Engineering Silicon to Porous Silicon and Silicon Nanowires by Metal-Assisted Chemical Etching: Role of Ag Size and Electron-Scavenging Rate on Morphology Control and Mechanism.
ABSTRACT: 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:Automatic release and vertical transferring of silicon/silicon oxide nanowire arrays with a high integrity are demonstrated by an Ag-assisted ammonia etching method. By adding a water steaming step between Ag-assisted HF/H2O2 and ammonia etching to form a SiOx protective layer sheathing Si nanowires, we can tune the composition of the nanowires from SiOx (0 ? x ? 2) to Si nanowires. Ag plays a key role to the neat and uniform release of Si/SiOx nanowire arrays from Si wafer in the ammonia etching process. The vertical Si nanowire array device, with both sides having high-quality Ohmic contact, can be transferred to arbitrary substrates, especially on a flexible substrate. The method developed here offers a facile method to realize flexible Si nanowire array functional devices.
Project description:Porous silicon nanowire is emerging as an interesting material system due to its unique combination of structural, chemical, electronic, and optical properties. To fully understand their formation mechanism is of great importance for controlling the fundamental physical properties and enabling potential applications. Here we present a systematic study to elucidate the mechanism responsible for the formation of porous silicon nanowires in a two-step silver-assisted electroless chemical etching method. It is shown that silicon nanowire arrays with various porosities can be prepared by varying multiple experimental parameters such as the resistivity of the starting silicon wafer, the concentration of oxidant (H(2)O(2)) and the amount of silver catalyst. Our study shows a consistent trend that the porosity increases with the increasing wafer conductivity (dopant concentration) and oxidant (H(2)O(2)) concentration. We further demonstrate that silver ions, formed by the oxidation of silver, can diffuse upwards and renucleate on the sidewalls of nanowires to initiate new etching pathways to produce a porous structure. The elucidation of this fundamental formation mechanism opens a rational pathway to the production of wafer-scale single crystalline porous silicon nanowires with tunable surface areas ranging from 370 to 30 m(2) g(-1) and can enable exciting opportunities in catalysis, energy harvesting, conversion, storage, as well as biomedical imaging and therapy.
Project description:We report the synthesis of vertical silicon nanowire array through a two-step metal-assisted chemical etching of highly doped n-type silicon (100) wafers in a solution of hydrofluoric acid and hydrogen peroxide. The morphology of the as-grown silicon nanowires is tunable from solid nonporous nanowires, nonporous/nanoporous core/shell nanowires, to entirely nanoporous nanowires by controlling the hydrogen peroxide concentration in the etching solution. The porous silicon nanowires retain the single crystalline structure and crystallographic orientation of the starting silicon wafer and are electrically conductive and optically active with visible photoluminescence. The combination of electronic and optical properties in the porous silicon nanowires may provide a platform for novel optoelectronic devices for energy harvesting, conversion, and biosensing.
Project description:Porous materials display enhanced scattering mechanisms that greatly influence their transport properties. Metal-assisted chemical etching (MACE) enables fabrication of porous silicon nanowires starting from a doped Si wafer by using a metal template that catalyzes the etching process. Here, we report on the low thermal conductivity (?) of individual porous Si nanowires (NWs) prepared from MACE, with values as low as 0.87?W·m-1·K-1 for 90?nm diameter wires with 35-40% porosity. Despite the strong suppression of long mean free path phonons in porous materials, we find a linear correlation of ? with the NW diameter. We ascribe this dependence to the anisotropic porous structure that arises during chemical etching and modifies the phonon percolation pathway in the center and outer regions of the nanowire. The inner microstructure of the NWs is visualized by means of electron tomography. In addition, we have used molecular dynamics simulations to provide guidance for how a porosity gradient influences phonon transport along the axis of the NW. Our findings are important towards the rational design of porous materials with tailored thermal and electronic properties for improved thermoelectric devices.
Project description:The nanoscale features in silicon nanowires (SiNWs) can suppress phonon propagation and strongly reduce their thermal conductivities compared to the bulk value. This work measures the thermal conductivity along the axial direction of SiNW arrays with varying nanowire diameters, doping concentrations, surface roughness, and internal porosities using nanosecond transient thermoreflectance. For SiNWs with diameters larger than the phonon mean free path, porosity substantially reduces the thermal conductivity, yielding thermal conductivities as low as 1 W/m/K in highly porous SiNWs. However, when the SiNW diameter is below the phonon mean free path, both the internal porosity and the diameter significantly contribute to phonon scattering and lead to reduced thermal conductivity of the SiNWs.
Project description:Silicon nanowires can enhance broadband optical absorption and reduce radial carrier collection distances in solar cell devices. Arrays of disordered nanowires grown by vapor-liquid-solid method are attractive because they can be grown on low-cost substrates such as glass, and are large area compatible. Here, we experimentally demonstrate that an array of disordered silicon nanowires surrounded by a thin transparent conductive oxide has both low diffuse and specular reflection with total values as low as < 4% over a broad wavelength range of 400?nm < ? < 650?nm. These anti-reflective properties together with enhanced infrared absorption in the core-shell nanowire facilitates enhancement in external quantum efficiency using two different active shell materials: amorphous silicon and nanocrystalline silicon. As a result, the core-shell nanowire device exhibits a short-circuit current enhancement of 15% with an amorphous Si shell and 26% with a nanocrystalline Si shell compared to their corresponding planar devices.
Project description:This article presents a study on Metal-Assisted Chemical Etching (MACE) of silicon in HF-H2O2 using silver nanoparticles as catalysts. Our aim is a better understanding of the process to elaborate new 3D submicrometric surface structures useful for light management. We investigated MACE over the whole range of silicon doping, i.e., p++, p+, p, p-, n, n+, and n++. We discovered that, instead of the well-defined and straight mesopores obtained in p and n-type silicon, in p++ and n++ silicon MACE leads to the formation of cone-shaped macropores filled with porous silicon. We account for the transition between these two pore-formation regimes (straight and cone-shaped pores) by modeling (at equilibrium and under polarization) the Ag/Si/electrolyte (HF) system. The model simulates the system as two nanodiodes in series. We show that delocalized MACE is explained by a large tunnel current contribution for the p-Si/Ag and n-Si/HF diodes under reverse polarization, which increases with the doping level and when the size of the nanocontacts (Ag, HF) decreases. By analogy with the results obtained on heavily doped silicon, we finally present a method to form size-controlled cone-shaped macropores in p silicon with silver nanoparticles. This shape, instead of the usual straight mesopores, is obtained by applying an external anodic polarization during MACE. Two methods are shown to be effective for the control of the macropore cone angle: one by adjusting the potential applied during MACE, the other by changing the H2O2 concentration. Under appropriate etching conditions, the obtained macropores exhibit optical properties (reflectivity ~3 %) similar to that of black silicon.
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:Silicon nanowire chips can function as sensors for cancer DNA detection, whereby selective functionalization of the Si sensing areas over the surrounding silicon oxide would prevent loss of analyte and thus increase the sensitivity. The thermal hydrosilylation of unsaturated carbon-carbon bonds onto H-terminated Si has been studied here to selectively functionalize the Si nanowires with a monolayer of 1,8-nonadiyne. The silicon oxide areas, however, appeared to be functionalized as well. The selectivity toward the Si-H regions was increased by introducing an extra HF treatment after the 1,8-nonadiyne monolayer formation. This step (partly) removed the monolayer from the silicon oxide regions, whereas the Si-C bonds at the Si areas remained intact. The alkyne headgroups of immobilized 1,8-nonadiyne were functionalized with PNA probes by coupling azido-PNA and thiol-PNA by click chemistry and thiol-yne chemistry, respectively. Although both functionalization routes were successful, hybridization could only be detected on the samples with thiol-PNA. No fluorescence was observed when introducing dye-labeled noncomplementary DNA, which indicates specific DNA hybridization. These results open up the possibilities for creating Si nanowire-based DNA sensors with improved selectivity and sensitivity.
Project description:Two-dimensional finite difference time domain (FDTD) simulations were performed for evaluating optical absorption enhancement and loss effects of triangular silver (Ag) nanowires embedded in silicon (Si) thin-film photovoltaic device structures. Near-bandgap absorption enhancement in Si was much larger than the reported values of other nanostructures from similar simulations. A nanowire with equal sides of 20 nm length showed 368-fold absorption enhancement whereas only 5× and 15× values of solid spherical and two-dimensional core-shell type nanostructures, respectively. Undesirable absorption loss in the metal of the nanowire was 3.55× larger than the absorption in Si which was comparable to the value reported for the spherical nanoparticle. Interestingly, as the height of the nanowire was increased to form a sharper tip, absorption loss showed a significant drop. For a nanowire with 20 nm base and 20 nm height, absorption loss was merely 1.91× larger than the absorption in Si at the 840 nm plasmon resonance. This drop could be attributed to weaker plasmon resonance manifested by lower metallic absorption in the spatial absorption map of the nanowire. However, absorption enhancement in Si was still large due to strong plasmonic fields at the sharper and longer tip, which was effective in enhancing absorption over a larger area in Si. Our work shows that the shape of a nanostructure and its optimization can significantly affect plasmonic absorption enhancement and loss performance in photovoltaic applications.