefully addressed. In particular, the pH of the CBD solution and its effect on the formation mechanisms of ZnO NWs and of nitrogen- and hydrogen-related defects in their center are still unexplored. By adjusting its value in a low- and high-pH region, we show the latent evolution of the morphological and optical properties of ZnO NWs, as well as the modulated incorporation of nitrogen- and hydrogen-related defects in their center using Raman and cathodoluminescence spectroscopy. The increase in pH is related to the increase in the oxygen chemical potential (µ O), for which the formation energy of hydrogen in bond-centered sites (HBC) and VZn-NO-H defect complexes is found to be unchanged, whereas the formation energy of zinc vacancy (VZn) and zinc vacancy-hydrogen (VZn-nH) complexes steadily decreases as shown from density-functional theory calculations. Revealing that these VZn-related defects are energetically favorable to form as µ O is increased, ZnO NWs grown in the high-pH region are found to exhibit a higher density of VZn-nH defect complexes than ZnO NWs grown in the low-pH region. Annealing at 450 °C under an oxygen atmosphere helps tuning the optical properties of ZnO NWs by reducing the density of HBC and VZn-related defects, while activating the formation of VZn-NO-H defect complexes. These findings show the influence of pH on the nature of Zn(ii) species, the electrostatic interactions between these species and ZnO NW surfaces, and the formation energy of the involved defects. They emphasize the crucial role of the pH of the CBD solution and open new possibilities for simultaneously engineering the morphology of ZnO NWs and the formation of nitrogen- and hydrogen-related defects.

Optimization Strategies Used for Boosting Piezoelectric Response of Biosensor Based on Flexible Micro-ZnO Composites.

Piezoelectric ZnO-based composites have been explored as a flexible and compact sensor for the implantable biomedical systems used in cardio surgery. In this work, a progressive development route was investigated to enhance the performance of piezoelectric composites incorporated with different shape, concentration and connectivity of ZnO fillers. ZnO microrods (MRs) have been successfully synthesized homogeneously in aqueous solution using a novel process-based on chemical bath deposition (CBD) method. The morphological analysis along with Raman scattering and cathodoluminescence spectroscopy of ZnO MRs confirm their high crystalline quality, their orientation along the polar c-axis and the presence of hydrogen-related defects acting as shallow donors in their center. The experimental characterizations highlight that ZnO MR-based composites, with a higher aspect ratio (AR), lead to a significant improvement in the mechanical, dielectric and piezoelectric properties as opposed to the ZnO microparticles (MP) counterparts. The dielectrophoretic (DEP) process is then subjected to both ZnO MP- and MR-based composites, whose performance is expected to be improved as compared to the randomly dispersed composites, thanks to the creation of chain-like structures along the electric field direction. Furthermore, a numerical simulation using COMSOL software is developed to evaluate the influence of the material structuration as well as the filler's shape on the electric field distribution within different phases (filler, matrix and interface) of the composites. Finally, the aligned MR piezoelectric composites are revealed to be high potential in the development of innovative compact and biocompatible force-sensing devices. Such a technological breakthrough allows the achievement of a real-time precise characterization of mitral valve (MV) coaptation to assist surgeons during MV repair surgery.

In situ analysis of the nucleation of O- and Zn-polar ZnO nanowires using synchrotron-based X-ray diffraction.

The selection of the polarity of ZnO nanowires grown by chemical bath deposition offers a great advantage for their integration into a wide variety of engineering devices. However, the nucleation process of ZnO nanowires and its dependence on their polarity is still unknown despite its importance for optimizing their morphology and properties and thus to enhance the related device performances. To tackle this major issue, we combine an in situ analysis of the nucleation process of O- and Zn-polar ZnO nanowires on O- and Zn-polar ZnO single crystals, respectively, using synchrotron radiation-based grazing incidence X-ray diffraction with ex situ transmission and scanning electron microscopy. We show that the formation of ZnO nanowires obeys three successive phases from the induction, through nucleation to growth phases. The characteristics of each phase, including the nucleation temperature, the shape and dimension of nuclei, as well as their radial and axial development are found to depend on the polarity of ZnO nanowires. A comprehensive description reporting the dominant physicochemical processes in each phase and their dependence on the polarity of ZnO nanowires is presented, revisiting their formation process step-by-step. These findings provide a deeper understanding of the phenomena at work during the growth of ZnO nanowires by chemical bath deposition and open the perspective to develop a more accurate control of their properties at each step of the formation process.

Chemical Synthesis of ß-Ga2O3 Microrods on Silicon and Its Dependence on the Gallium Nitrate Concentration.

ß-Ga2O3 microrods have attracted increasing attention for their integration into solar blind/UV photodetectors and gas sensors. However, their synthesis using a low-temperature chemical route in aqueous solution is still under development, and the physicochemical processes at work have not yet been elucidated. Here, we develop a double-step process involving the growth of α-GaOOH microrods on silicon using chemical bath deposition and their further structural conversion to ß-Ga2O3 microrods by postdeposition thermal treatment. It is revealed that the concentration of gallium nitrate has a drastic effect on tuning the morphology, dimensions (i.e., diameter and length), and density of α-GaOOH microrods over a broad range, in turn governing the morphological properties of ß-Ga2O3 microrods. The physicochemical processes in aqueous solution are investigated by thermodynamic computations yielding speciation diagrams of Ga(III) species and theoretical solubility plots of GaOOH(s). In particular, the qualitative evolution of the morphological properties of α-GaOOH microrods with the concentration of gallium nitrate is found to be correlated with the supersaturation in the bath and discussed in light of the standard nucleation and growth theory. Interestingly, the structural conversion following the thermal treatment at 900 °C in air results in the formation of pure ß-Ga2O3 microrods without any residual minor phases and with tunable morphology and improved structural ordering. These findings reporting a double-step process for forming high-quality pure ß-Ga2O3 microrods on silicon open many perspectives for their integration onto a large number of substrates for solar blind/UV photodetection and gas sensing.

Morphology Transition of ZnO from Thin Film to Nanowires on Silicon and its Correlated Enhanced Zinc Polarity Uniformity and Piezoelectric Responses.

ZnO thin films and nanostructures have received increasing interest in the field of piezoelectricity over the last decade, but their formation mechanisms on silicon when using pulsed-liquid injection metal-organic chemical vapor deposition (PLI-MOCVD) are still open to a large extent. Also, the effects of their morphology, dimensions, polarity, and electrical properties on their piezoelectric properties have not been completely decoupled yet. By only tuning the growth temperature from 400 to 750 °C while fixing the other growth conditions, the morphology transition of ZnO deposits on silicon from stacked thin films to nanowires through columnar thin films is shown. A detailed analysis of their formation mechanisms is further provided. The present transition is associated with strong enhancement of their crystallinity and growth texture along the c-axis together with a massive relaxation of the strain in nanowires. It is also related to a prevailed zinc polarity, for which its uniformity is strongly improved in nanowires. The nucleation of basal-plane stacking faults of I1-type in nanowires is also revealed and related to an emission line at about 3.326 eV in cathodoluminescence spectra, further exhibiting fairly low phonon coupling. Interestingly, the transition is additionally associated with a significant improvement of the piezoelectric amplitude, as determined by piezoresponse force microscopy measurements. The Zn-polar domains exhibit a larger piezoelectric amplitude than the O-polar domains, showing the importance of controlling the polarity in these deposits as a prerequisite to enhance the performances of piezoelectric devices. The present findings demonstrate the high potential in using the PLI-MOCVD system to form ZnO with different morphologies and polarity uniformity on silicon. They further reveal unambiguously the superiority of nanowires over thin films for piezoelectric devices.

Formation mechanisms of ZnO nanowires on polycrystalline Au seed layers for piezoelectric applications.

ZnO nanowires are considered as attractive building blocks for piezoelectric devices, including nano-generators and stress/strain sensors. However, their integration requires the use of metallic seed layers, on top of which the formation mechanisms of ZnO nanowires by chemical bath deposition are still largely open. In order to tackle that issue, the nucleation and growth mechanisms of ZnO nanowires on top of Au seed layers with a thickness in the range of 5-100 nm are thoroughly investigated. We show that the ZnO nanowires present two different populations of nano-objects with a given morphology. The majority primary population is made of vertically aligned ZnO nanowires, which are heteroepitaxially formed on top of the Au (111) grains. The resulting epitaxial strain is found to be completely relieved at the Au/ZnO interface. In contrast, the minority secondary population is composed of ZnO nanowires with a significant mean tilt angle around 20° with respect to the normal to the substrate surface, which are presumably formed on the (211) facets of the Au (111) grains. The elongation of ZnO nanowires is further found to be limited by the surface reaction at the c-plane top facet in the investigated conditions. By implementing the selective area growth using electron beam lithography, the position of ZnO nanowires is controlled, but the two populations still co-exist in the ensemble. These findings provide an in-depth understanding of the formation mechanisms of ZnO nanowires on metallic seed layers, which should be taken into account for their more efficient integration into piezoelectric devices.

Spontaneous shape transition of thin films into ZnO nanowires with high structural and optical quality.

ZnO nanowires are usually formed by physical and chemical deposition techniques following the bottom-up approach consisting in supplying the reactants on a nucleation surface heated at a given temperature. We demonstrate an original alternative approach for the formation of ZnO nanowire arrays with high structural and optical quality, which is based on the spontaneous transformation of a ZnO thin film deposited by sol-gel process following a simple annealing. The development of these ZnO nanowires occurs through successive shape transitions, including the intermediate formation of pyramid-shaped islands. Their nucleation under near-equilibrium conditions is expected to be governed by thermodynamic considerations via the total free energy minimization related to the nanowire shape. It is further strongly assisted by the drastic reordering of the matter and by recrystallization phenomena through the massive transport of zinc and oxygen atoms towards the localized growth areas. The spontaneous shape transition process thus combines the easiness and low-cost of sol-gel process and simple annealing with the assets of the vapor phase deposition techniques. These findings cast a light on the fundamental mechanisms driving the spontaneous formation of ZnO nanowires and, importantly, reveal the great technological potential of the spontaneous shape transition process as a promising alternative approach to the more usual bottom-up approach.

Selective area growth of well-ordered ZnO nanowire arrays with controllable polarity.

Controlling the polarity of ZnO nanowires in addition to the uniformity of their structural morphology in terms of position, vertical alignment, length, diameter, and period is still a technological and fundamental challenge for real-world device integration. In order to tackle this issue, we specifically combine the selective area growth on prepatterned polar c-plane ZnO single crystals using electron-beam lithography, with the chemical bath deposition. The formation of ZnO nanowires with a highly controlled structural morphology and a high optical quality is demonstrated over large surface areas on both polar c-plane ZnO single crystals. Importantly, the polarity of ZnO nanowires can be switched from O- to Zn-polar, depending on the polarity of prepatterned ZnO single crystals. This indicates that no fundamental limitations prevent ZnO nanowires from being O- or Zn-polar. In contrast to their catalyst-free growth by vapor-phase deposition techniques, the possibility to control the polarity of ZnO nanowires grown in solution is remarkable, further showing the strong interest in the chemical bath deposition and hydrothermal techniques. The single O- and Zn-polar ZnO nanowires additionally exhibit distinctive cathodoluminescence spectra. To a broader extent, these findings open the way to the ultimate fabrication of well-organized heterostructures made from ZnO nanowires, which can act as building blocks in a large number of electronic, optoelectronic, and photovoltaic devices.

Stability of high temperature chemical vapor deposited silicon based structures on metals for solar conversion.

Highly crystallized silicon layers were grown on metal sheets at high temperature (950 degrees C) by thermal CVD from silane. An intermediate buffer layer was mandatory to prevent interdiffusion and silicide formation but also to compensate lattice parameters and thermal expansion coefficients mismatches between metal and silicon and ideally transfer some crystalline properties (grain size, texture) from the substrate to the silicon layer. After a thermodynamic study, aluminum nitride or titanium nitride diffusion barrier layers were selected and processed by CVD. The structure and the interfaces stabilities of these silicon/nitride/metal stacks were studied by field effect gun scanning and transmission electron microscopy, X-ray diffraction, Raman and energy dispersive X-ray spectroscopy. As a result, TiN deposited by CVD appears to be an efficient material as a buffer layer between steel and silicon.