Bulk Micromachining of Si by Metal‐assisted Chemical Etching

Bulk micromachining of Si is demonstrated by the well‐known metal‐assisted chemical etching (MaCE). Si microstructures, having lateral dimension from 5 μm up to millimeters, are successfully sculpted deeply into Si substrate, as deep as >100 μm. The key ingredient of this success is found to be the optimizations of catalyst metal type and its morphology. Combining the respective advantages of Ag and Au in the MaCE as a Ag/Au bilayer configuration leads to quite stable etch reaction upon a prolonged etch duration up to >5 h. Further, the permeable nature of the optimized Ag/Au bilayer metal catalyst enables the etching of pattern features having very large lateral dimension. Problems such as the generation of micro/nanostructures and chemical attacks on the top of pattern surface are successfully overcome by process optimizations such as post‐partum sonication treatment and etchant formulation control. The method can also be successful to vertical micromachining of Si substrate having other crystal orientations than Si(100), such as Si(110) and Si(111). The simple, easy, and low‐cost nature of present approach may be a great help in bulk micromachining of Si for various applications such as microelectromechanical system (MEMS), micro total analysis system (μTAS), and so forth.     

Facile and Clean Release of Vertical Si Nanowires by Wet Chemical Etching Based on Alkali Hydroxides

A simple method to release Si nanowires (SiNWs) from a substrate, with their original length almost intact, is demonstrated. By exploiting the unique chemistry involved for the fabrication of vertical arrays of SiNWs in metal‐assisted chemical etching (MaCE) based either on HF/AgNO₃ or HF/H₂O₂ chemistries, wet etching with alkali hydroxides such as NaOH or KOH preferentially attacks the bottom part of the vertical SiNWs. A protective layer of Si oxide is found to exist on the outer wall of the SiNWs and to play the key role of etch mask during the release‐etching by alkali hydroxides. The clean release of SiNWs also enables the repeated use of the Si substrate for the fabrication of vertical SiNW arrays by MaCE. The released SiNWs are further used for the fabrication of field‐effect transistors on a flexible plastic substrate. The method developed here, when combined with a suitable assembling technique, can be very useful in implementing flexible electronics, or in the fabrication of SiNW composites with other functional materials.     

Effects of metal layer morphology to silicon nanostructure formation in metal-assisted etching

This study presents a rapid and simple approach for creating silicon nanostructures using metal-assisted etching. The thickness of the metal layer was found to be a key process parameter affecting the surface morphology of silicon nanostructures. Au and Ag layers with a thickness of 3 nm, 5 nm, and 10 nm were used to study the effects of metal catalyst thickness on silicon nanostructure morphology. The experimental results show that the surface morphology of metal has a significant influence on the silicon nanostructure morphology, such that the silicon nanostructures transform from porous silicon surfaces into filament nanostructures or silicon nanowire with increasing thicknesses of both the Au and Ag metal layers.     

Directed 2D-to-3D pattern transfer method for controlled fabrication of topologically complex 3D features in silicon

A process that allows control over the 3D motion of catalyst nanostructures during metal-assisted chemical etching by their local pinning prior to etching is demonstrated. The pinning material acts as a fulcrum for rotation of the catalyst structures resulting in etching of silicon features with rotational geometry.     

Metal‐Assisted Chemical Etching of Silicon: A Review

This article presents an overview of the essential aspects in the fabrication of silicon and some silicon/germanium nanostructures by metal‐assisted chemical etching. First, the basic process and mechanism of metal‐assisted chemical etching is introduced. Then, the various influences of the noble metal, the etchant, temperature, illumination, and intrinsic properties of the silicon substrate (e.g., orientation, doping type, doping level) are presented. The anisotropic and the isotropic etching behaviors of silicon under various conditions are presented. Template‐based metal‐assisted chemical etching methods are introduced, including templates based on nanosphere lithography, anodic aluminum oxide masks, interference lithography, and block‐copolymer masks. The metal‐assisted chemical etching of other semiconductors is also introduced. A brief introduction to the application of Si nanostructures obtained by metal‐assisted chemical etching is given, demonstrating the promising potential applications of metal‐assisted chemical etching. Finally, some open questions in the understanding of metal‐assisted chemical etching are compiled.     

交替刻蚀制备有序锯齿形硅纳米线阵列及其光学性能研究

采用金属催化化学刻蚀法(MCCE),以金属Ag为催化剂,在HF与H2O2体系中通过交替刻蚀在P(111)硅衬底上制备出锯齿形硅纳米线阵列.利用扫描电子显微镜对硅纳米线的形貌进行了表征,研究了HF浓度与H2O2浓度对纳米线刹蚀方向的调控作用.选取不同的HF与H2O2浓度配比,分别对硅基底各向同性刻蚀与各向异性刻蚀进行调控,使得刻蚀方向对溶液浓度的变化能够快速响应.在溶液Ⅰ([HF]=2.3 mol/L,[H2O2]=0.4 mol/L)与溶液Ⅱ([HF]=9.2 mol/L,[H2O2]=0.04 mol/L)中交替刻蚀,制备出刻蚀方向高度可控的大规模锯齿形硅纳米线.利用紫外-可见分光光度计对锯齿形硅纳米线的减反射性能进行研究,结果表明,其表现出优异的减反特性,最低反射率为5.9％.纳米线形貌的高度可控性使其在微电子器件领域也具有巨大的应用前景.     

Patterning of various silicon structures via polymer lithography and catalytic chemical etching

We demonstrate a facile fabrication of a rich variety of silicon patterns with different length scales by combining polymer lithography and a metal-assisted chemical etching method. Several types of polymer patterns were fabricated on silicon substrates, and silver layers were deposited on the patterned silicon surfaces and used to etch the silicon beneath. Various silicon patterns including topographic lines, concentric rings, and square arrays were created at a micro-?and nanoscale after etching the silicon and subsequent removal of the patterned polymer masks. Alternatively, the arrays of sub-30?nm silicon nanowires were produced by a chemical etching of the silicon wafer which was covered with highly ordered polystyrene-block-polyvinylpyridine (PS-b-PVP) micellar films. In addition, silicon nanohole arrays were also generated by etching with hexagonally packed silver nanoparticles that were prepared using PS-b-PVP block copolymer templates.     

Novel fabrication method of diverse one-dimensional Pt/ZnO hybrid nanostructures and its sensor application

A novel low-temperature, solution-phase method for the facile fabrication of a variety of one-dimensional (1D) metal/metal oxide hybrid nanostructures has been developed. This method is based on the wet chemical synthesis of metal oxide nanowires, followed by the surface coating of metal nanoparticles on metal oxide nanowire templates via reduction of metal ions along with controlled etching of metal oxide nanowires at the core, all in a low-temperature liquid environment. As a proof-of-concept, we applied this method to the fabrication of various 1D Pt/ZnO hybrid nanostructures including Pt nanoparticle-coated ZnO nanowires/nanotubes and Pt nanotubes on silicon and polymer substrates. The diverse morphology tuning is attributed to the control of pH in the solution with different metal precursor concentrations and amounts of reducing agent. The change of morphology, crystalline structure, and composition of various 1D Pt/ZnO hybrid nanostructures was observed by SEM, TEM (HRTEM), XRD and ICP-AES, respectively. Further, we have demonstrated a highly sensitive strain sensor (gauge factor = 15) with a Pt nanotube film fabricated by the developed method on a flexible polymer substrate.     

电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构

量子限制效应使硅纳米线具有良好的场致发射特性,结合多孔硅的准弹道电子漂移模型可提高场发射器件的性能.传统的金属辅助化学刻蚀法制备硅纳米线的效率较低,本研究在传统方法的基础上引入恒流源,提出电催化金属辅助化学刻蚀法,高效制备了硅纳米线/多孔硅复合结构.在外加30 mA恒定电流的条件下,硅纳米线的平均制备速率可达308 n...     

Programmable Self‐Assembling 3D Architectures Generated by Patterning of Swellable MOF‐Based Composite Films

The integration of swellable metal–organic frameworks (MOFs) into polymeric composite films is a straightforward strategy to develop soft materials that undergo reversible shape transformations derived from the intrinsic flexibility of MOF crystals. However, a crucial step toward their practical application relies on the ability to attain specific and programmable actuation, which enables the design of self‐shaping objects on demand. Herein, a chemical etching method is demonstrated for the fabrication of patterned composite films showing tunable self‐folding response, predictable and reversible 2D‐to‐3D shape transformations triggered by water adsorption/desorption. These films are fabricated by selective removal of swellable MOF crystals allowing control over their spatial distribution within the polymeric film. Upon exposure to moisture, various programmable 3D architectures, which include a mechanical gripper, a lift, and a unidirectional walking device, are generated. Remarkably, these 2D‐to‐3D shape transformations can be reversed by light‐induced desorption. The reported strategy offers a platform for fabricating flexible MOF‐based autonomous soft mechanical devices with functionalities for micromanipulation, automation, and robotics.     

Metal-assisted electrochemical etching of silicon

In this paper the metal-assisted electrochemical etching of silicon is introduced. By electrochemical measurement and sequent simulation, it is revealed that the potential of the valence band maximum at the silicon/metal interface is more negative than that of the silicon/electrolyte interface. Accordingly, holes injected from the back contact are driven preferentially to the silicon/metal interface. Consequently, silicon below metal is electrochemically etched much faster than a naked silicon surface without metal coverage. Metals such as Ag and Cu have been utilized to catalyze the electrochemical etching. Feature sizes as small as 30 nm can be achieved by metal-assisted electrochemical etching. Meanwhile, the metal-assisted electrochemical etching method enables convenient control over the etching direction of non-(100) substrates, and facilitates the fabrication of orientation-modulated silicon nanostructures.     

Formation and mechanism of silicon nanostructures by Ni-assisted etching

Instead of noble metal like Pt, Au and Ag, cheap Ni nanoparticles (Ni NPs) were used to fabricate silicon nanostructures. Ni was found to be etched off during the etching process, while forming silicon nanostructures with very low reflectance of 1.59 % from 400 to 900 nm. The formation mechanism of silicon nanostructures by Ni-assisted etching was presented from the point of view of the low electronegativity of Ni. The Ni NPs were found being etched off during the assisted etching process, which implies that the transfer rate of electrons from Si to Ni is slower than that from Ni to O^? in the case of using Ni as assisted metal. The reason of sparser and deeper silicon nanostructures etched in lower H₂O₂ concentration solution is that the Ni NPs can be lasted for longer time in the etching solution with lower H₂O₂ concentration so that more silicon atoms will be oxidized and then removed for those under Ni NPs due to the hole transfer and those where uncovered by Ni NPs due to the hole diffusion.     

Effect of the on/off cyclic modulation time ratio of C2H2/H2 flow on the low temperature deposition of carbon nanofilaments

Low temperature (less than 600 degrees C) deposition of carbon nanofilaments (CNFs) could be achieved on the silicon oxide substrate by thermal chemical vapor deposition system. We used Fe(CO)5 as the catalyst precursor for CNFs formation. For the enhancement of CNFs formation density, the source gas flow was intentionally manipulated as the cyclic on/off modulation of C2H2/H2 flow during the initial deposition stage. The CNFs formation density on silicon oxide substrate could be much enhanced by the cyclic modulation process having the higher growing/etching time ratio (180/30 s). Furthermore, the lattice structures of CNFs developed into carbon nanotubes at the higher growing/etching time ratio (180/30 s) case. The solely hydrogen gas feeding (C2H2 flow off) time during the initial deposition stage seems to play an important role for the variation in the CNFs formation characteristics by the cyclic modulation process.     

High-voltage nanoimprint lithography of refractory metal films

Local oxidation of metal, semiconductor, and polymer surfaces has provided a common basis from which to explore fundamental principles of nanolithography and prototype functional nanostructures for many years now. This article summarizes an investigation of local oxidation for iron and Group IV metal thin films using both scanning probe microscopy and high-voltage nanoimprinting methods. We illustrate how the underlying kinetics of metal oxidation in the presence of nitrogen, which is incorporated into the metal film during the growth process, is dramatically enhanced compared with that of single-crystal silicon. We then go on to demonstrate subsequent selective etching of latent features and a potential magnetic application.     

<Emphasis Type="Italic">In situ</Emphasis> grazing-incidence small-angle X-ray scattering observation of block-copolymer templated formation of magnetic nanodot arrays and their magnetic properties

The fabrication of bit-patterned media (BPM) is crucial for new types of hard disk drives.The development of methods for the production of BPM is progressing rapidly.Conventional lithography reaches the limit regarding lateral resolution,and new routes are needed.In this study,we mainly focus on the dependence of the size and shape of magnetic nanodots on the Ar+-ion etching duration,using silica dots as masks.Two-dimensional (2D) arrays of magnetic nanostructures are created using silica-filled diblock-copolymer micelles as templates.After the self-assembly of the micelles into 2D hexagonal arrays,the polymer shell is removed,and the SiO2 cores are utilized to transform the morphology into a (Co/Pt)2-multilayer via ion etching under normal incidence.The number of preparation steps is kept as low as possible to simplify the formation of the nanostructure arrays.High-resolution in situ grazing-incidence small-angle X-ray scattering (GISAXS) investigations are performed during the Ar+-ion etching to monitor and control the fabrication process.The in situ investigation provides information on how the etching conditions can be improved for further ex situ experiments.The GISAXS patterns are compared with simulations.We observe that the dots change in shape from cylindrical to conical during the etching process.The magnetic behavior is studied by utilizing the magneto-optic Kerr effect.The Co/Pt dots exhibit different magnetic behaviors depending on their size,interparticle distance,and etching time.They show ferromagnetism with an easy axis of magnetization perpendicular to the film.A systematic dependence of the coercivity on the dot size is observed.     

Surface morphology and structural analysis of fluorocarbon nano-rings formation through EBL and SiO2 plasma etching

This paper reports the formation of nano-scale ring-shaped fluorocarbon macromolecules during silicon dioxide SiO₂ reactive ion etching (RIE). This nanostructure was created on a SiO₂ substrate with poly methyl methacrylate (PMMA) mask during the RIE process, using trifluoromethane (CHF₃) and oxygen etchants. Variation in etching time results in the creation of square, double concentric, and flower-shaped nano-rings around SiO₂ micro-pits. In addition, increasing the etching times leads to an increase in ring width. The formation of these nano-rings is shown by a deposition of passivation layer, consisting of silicon oxide, Si_xO_y and fluorocarbon, C_xF_y, on sidewalls during SiO₂ etching in fluorocarbon plasma. Field Emission Scanning Electron Microscopy (FESEM) and Energy-dispersive X-ray (EDX) were utilized to investigate the morphology and the structure of the nano-rings. Results show that the flower-shaped nano-rings were created on the surface of silicon for 8 min of etching time. These fluorocarbon nano-rings could be used as nano-scale templates.     

化学蚀刻法制备纳米硅线作为高能锂离子电池的负极

采用金属催化剂诱导化学蚀刻法首先在单晶硅片上制备出具有高长径比的纳米硅线阵列, 然后通过超声振荡法将硅线阵列破碎为纳米硅线粉体, 最后将其作为锂离子电池的负极材料, 系统研究了金属银催化剂制备过程和各向异性化学蚀刻过程对硅片表面形貌特征的影响, 发现银催化剂在蚀刻过程出现溶解/再沉积现象。通过优化AgNO₃、HF、H₂O₂等试剂的浓度, 在大面积范围内得到了高长径比的纳米硅线阵列。借助超声波的作用将硅线从硅片上切割下来, 制备成纳米硅线负极进行了充放电循环测试, 观察到标准的硅锂合金/去合金化反应平台, 前五次循环的比容量均超过1800 mAh/g。     

Fast release process of metal structure using chemical dry etching of sacrificial Si layer

An ultra-fast removal process of a silicon sacrificial layer for the selective release of a metal structure on a Si substrate was studied, which uses a chemical dry etching method. The chemical dry etching of a Si layer was performed in an NF₃ remote plasma with the direct injection of additive nitric oxide (NO) gas. When the NO gas was injected into the chamber into which F radicals were supplied from a remote plasma source using NF₃ input gas, the silicon layer was removed selectively and the metal structure could be released easily. It was found that the etch rate on the sidewall (up to ≅ 18.7 μm/min for an opening width of 100 μm) and the bottom (up to ≅ 24.5 μm/min for an opening width of 100 μm) depends on the NO/(NO + Ar) gas flow ratio, time duration, and opening width. The developed dry etching process could be used to release a Ni structure with near infinite selectivity in a very short time. The process is well suited for fabricating various devices which require a suspended structure, such as in radio-frequency microelectromechanical system switches, tunable capacitors, high-Q suspended inductors and suspended-gate metal-oxide semiconductor field-effect transistors.     

Large scale 3D vertical assembly of single-wall carbon nanotubes at ambient temperatures

We demonstrate three-dimensional directed assembly of single-wall carbon nanotubes (SWNT) into porous alumina nanotemplates on silicon substrates by means of electrophoresis and dielectrophoresis at ambient temperatures. Assembled SWNT provided an interconnection between the surface and base of the nanotemplate. I-V measurements clearly show that the connection between silicon and SWNT is established inside the templates. This technique is particularly useful for large scale, rapid, 3D assembly of SWNT over centimeter square areas under mild conditions for nanoscale electronics applications.     

Influence of two-tier structuring on the performance of black silicon-based MSM photodetectors

Black silicon, fabricated by alkaline anisotropic etching along with metal-assisted etching, consists of regular distributed micro-scale pyramids and irregular distributed nano-scale pores, in which the pore size plays an important role in the performance of the black silicon-based metal–semiconductor–metal photodetectors (BS MSM PDs). It is found that the dark current characteristic of BS MSM PD is different from that of traditional silicon MSM PD, and the former has negative differential resistance in part of its operating range because of the quantum tunneling effect exists in black silicon. Moreover, it is interesting to note that BS MSM PD with longer metal-assisted etching time (larger nanopore size) has higher responsivity at high bias voltage but lower responsivity at low bias voltage.