Effect of noble metal catalyst species on the morphology of macroporous silicon formed by metal-assisted chemical etching

Macroporous silicon with ordered pore intervals was fabricated by the site-selective chemical etching of a Si substrate using patterned noble-metal thin films as a catalyst. The morphology of the etched silicon surface and the etching rate was affected by the shape of deposits and metal catalyst species such as Pt-Pd, Au, and Pt. The etching rate increased in the following order: Au < Pt ≤ Pt-Pd. The pores of macroporous silicon prepared by using Pt-Pd catalyst were conical in shape because of the chemical dissolution of the surface of the macropores. On the other hand, by using Au catalyst, relatively straight pores with uniform diameter were formed in the direction of pore depth. The morphology of macroporous silicon was assumed to be affected by the difference in the shape of metal catalysts and the diffusion behaviour of injected positive holes at the silicon/metal interface.     

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.     

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.     

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.     

流体微通道浸泡蚀刻技术实验

微细加工技术是伴随着微制造的出现而产生的一类新型现代化制造技术,它实现了微小尺度范围内的机械加工和装配。化学蚀刻技术是微细加工技术主要的加工方法之一,包括浸泡、鼓泡、喷淋等方法,其中浸泡式蚀刻方法相对来说设备简单、操作方便、节约成本。本文采用单因素浸泡式方法对不锈钢板蚀刻进行了实验研究,研究了蚀刻时间、蚀刻液组分浓度及温度等因素对化学蚀刻质量的影响。结果表明,蚀刻液中FeCl₃浓度、H₃PO₄浓度、温度等对蚀刻速度、蚀刻均匀性、侧蚀及粗糙度有较大的影响。研究结果对流体微细通道的制造提供了初步工艺参数。     

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.     

Non-damage deep etching of SiC by hybrid laser-high temperature chemical processing

SiC is considered as preferred material for micro-electro-mechanical system in the future. The excellent mechanical property and chemical stability make it difficult to perform deep etching. The hybrid laser-high temperature chemical etching is investigated to realize non-damage deep etching of SiC. The influences of defocus, laser pulse interval, laser intensity, and pulse number on etching depth are researched. The optimized laser parameter for SiC non-damage deep etching is laser intensity of 10 × 10⁹ W/cm² with a pulse interval of 10 ms. In order to analyze the interaction mechanism, the temperature field and laser-induced liquid jet in the liquid environment are calculated numerically. It is concluded that the material removal mechanism consists of laser heating vaporization during laser pulse, mechanical effect of laser-induced liquid jet impact between two adjacent laser pulses and chemical etching in laser-induced local high-temperature environment. The chemical reaction between SiC and mixture of HF, and HNO₃ solution produces gases and fluosilicic acid and effectively reduces the roughness of the modified layer making the surface smoother, and also removes the microcracks on the side wall of the etched region.     

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.     

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.     

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.     

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 nanostructured silicon surfaces by stain etching

In this work, we report the fabrication of ordered silicon structures by chemical etching of silicon in vanadium oxide (V₂O₅)/hydrofluoric acid (HF) solution. The effects of the different etching parameters including the solution concentration, temperature, and the presence of metal catalyst film deposition (Pd) on the morphologies and reflective properties of the etched Si surfaces were studied. Scanning electron microscopy (SEM) was carried out to explore the morphologies of the etched surfaces with and without the presence of catalyst. In this case, the attack on the surfaces with a palladium deposit begins by creating uniform circular pores on silicon in which we distinguish the formation of pyramidal structures of silicon. Fourier transform infrared spectroscopy (FTIR) demonstrates that the surfaces are H-terminated. A UV-Vis-NIR spectrophotometer was used to study the reflectance of the structures obtained. A reflectance of 2.21% from the etched Si surfaces in the wavelength range of 400 to 1,000 nm was obtained after 120 min of etching while it is of 4.33% from the Pd/Si surfaces etched for 15 min.     

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.     

Formation mechanism of SiGe nanorod arrays by combining nanosphere lithography and Au-assisted chemical etching

ABSTRACT: The formation mechanism of SiGe nanorod (NR) arrays fabricated by combining nanosphere lithography and Au-assisted chemical etching has been investigated. By precisely controlling the etching rate and time, the lengths of SiGe NRs can be tuned from 300 nm to 1 μm. The morphologies of SiGe NRs were found to change dramatically by varying the etching temperatures. We propose a mechanism involving a locally temperature-sensitive redox reaction to explain this strong temperature dependence of the morphologies of SiGe NRs. At a lower etching temperature, both corrosion reaction and Au-assisted etching process were kinetically impeded, whereas at a higher temperature, Au-assisted anisotropic etching dominated the formation of SiGe NRs. With transmission electron microscopy and scanning electron microscopy analyses, this study provides a beneficial scheme to design and fabricate low-dimensional SiGe-based nanostructures for possible applications.     

氢氧化四甲基铵腐蚀硅性能的改善

An optimal concentration of the etching solution for deep etching of silicon, including 3% tetramethyl ammonium hydroxide and 0.3% (NH4)2S208, was achieved in this paper. For this etching solution, the etching rates of silicon and silicon dioxide were about 1.1μm.min^-1 and 0.5 nm.min^-1, respectively. The etching ratio between (100) and (111) planes was about 34:1, and the etched surface was very smooth.     

Metal-assisted chemical etching of silicon in HF-H2O2

Metal-assisted etching of silicon in HF/H₂O₂/H₂O solutions with Ag nanoparticles as catalyst agents was investigated. SEM observations and etch rate measurements were carried out as a function of the etching solution composition. Depending on the relative amount of HF and H₂O₂, different regimes of dissolution take place and a strong similarity with the etching in HF-HNO₃ solution is evidenced, for the first time. Formation of meso- and macroporous Si, etched craters and polished Si are observed as the HF/H₂O₂ ratio decreases. The dissolution mechanisms are discussed on the basis of a localized hole injection from the Ag nanoparticles into Si and in terms of the well known chemistry of Si dissolution in HF-based chemical and electrochemical systems. At high HF/H₂O₂ ratio, there is no formation of oxide at the surface. Hole injection and Si dissolution occur at the level of the Ag nanoparticle only, resulting in the formation of meso and macropores depending on the Ag nanoparticle size. At low HF/H₂O₂ ratio, the Si surface is oxidized, the injected holes are homogeneously distributed and thus polishing occurs. There is an intermediate range of composition in which injected holes diffuse away from the Ag nanoparticles and cone-shaped macropores, several tens of nm in diameter are formed.     

氢气刻蚀法制备Pt/CNTs复合材料及其热稳定性

采用碳化硅高温热分解法制备整齐排列的直立碳纳米管阵列,并对其进行Pt金属粒子修饰,通过氢气刻蚀法可以将闭口碳纳米管阵列开口,并将Pt纳米粒子嵌入到碳纳米管中。这种新型Pt/CNTs复合材料具有独特的电子限域效应,有助于抑制金属催化剂的烧结,对提高其后续催化活性和应用性能有着重要意义。     

Synthesis of high-density arrays of graphene nanoribbons by anisotropic metal-assisted etching

We demonstrate the synthesis of highly aligned dense arrays of graphene nanoribbons (GNRs) based on metal-assisted etching of chemical vapor deposition-grown single-layer graphene. In order to obtain GNR arrays, controlling the direction of the etching becomes an important task. Crystalline surfaces of r- and a-planes of sapphire (α-Al₂O₃) were found to induce anisotropic etching of the graphene along their specific crystallographic directions. In contrast, anisotropic surface of ST-cut quartz induced few etching lines. We found that the graphene etching is strongly dependent on the metal species; the order of the catalytic activity of metal nanoparticles is Ni > Fe > > Cu. Etching temperature and H₂ concentration also strongly influenced the density and quality of the etching lines. Our anisotropic graphene etching is expected to offer a new route toward the synthesis of high density GNR array in large area without relying on any lithographic techniques for future electronic devices.     

Fabrication mechanism of friction-induced selective etching on Si(100) surface

As a maskless nanofabrication technique, friction-induced selective etching can easily produce nanopatterns on a Si(100) surface. Experimental results indicated that the height of the nanopatterns increased with the KOH etching time, while their width increased with the scratching load. It has also found that a contact pressure of 6.3 GPa is enough to fabricate a mask layer on the Si(100) surface. To understand the mechanism involved, the cross-sectional microstructure of a scratched area was examined, and the mask ability of the tip-disturbed silicon layer was studied. Transmission electron microscope observation and scanning Auger nanoprobe analysis suggested that the scratched area was covered by a thin superficial oxidation layer followed by a thick distorted (amorphous and deformed) layer in the subsurface. After the surface oxidation layer was removed by HF etching, the residual amorphous and deformed silicon layer on the scratched area can still serve as an etching mask in KOH solution. The results may help to develop a low-destructive, low-cost, and flexible nanofabrication technique suitable for machining of micro-mold and prototype fabrication in micro-systems.     

Fabrication of rhenium nanowires by selective etching of eutectic alloys

Rhenium nanowires have been fabricated via directional solidification and selective etching of a eutectic alloy. A NiAl-1.5 at.%Re eutectic alloy was directionally solidified using a constant growth rate and temperature gradient, in the Bridgman-type directional solidification furnace. The selective dissolution of the NiAl matrix was achieved with a mixture of HCl:H₂O₂, and produced an anisotropic etching of the eutectic, with the favoured etching directions aligned in parallel. The corroded surface was dominated by long rhenium fibres (diameter ∼400 nm), although shorter, and sometimes more rectangular wires were also observed in some sections. Digestion of the NiAl-Re eutectic in sulphuric acid, on the other hand, produced mainly long rhenium fibres of consistent shape and length. Both etching procedures might subsequently be applied for the preparation of nanodisc electrode arrays by embedding the obtained Re nanowires into a polymer and grinding until the wires are exposed. The reduction on the electrode area inherent in the use of such nanoelectrodes would allow a considerable increase in the signal-to-noise ratio, thus favouring the system for its application in analytical sensors. The use of rhenium in the electrode formation might also favour its application in high-temperature measurements.