Triangle pore arrays fabricated on Si (111) substrate by sphere lithography combined with metal-assisted chemical etching and anisotropic chemical etching

ABSTRACT: The morphological change of silicon macropore arrays formed by metal-assisted chemical etching using shape-controlled Au thin film arrays was investigated during anisotropic chemical etching in tetramethylammonium hydroxide (TMAH) aqueous solution. After the deposition of Au as the etching catalyst on (111) silicon through a honeycomb mask prepared by sphere lithography, the specimens were etched in a mixed solution of HF and H2O2 at room temperature, resulting in the formation of ordered macropores in silicon along the [111] direction, which is not achievable by conventional chemical etching without a catalyst. In the anisotropic etching in TMAH, the macropores changed from being circular to being hexagonal and finally to being triangular owing to the difference in etching rate between the crystal planes.     

Sub-100-nm ordered silicon hole arrays by metal-assisted chemical etching

Sub-100-nm silicon nanohole arrays were fabricated by a combination of the site-selective electroless deposition of noble metals through anodic porous alumina and the subsequent metal-assisted chemical etching. Under optimum conditions, the formation of deep straight holes with an ordered periodicity (e.g., 100 nm interval, 40 nm diameter, and high aspect ratio of 50) was successfully achieved. By using the present method, the fabrication of silicon nanohole arrays with 60-nm periodicity was also achieved.     

Lithography-free fabrication of silicon nanowire and nanohole arrays by metal-assisted chemical etching

We demonstrated a novel, simple, and low-cost method to fabricate silicon nanowire (SiNW) arrays and silicon nanohole (SiNH) arrays based on thin silver (Ag) film dewetting process combined with metal-assisted chemical etching. Ag mesh with holes and semispherical Ag nanoparticles can be prepared by simple thermal annealing of Ag thin film on a silicon substrate. Both the diameter and the distribution of mesh holes as well as the nanoparticles can be manipulated by the film thickness and the annealing temperature. The silicon underneath Ag coverage was etched off with the catalysis of metal in an aqueous solution containing HF and an oxidant, which form silicon nanostructures (either SiNW or SiNH arrays). The morphologies of the corresponding etched SiNW and SiNH arrays matched well with that of Ag holes and nanoparticles. This novel method allows lithography-free fabrication of the SiNW and SiNH arrays with control of the size and distribution.     

Antireflective silicon nanostructures with hydrophobicity by metal-assisted chemical etching for solar cell applications

We present broadband antireflective silicon (Si) nanostructures with hydrophobicity using a spin-coated Ag ink and by subsequent metal-assisted chemical etching (MaCE). Improved understanding of MaCE, by conducting parametric studies on optical properties, reveals a design guideline to achieve considerably low solar-weighted reflectance (SWR) in the desired wavelength ranges. The resulting Si nanostructures show extremely low SWR (1.96%) and angle-dependent SWR (<4.0% in the range of 0° to 60°) compared to that of bulk Si (SWR, 35.91%; angle-dependent SWR, 37.11%) in the wavelength range of 300 to 1,100 nm. Relatively large contact angle (approximately 102°) provides a self-cleaning capability on the solar cell surface.     

The mechanism of galvanic/metal-assisted etching of silicon

Metal-assisted etching is initiated by hole injection from an oxidant catalyzed by a metal nanoparticle or film on a Si surface. It is shown that the electronic structure of the metal/Si interface, i.e., band bending, is not conducive to diffusion of the injected hole away from the metal in the case of Ag or away from the metal/Si interface in the cases of Au, Pd, and Pt. Since holes do not diffuse away from the metals, the electric field resulting from charging of the metal after hole injection must instead be the cause of metal-assisted etching.     

Optical properties of silicon nanowire arrays formed by metal-assisted chemical etching: evidences for light localization effect

We study the structure and optical properties of arrays of silicon nanowires (SiNWs) with a mean diameter of approximately 100 nm and length of about 1–25 μm formed on crystalline silicon (c-Si) substrates by using metal-assisted chemical etching in hydrofluoric acid solutions. In the middle infrared spectral region, the reflectance and transmittance of the formed SiNW arrays can be described in the framework of an effective medium with the effective refractive index of about 1.3 (porosity, approximately 75%), while a strong light scattering for wavelength of 0.3 ÷ 1 μm results in a decrease of the total reflectance of 1%-5%, which cannot be described in the effective medium approximation. The Raman scattering intensity under excitation at approximately 1 μm increases strongly in the sample with SiNWs in comparison with that in c-Si substrate. This effect is related to an increase of the light-matter interaction time due to the strong scattering of the excitation light in SiNW array. The prepared SiNWs are discussed as a kind of ‘black silicon’, which can be formed in a large scale and can be used for photonic applications as well as in molecular sensing.     

Fabrication of porous silicon by metal-assisted etching using highly ordered gold nanoparticle arrays

ABSTRACT: A simple method for the fabrication of porous silicon (Si) by metal-assisted etching was developed using gold nanoparticles as catalytic sites. Etching masks were prepared by spin-coating of colloidal gold nanoparticles onto Si. Appropriate functionalization of the gold nanoparticle surface prior to the deposition step enabled the formation of quasi-hexagonally ordered arrays by self-assembly which were translated into an array of pores by subsequent etching in a HF solution containing H2O2. The quality of the pattern transfer depended on the chosen preparation conditions for the gold nanoparticle etching mask. The influence of the Si surface properties were investigated by using either hydrophilic or hydrophobic Si substrates resulting from piranha solution or HF treatment, respectively. The polymer coated gold nanoparticles had to be thermally treated in order to provide direct contact at the metal/Si interface which is required for the following metal-assisted etching. Plasma-treatment as well as flame annealing were successfully applied. Best results were obtained for Si substrates which were treated with HF prior to spin-coating and flame annealed in order to remove the polymer matrix. The presented method opens up new resources for the fabrication of porous silicon by metal-assisted etching. Here, the vast variety of metal nanoparticles accessible by well-established wet-chemical synthesis can be employed for the fabrication of the etching masks.     

Optical assessment of silicon nanowire arrays fabricated by metal-assisted chemical etching

Silicon nanowire (SiNW) arrays were prepared on silicon substrates by metal-assisted chemical etching and peeled from the substrates, and their optical properties were measured. The absorption coefficient of the SiNW arrays was higher than that for the bulk silicon over the entire region. The absorption coefficient of a SiNW array composed of 10-μm-long nanowires was much higher than the theoretical absorptance of a 10-μm-thick flat Si wafer, suggesting that SiNW arrays exhibit strong optical confinement. To reveal the reason for this strong optical confinement demonstrated by SiNW arrays, angular distribution functions of their transmittance were experimentally determined. The results suggest that Mie-related scattering plays a significant role in the strong optical confinement of SiNW arrays.     

Formation of silicon nanowire packed films from metallurgical-grade silicon powder using a two-step metal-assisted chemical etching method

In this work, we use a two-step metal-assisted chemical etching method to produce films of silicon nanowires shaped in micrograins from metallurgical-grade polycrystalline silicon powder. The first step is an electroless plating process where the powder was dipped for few minutes in an aqueous solution of silver nitrite and hydrofluoric acid to permit Ag plating of the Si micrograins. During the second step, corresponding to silicon dissolution, we add a small quantity of hydrogen peroxide to the plating solution and we leave the samples to be etched for three various duration (30, 60, and 90 min). We try elucidating the mechanisms leading to the formation of silver clusters and silicon nanowires obtained at the end of the silver plating step and the silver-assisted silicon dissolution step, respectively. Scanning electron microscopy (SEM) micrographs revealed that the processed Si micrograins were covered with densely packed films of self-organized silicon nanowires. Some of these nanowires stand vertically, and some others tilt to the silicon micrograin facets. The thickness of the nanowire films increases from 0.2 to 10 μm with increasing etching time. Based on SEM characterizations, laser scattering estimations, X-ray diffraction (XRD) patterns, and Raman spectroscopy, we present a correlative study dealing with the effect of the silver-assisted etching process on the morphological and structural properties of the processed silicon nanowire films.     

Gold-thickness-dependent Schottky barrier height for charge transfer in metal-assisted chemical etching of silicon

Large-area, vertically aligned silicon nanowires with a uniform diameter along the height direction were fabricated by combining in situ-formed anodic aluminum oxide template and metal-assisted chemical etching. The etching rate of the Si catalyzed using a thick Au mesh is much faster than that catalyzed using a thin one, which is suggested to be induced by the charge transport process. The thick Au mesh in contact with the Si produces a low Au/Si Schottky barrier height, facilitating the injection of electronic holes from the Au to the Si, thus resulting in a high etching rate.     

Si nanowires by a single-step metal-assisted chemical etching process on lithographically defined areas: formation kinetics

In this paper, we investigate the formation kinetics of Si nanowires [SiNWs] on lithographically defined areas using a single-step metal-assisted chemical etching process in an aqueous HF/AgNO₃ solution. We show that the etch rate of Si, and consequently, the SiNW length, is much higher on the lithographically defined areas compared with that on the non-patterned areas. A comparative study of the etch rate in the two cases under the same experimental conditions showed that this effect is much more pronounced at the beginning of the etching process. Moreover, it was found that in both cases, the nanowire formation rate is linear with temperature in the range from 20°C to 50°C, with almost the same activation energy, as obtained from an Arrhenius plot (0.37 eV in the case of non-patterned areas, while 0.38 eV in the case of lithographically patterned areas). The higher etch rate on lithographically defined areas is mainly attributed to Si surface modification during the photolithographic process.PACS: 68; 68.65-k.     

Hydrodeoxygenation of guaiacol on noble metal catalysts

Hydrodeoxygenation (HDO) performed at high temperatures and pressures is one alternative for upgrading of pyrolysis oils from biomass. Studies on zirconia-supported mono- and bimetallic noble metal (Rh, Pd, Pt) catalysts showed these catalysts to be active and selective in the hydrogenation of guaiacol (GUA) at 100 °C and in the HDO of GUA at 300 °C. GUA was used as model compound for wood-based pyrolysis oil. At the temperatures tested, the performance of the noble metal catalysts, especially the Rh-containing catalysts was similar or better than that of the conventional sulfided CoMo/Al₂O₃ catalyst. The carbon deposition on the noble metal catalysts was lower than that on the sulfided CoMo/Al₂O₃ catalyst. The performance of the Rh-containing catalysts in the reactions of GUA at the tested conditions demonstrates their potential in the upgrading of wood-based pyrolysis oils.     

Hydrodeoxygenation of dibenzofuran over noble metal supported on mesoporous zeolite

Hydrodeoxygenation has been considered to be one of the most promising methods for bio-oil upgrading. In this paper, the catalytic performance of noble metal supported on mesoporous zeolite in model bio-oil compound hydrodeoxygenation was examined. Dibenzofuran was chosen here because of its refractory nature and large molecular size. Our results indicate that Pt supported on mesoporous ZSM-5 show better performance in dibenzofuran hydrodeoxygenation than Pt/ZSM-5 and Pt/Al₂O₃. The excellent catalytic performance is attributed to the combination of strong acidity and mesopore structure in mesoporous zeolite.     

Fabrication and photocatalytic properties of silicon nanowires by metal-assisted chemical etching: effect of H2O2 concentration

In the current study, monocrystalline silicon nanowire arrays (SiNWs) were prepared through a metal-assisted chemical etching method of silicon wafers in an etching solution composed of HF and H₂O₂. Photoelectric properties of the monocrystalline SiNWs are improved greatly with the formation of the nanostructure on the silicon wafers. By controlling the hydrogen peroxide concentration in the etching solution, SiNWs with different morphologies and surface characteristics are obtained. A reasonable mechanism of the etching process was proposed. Photocatalytic experiment shows that SiNWs prepared by 20% H₂O₂ etching solution exhibit the best activity in the decomposition of the target organic pollutant, Rhodamine B (RhB), under Xe arc lamp irradiation for its appropriate Si nanowire density with the effect of Si content and contact area of photocatalyst and RhB optimized.     

Structure,morphology, and photoluminescence of porous Si nanowires: effect of different chemical treatments

The structure and light-emitting properties of Si nanowires (SiNWs) fabricated by a single-step metal-assisted chemical etching (MACE) process on highly boron-doped Si were investigated after different chemical treatments. The Si nanowires that result from the etching of a highly doped p-type Si wafer by MACE are fully porous, and as a result, they show intense photoluminescence (PL) at room temperature, the characteristics of which depend on the surface passivation of the Si nanocrystals composing the nanowires. SiNWs with a hydrogen-terminated nanostructured surface resulting from a chemical treatment with a hydrofluoric acid (HF) solution show red PL, the maximum of which is blueshifted when the samples are further chemically oxidized in a piranha solution. This blueshift of PL is attributed to localized states at the Si/SiO₂ interface at the shell of Si nanocrystals composing the porous SiNWs, which induce an important pinning of the electronic bandgap of the Si material and are involved in the recombination mechanism. After a sequence of HF/piranha/HF treatment, the SiNWs are almost fully dissolved in the chemical solution, which is indicative of their fully porous structure, verified also by transmission electron microscopy investigations. It was also found that a continuous porous Si layer is formed underneath the SiNWs during the MACE process, the thickness of which increases with the increase of etching time. This supports the idea that porous Si formation precedes nanowire formation. The origin of this effect is the increased etching rate at sites with high dopant concentration in the highly doped Si material.     

A periodic array of silicon pillars fabricated by photoelectrochemical etching

A periodic array of silicon pillars was photoelectrochemically fabricated using the two-step etching process with a n-type Si (1 0 0) substrate. Two key factors, backside illumination and anodic bias, were required to obtain a high-aspect ratio macropore array of silicon. It was found that the initial pore could be separated into two different pores when the applied anodic bias was greater than a certain critical value. The pore size of the macroporous silicon with a high porosity was increased by anisotropic etching in an alkaline solution. Due to destruction of the pore sidewalls, KOH etching allowed for the fabrication of silicon pillars on a large-scale wafer with an improved uniformity. The anisotropic etching behavior of KOH solution led to necking of the silicon pillars when the etching time exceeded 60 s.     

Template-free fabrication of silicon micropillar/nanowire composite structure by one-step etching

A template-free fabrication method for silicon nanostructures, such as silicon micropillar (MP)/nanowire (NW) composite structure is presented. Utilizing an improved metal-assisted electroless etching (MAEE) of silicon in KMnO₄/AgNO₃/HF solution and silicon composite nanostructure of the long MPs erected in the short NWs arrays were generated on the silicon substrate. The morphology evolution of the MP/NW composite nanostructure and the role of self-growing K₂SiF₆ particles as the templates during the MAEE process were investigated in detail. Meanwhile, a fabrication mechanism based on the etching of silver nanoparticles (catalyzed) and the masking of K₂SiF₆ particles is proposed, which gives guidance for fabricating different silicon nanostructures, such as NW and MP arrays. This one-step method provides a simple and cost-effective way to fabricate silicon nanostructures.     

Effect of the nature of the support on the catalytic performance of noble metal catalysts for the water–gas shift reaction

The catalytic activity of supported noble metal catalysts (Pt, Rh, Ru, and Pd) for the WGS reaction is investigated with respect to the physichochemical properties of the metallic phase and the support. It has been found that, for all metal-support combinations investigated, Pt is much more active than Pd, while Rh and Ru exhibit intermediate activity. The turnover frequency (TOF) of CO conversion does not depend on metal loading, dispersion or crystallite size, but depends strongly on the nature of the metal oxide carrier. In particular, catalytic activity of Pt and Ru catalysts, is 1-2 orders of magnitude higher when supported on “reducible” (TiO₂, CeO₂, La₂O₃, and YSZ) rather than on “irreducible” (Al₂O₃, MgO, and SiO₂) metal oxides. In contrast to what has been found in our previous study over Pt/TiO₂ catalysts, catalytic activity of dispersed Pt does not depend on the structural and morphological characteristics of CeO₂, such as specific surface area or primary crystallite size.     

The study on the application of solid-state method for synthesizing the polyaniline/noble metal (Au or Pt) hybrid materials

The solid-state method was applied for synthesizing polyaniline (PANI)/noble metal hybrid materials with the presence of HAuCl₄·4H₂O or H₂PtCl₆·6H₂O in the reaction medium. The structure, morphology, and electrochemical activity of the composites were characterized by Fourier transform infrared (FTIR) spectra, UV-visible (vis) absorption spectra, energy dispersive spectrum (EDS), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and cyclic voltammetry. The results from FTIR and UV-vis spectra showed that the oxidation degree and doping level of the PANI in composites can be influenced by HAuCl₄·4H₂O and H₂PtCl₆·6H₂O. The EDS data demonstrated that the composites contain a certain amount of Au (or Pt) element. XRD analysis indicated the presence of crystalline-state Au particles in PANI matrix prepared from the presence of HAuCl₄·4H₂O and revealed that the H₂PtCl₆·6H₂O cannot be converted into metal Pt. The TEM and SEM images implied that the Au particles did exist in the polymer matrix with the size of about 20 nm. The enzymeless H₂O₂ sensor constructed with PANI/Au composite from the presence of HAuCl₄·4H₂O showed a short response time (within 5 s) and displayed an excellent performance in wide linear range.     

Effect of potential steps on porous silicon formation

Porous silicon microstructures were fabricated by applying potential steps through which both anodic and cathodic potentials were periodically applied to silicon wafers. The electrochemical behaviors of porous silicon layers were examined by performing polarization measurements, followed by analyzing the open-circuit potential (E_ocp) and the reaction rate in terms of corrosion current density (j_corr). The surface morphologies and surface products of porous silicon were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It was found that the values of E_ocp and j_corr varied more significantly and irregularly during different polarization stages when the potentials were continuously applied to the wafer surface, while virtually unchanged after 2 min of periodic potential application. In addition, slower reaction rates were observed with applying potential steps, as indicated by smaller values of j_corr. The enhancement on refreshment of silicon surfaces by periodic potential polarization significantly accelerated the growth of porous silicon. The microstructures became more uniformed and better defined due to the improved passivating nature of wafer surfaces.