Continuous-flow mass production of silicon nanowires via substrate-enhanced metal-catalyzed electroless etching of silicon with dissolved oxygen as an oxidant.
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ABSTRACT: Silicon nanowires (SiNWs) are attracting growing interest due to their unique properties and promising applications in photovoltaic devices, thermoelectric devices, lithium-ion batteries, and biotechnology. Low-cost mass production of SiNWs is essential for SiNWs-based nanotechnology commercialization. However, economic, controlled large-scale production of SiNWs remains challenging and rarely attainable. Here, we demonstrate a facile strategy capable of low-cost, continuous-flow mass production of SiNWs on an industrial scale. The strategy relies on substrate-enhanced metal-catalyzed electroless etching (MCEE) of silicon using dissolved oxygen in aqueous hydrofluoric acid (HF) solution as an oxidant. The distinct advantages of this novel MCEE approach, such as simplicity, scalability and flexibility, make it an attractive alternative to conventional MCEE methods.
Project description:In this article, we report an electroless method to fabricate porous hexagonal silicon carbide and hexagonal silicon carbide nanoparticles (NPs) as small as 1 nm using wet chemical stain etching. We observe quantum confinement effect for ultrasmall hexagonal SiC NPs in contrast to the cubic SiC NPs. We attribute this difference to the various surface terminations of the two polytypes of SiC NPs.
Project description:III-V semiconductor nanowires deterministically placed on top of silicon electronic platform would open many avenues in silicon-based photonics, quantum technologies and energy harvesting. For this to become a reality, gold-free site-selected growth is necessary. Here, we propose a mechanism which gives a clear route for maximizing the nanowire yield in the self-catalyzed growth fashion. It is widely accepted that growth of nanowires occurs on a layer-by-layer basis, starting at the triple-phase line. Contrary to common understanding, we find that vertical growth of nanowires starts at the oxide-substrate line interface, forming a ring-like structure several layers thick. This is granted by optimizing the diameter/height aspect ratio and cylindrical symmetry of holes, which impacts the diffusion flux of the group V element through the well-positioned group III droplet. This work provides clear grounds for realistic integration of III-Vs on silicon and for the organized growth of nanowires in other material systems.
Project description:Stream water dissolved oxygen was monitored in a 3.2km2 moorland headwater catchment in the Scottish Highlands. The stream consists of three 1st order headwaters and a 2nd order main stem. The stream network is fringed by peat soils with no riparian trees, though dwarf shrubs provide shading in the lower catchment. Dissolved oxygen (DO) is regulated by the balance between atmospheric re-aeration and the metabolic processes of photosynthesis and respiration. DO was continuously measured for >1 year and the data used to calibrate a mass balance model, to estimate primary production, respiration and re-aeration for a 1st order site and in the 2nd order main stem. Results showed that the stream was always heterotrophic at both sites. Sites were most heterotrophic in the summer reflecting higher levels of stream metabolism. The 1st order stream appeared more heterotrophic which was consistent with the evident greater biomass of macrophytes in the 2nd order stream, with resulting higher primary productivity. Comparison between respiration, primary production, re-aeration and potential physical controls revealed only weak relationships. However, the most basic model parameters (e.g. the parameter linking light and photosynthesis) controlling ecosystem processes resulted in significant differences between the sites which seem related to the stream channel geometry.
Project description:We demonstrate controlled fabrication of porous Si (PS) and vertically aligned silicon nanowires array starting from bulk silicon wafer by simple chemical etching method, and the underlying mechanism of nanostructure formation is presented. Silicon-oxidation rate and the electron-scavenging rate from metal catalysis play a vital role in determining the morphology of Si nanostructures. The size of Ag catalyst is found to influence the Si oxidation rate. Tunable morphologies from irregular porous to regular nanowire structure could be tailored by controlling the size of Ag nanoparticles and H2O2 concentration. Ag nanoparticles of size around 30 nm resulted in irregular porous structures, whereas discontinuous Ag film yielded nanowire structures. The depth of the porous Si structures and the aspect ratio of Si nanowires depend on H2O2 concentration. For a fixed etching time, the depth of the porous structures increases on increasing the H2O2 concentration. By varying the H2O2 concentration, the surface porosity and aspect ratio of the nanowires were controlled. Controlling the Ag catalyst size critically affects the morphology of the etched Si nanostructures. H2O2 concentration decides the degree of porosity of porous silicon, dimensions and surface porosity of silicon nanowires, and etch depth. The mechanisms of the size- and H2O2-concentration-dependent dissociation of Ag and the formation of porous silicon and silicon nanowire are described in detail.
Project description:The outstanding electrical, optical, and mechanical properties of silver nanowire transparent electrodes are attractive for use in many optoelectronic devices, and the recent developments related to these electrodes have led to their commercialization. To more fully utilize the advantages of this technology, developing new process technologies in addition to performance improvements is important. In this report, we propose a novel ultra-simple patterning technology to generate a silver nanowire transparent layer and a unique patterned structure with continuously distributed silver nanowires without any etched areas. The patterning is conducted by exposure to ultraviolet light and rinsing. The exposed and unexposed regions of the resulting layer have dramatically different electrical conductivities, which produces an electrical pathway without using any etching or lift-off processes. The unique patterned structure produced by this etching-free method creates hardly any optical difference between the two regions and results in excellent visibility of the patterned transparent electrode layer.
Project description:A deep etching method for silicon "micro"structures was successfully developed. This wet etching process is based on metal-assisted chemical etching (MACE), which was previously mainly utilized to etch the features that have lateral dimensions of "nanometers." In this novel MACE, the critical improvement was to promote the "out-of-plane" mass transfer at the metal/Si interface with an ultrathin metal film. This enabled us to etch micrometer-wide holes, which was previously challenging due to the mass transport limitation. In addition, it was found that when ethanol was used as a solvent instead of water, the formation of porous defects was suppressed. Under the optimized etch conditions, deep (>200 μm) and vertical (>88°) holes could be carved out at a fast etch rate (>0.4 μm/min). This novel deep MACE will find utility in applications such as microelectromechanical systems (MEMS) devices or biosensors.
Project description:An efficient copper-catalyzed direct o-acyloxylation of 2-phenylpyridine with carboxylic acids using oxygen as the oxidant has been developed. Various acids including aromatic acids, cinnamic acids and aliphatic acids are effective acyloxylation reagents and provide the desired products in moderate to excellent yields. The reaction proceeds well under an oxygen atmosphere, making this method potentially practical.
Project description:The growth of epitaxial Si nanowires by a metal-catalyst-free process has been investigated as an alternative to the more common metal-catalyzed vapor-liquid-solid process. The well-aligned Si nanowires are successfully grown on a (111)-oriented Si substrate without any metal catalysts by a thermal treatment using silicon sulfide as a Si source at approximately 1200 °C. The needle-shaped Si nanowires, which have a core-shell structure that consists of a single-crystalline Si core along the <111> direction consistent with the substrate direction and a surface coating of silicon oxide, are grown by a metal-catalyst-free process. In this process, the silicon sulfide in the liquid phase facilitates the nucleation and nanowire growth. In contrast, oxygen-rich nanowires that consist of crystalline Si at the tip and lumpy silicon oxide on the body are observed in a sample grown at 1300 °C, which disturbs the epitaxial growth of Si nanowires.
Project description:In this work we demonstrate a new approach towards the electroless deposition of tellurium nanowires in deep eutectic solvents. Unlike most electroless deposition where the substrate is sacrificed to drive the reduction, our process uses immobilised silver epoxy islands on gold films to give localised galvanic displacement of the silver, resulting in an even growth of wires across the entire gold electrode surface. We demonstrate the strong dependence of the nanostructure on the experimental conditions, with changes in bath temperature, tellurium concentration and the halide component of the solvent leading to sizeable alterations in the nanowire geometry. This demonstrates electroless deposition as a promising synthetic route towards low-dimensional tellurium nanostructures.
Project description:Metal-assisted chemical etching (MACE) is a widely applied process for fabricating Si nanostructures. As an electroless process, it does not require a counter electrode, and it is usually considered that only holes in the Si valence band contribute to the process. In this work, a charge carrier collecting p-n junction structure coated with silver nanoparticles is used to demonstrate that also electrons in the conduction band play a fundamental role in MACE, and enable an electroless chemical energy conversion process that was not previously reported. The studied structures generate electricity at a power density of 0.43 mW/cm2 during MACE. This necessitates reformulating the microscopic electrochemical description of the Si-metal-oxidant nanosystems to separately account for electron and hole injections into the conduction and valence band of Si. Our work provides new insight into the fundamentals of MACE and demonstrates a radically new route to chemical energy conversion by solar cell-inspired devices.