Layer-by-layer removal of insulating few-layer mica flakes for asymmetric ultra-thin nanopore fabrication

We demonstrate an elaborate method to controllably fabricate ultra-thin nanopores by layer-by-layer removal of insulating few-layer mica flakes with atomic force microscopy (AFM). The fabricated nanopores are geometrically asymmetric, like an inverted quadrangular frustum pyramid. The nanopore geometry can be engineered by finely tuning the mechanical load on the AFM tip and the scanning area. Particularly noteworthy is that the nanopores can also be fabricated in suspended few-layer mica membranes on a silicon window, and may find potential use as functional components in nanofluidic devices.      

电化学制备Bi2Te3纳米线用于微型温差发电器

借助于电化学沉积的方法，在氧化铝纳米孔内生长Bi2Te3材料，从而形成温差电纳米线阵列．利用SEM,XRD and TEM分析手段对制备的纳米线形貌和结构进行了分析，测量了纳米线的组成和温差电性能．p型和n型Bi2Te3纳米线材料的Seebeck系数经过测量分别为260μV／K和-188μV／K（307K），比同类的块状温差电材料性能高．同时研究了沉积电位对氧化铝模板中纳米孔的填充率的影响，并对纳米线阵列的电阻进行了测量．尝试了利用n型和P型Bi2Te3纳米线阵列制备一种新型的微型温差发电器．     

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。     

Fabrication of slantingly-aligned silicon nanowire arrays for solar cell applications

Large-area slantingly-aligned silicon nanowire arrays (SA-SiNW arrays) on Si(111) substrate have been fabricated by wet chemical etching with dry metal deposition method and employed in the fabrication of solar cells for the first time. The formation of SA-SiNW arrays possibly results from the anisotropic etching of silicon by silver catalysts. Superior to the previous cells fabricated with vertically-aligned silicon nanowire arrays (VA-SiNW arrays), the SA-SiNW array solar cells exhibit a highest power conversion efficiency of?11.37%. The improved device performance is attributed to the integration of the excellent anti-reflection property of the arrays and the better electrical contact of the cell as a result of the special slantingly-aligned structure. The high surface recombination velocity of minority carriers in SiNW arrays is still the main limitation on cell performance.     

Fabrication of large area high density, ultra-low reflection silicon nanowire arrays for efficient solar cell applications

High density vertically aligned and high aspect ratio silicon nanowire (SiNW) arrays have been fabricated on a Si substrate using a template and a catalytic etching process. The template was formed from polystyrene (PS) nanospheres with diameter 30–50 nm and density 10¹⁰/cm², produced by nanophase separation of PS-containing block-copolymers. The length of the SiNWs was controlled by varying the etching time with an etching rate of 12.5 nm/s. The SiNWs have a biomimetic structure with a high aspect ratio (∼100), high density, and exhibit ultra-low reflectance. An ultra-low reflectance of approximately 0.1% was achieved for SiNWs longer than 750 nm. Well-aligned SiNW/poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) heterojunction solar cells were fabricated. The n-type silicon nanowire surfaces adhered to PEDOT:PSS to form a core-sheath heterojunction structure through a simple and efficient solution process. The large surface area of the SiNWs ensured efficient collection of photogenerated carriers. Compared to planar cells without the nanowire structure, the SiNW/PEDOT:PSS heterojunction solar cell exhibited an increase in short-circuit current density from 2.35 mA/cm² to 21.1 mA/cm² and improvement in power conversion efficiency from 0.4% to 5.7%.      

Facile fabrication of Si nanowire arrays for solar cell application

Large-area Si nanowire arrays have been fabricated on phosphorus doped Si surface by a facile silver-catalyzed chemical etching process. The solar cell incorporated with Si nanowire arrays shows a power conversion efficiency of 6.69% with an open circuit voltage of 558 mV and a short circuit current density of 25.13 mA/cm2 under AM 1.5 G illumination without using any extra antireflection layer and surface passivation technique. The high power conversion efficiency of Si nanowires based-solar cell is attributed to the low reflectance loss of Si nanowire arrays for incident sunlight. Optimization of electrical contact and phosphorus diffusion process will be critical to improve the performance of Si nanowires-based solar cell in the future.     

Electro-codeposition synthesis and room temperature ferromagnetic anisotropy of high concentration Fe-doped ZnO nanowire arrays

Fe-doped ZnO dilute magnetic semiconductor (DMS) nanowire arrays were fabricated in anodic aluminum oxide (AAO) membranes using electro-codeposition followed by long-time anneal process. The morphology, chemical composition and crystal structure were characterized by field emission scanning electron microscope (FE-SEM), high resolution transmission electron microscope (HRTEM) equipped with an energy dispersive x-ray spectrometer, and X-ray diffraction (XRD) spectroscopy. The results prove that the Fe has been successfully doped in the lattice of ZnO nanowire arrays and the estimated Fe atomic ratio is around 22%. Micro-superconducting quantum interference device (SQUID) shows that the nanowire arrays exhibit room temperature (300 K) ferromagnetic and anisotropic ferromagnetic behavior which may be a consequence of the easy magnetization direction along the wire axes and magnetostatic interaction.     

Formation of uniform and square nanopore arrays on (100) InP surfaces by a two-step etching method

Uniform and square single-crystal InP nanopore arrays have been successfully fabricated on a (100) n-InP surface by a two-step etching method. The characteristic of slow etching rates in four equivalent crystalline (011) facets of (100) n-InP in a mixture of pure HCl and pure H(3)PO(4) has been found, which is the main reason for the formation of square single-crystal InP nanopores. The distribution of nanopores can be closely associated with the distribution of carriers in the semiconductor during the electrochemical etching process. An oscillating behaviour of current has been observed, which can probably be attributed to the oscillations in concentration of the electrolyte at the pore tips caused by diffusion of the electrolyte in the nanopore channels.     

<Emphasis Type="Italic">In situ</Emphasis> etching for total control over axial and radial nanowire growth

We report a method using in situ etching to decouple the axial from the radial nanowire growth pathway, independent of other growth parameters. Thereby a wide range of growth parameters can be explored to improve the nanowire properties without concern of tapering or excess structural defects formed during radial growth. We demonstrate the method using etching by HCl during InP nanowire growth. The improved crystal quality of etched nanowires is indicated by strongly enhanced photoluminescence as compared to reference nanowires obtained without etching.      

Enhancement of the coercivity of electrodeposited nickel nanowire arrays

In the present study, the single-crystal Ni nanowire arrays with a preferred growth along the [110] direction have been prepared by the deposition of Ni into the alumina template with nanopores at a current density of 2.0 mA/cm². The single-crystal Ni nanowire arrays show a magnetic anisotropy with the easy axis parallel to the nanowires and an enhanced coercivity as compared with the polycrystalline Ni nanowire arrays. A large coercivity of 1110 Oe together with a high remanence M_r = 0.92M_s is observed for 15-nm diameter single-crystal Ni nanowire arrays. The preferred growth mechanism of the single-crystal nanowires is briefly discussed.     

Effect of electroless etching parameters on the growth and reflection properties of silicon nanowires

Vertically aligned silicon nanowire (Si NW) arrays have been fabricated over large areas using an electroless etching (EE) method, which involves etching of silicon wafers in a silver nitrate and hydrofluoric acid based solution. A detailed parametric study determining the relationship between nanowire morphology and time, temperature, solution concentration and starting wafer characteristics (doping type, resistivity, crystallographic orientation) is presented. The as-fabricated Si NW arrays were analyzed by field emission scanning electron microscope (FE-SEM) and a linear dependency of nanowire length to both temperature and time was obtained and the change in the growth rate of Si NWs at increased etching durations was shown. Furthermore, the effects of EE parameters on the optical reflectivity of the Si NWs were investigated in this study. Reflectivity measurements show that the 42.8% reflectivity of the starting silicon wafer drops to 1.3%, recorded for 10 μm long Si NW arrays. The remarkable decrease in optical reflectivity indicates that Si NWs have a great potential to be utilized in radial or coaxial p-n heterojunction solar cells that could provide orthogonal photon absorption and enhanced carrier collection.     

Investigating the influence of fabrication process and crystal orientation on shear strength of silicon microcomponents

A summary of the influence of microfabrication processes (wet and dry etching) and crystal orientation on the effective shear strength of microridges is addressed in this paper. Test results indicate that both crystal orientation and geometry plays an important role in determining the strength. The largest shear strengths obtained were for triangular and rectangular ridges fabricated with wet etching and deep RIE respectively. Both of these structures had similar crystal orientations. These strength values were approximately 3.5 times larger than the lowest strengths measured for wet etching structures. Using Chlorine RIE, we were able to demonstrate the influence of crystal orientation on strength, with microridges of {110} sidewall made on a (100) wafer the largest. For wet etching, we found that the strength was concentration dependent. For example, a 45% KOH fabricated structure produced strength values 65% higher than 30% KOH fabricated ones (note crystal orientation the same). This was attributed to a geometric effect, that is the 45% KOH solution had a V shaped bottom while the 30% KOH had a flat bottom. EDP and TMAH values had similar strengths to the 30% KOH solution (note similar crystal orientation). Therefore, microcomponent strength is strongly dependent upon fabrication process as well as crystal orientation.     

Ultra-dense planar metallic nanowire arrays with extremely large anisotropic optical and magnetic properties

A nanofabrication method for the production of ultra-dense planar metallic nanowire arrays scalable to wafer-size is presented. The method is based on an efficient template deposition process to grow diverse metallic nanowire arrays with extreme regularity in only two steps. First, III–V semiconductor substrates are irradiated by a low-energy ion beam at an elevated temperature, forming a highly ordered nanogroove pattern by a “reverse epitaxy” process due to self-assembly of surface vacancies. Second, diverse metallic nanowire arrays (Au, Fe, Ni, Co, FeAl alloy) are fabricated on these III–V templates by deposition at a glancing incidence angle. This method allows for the fabrication of metallic nanowire arrays with periodicities down to 45 nm scaled up to wafer-size fabrication. As typical noble and magnetic metals, the Au and Fe nanowire arrays produced here exhibited large anisotropic optical and magnetic properties, respectively. The excitation of localized surface plasmon resonances (LSPRs) of the Au nanowire arrays resulted in a high electric field enhancement, which was used to detect phthalocyanine (CoPc) in surface-enhanced Raman scattering (SERS). Furthermore, the Fe nanowire arrays showed a very high in-plane magnetic anisotropy of approximately 412 mT, which may be the largest in-plane magnetic anisotropy field yet reported that is solely induced via shape anisotropy within the plane of a thin film.

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Fabrication and magnetic properties of Fe<Subscript>3</Subscript>Co<Subscript>7</Subscript> alloy nanowire arrays

Fe₃Co₇ alloy nanowire arrays have been fabricated by direct current electrodeposition of Fe²⁺ and Co²⁺ into anodic aluminum oxide (AAO) templates. The phase structure and magnetic properties of the nanowires were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). Magnetic measurements show that the coercivity and remanence of the as-deposited Fe₃Co₇ Alloy nanowires increase dramatically after heat-treatment at 773 K for 2 h, and the nanowire arrays exhibit uniaxial magnetic anisotropy with easy magnetization direction along the nanowire axes owing to the large shape anisotropy. The great difference between practical coercivity and ideal coercivity was also discussed in detail.     

Electrochemical Fabrication of Metallic Nanowires and Metal Oxide Nanopores

A nuclear track etched polycarbonate membrane filter with numerous cylindrical nanopores was applied as a nanoporous template for growing metallic nanowires. Nickel, cobalt, and iron nanowires were electrodeposited into the cylindrical nanopores. Cathodic polarization curves were measured to determine an optimum condition for growing nanowires. The shape of nanowires was observed using scanning electron microscope (SEM) and the crystal structure was analyzed using transmission electron microscopy (TEM). Diameter and length of nanowires corresponded to those of nanopores and each nanowire was composed of a single crystal. Anodized aluminum oxide films were also fabricated as a novel nanoporous template. The pore length and diameter was controlled changing anodizing conditions. Ordering behavior of nanopores array in an anodized aluminum oxide film was also investigated to make a novel nanoporous template with a highly ordered honeycomb array of nanopores.     

Self-organized magnetic nanowire arrays based on alumina and titania templates

Densely packed arrays of magnetic nanowires have been synthesized by electrodeposition filling of nanopores in alumina and titania membranes formed by self-assembling during anodization process. Emphasis is made on the control of the production parameters leading to ordering degree and lattice parameter of the array as well as nanowires diameter and length. Structural, morphological and magnetic properties exhibited by nanowire arrays have been studied for several nanowire compositions, different ordering degree and for different nanowire aspect ratios. The magnetic behaviour of nanowires array is governed by the balance between different energy contributions: shape anisotropy of individual nanowires, the magnetostatic interaction of dipolar origin among nanowires, and magnetocrystalline and magnetoelastic anisotropies induced by the pattern templates. These novel nanocomposites, based on ferromagnetic nanowires embedded in anodic nanoporous templates, are becoming promising candidates for technological applications such as functionalised arrays for magnetic sensing, ultrahigh density magnetic storage media or spin-based electronic devices.     

Periodic arrays of deep nanopores made in silicon with reactive ion etching and deep UV lithography

We report on the fabrication of periodic arrays of deep nanopores with high aspect ratios in crystalline silicon. The radii and pitches of the pores were defined in a chromium mask by means of deep UV scan and step technology. The pores were etched with a reactive ion etching process with SF(6), optimized for the formation of deep nanopores. We have realized structures with pitches between 440 and 750?nm, pore diameters between 310 and 515?nm, and depth to diameter aspect ratios up to 16. To the best of our knowledge, this is the highest aspect ratio ever reported for arrays of nanopores in silicon made with a reactive ion etching process. Our experimental results show that the etching rate of the nanopores is aspect-ratio-dependent, and is mostly influenced by the angular distribution of the etching ions. Furthermore we show both experimentally and theoretically that, for sub-micrometer structures, reducing the sidewall erosion is the best way to maximize the aspect ratio of the pores. Our structures have potential applications in chemical sensors, in the control of liquid wetting of surfaces, and as capacitors in high-frequency electronics. We demonstrate by means of optical reflectivity that our high-quality structures are very well suited as photonic crystals. Since the process studied is compatible with existing CMOS semiconductor fabrication, it allows for the incorporation of the etched arrays in silicon chips.     

Reshaping the tips of ZnO nanowires by pulsed laser irradiation

Vertically aligned ZnO nanowires have been synthesized by a hydrothermal method. After being irradiated by a short laser pulse, the tips of the as-synthesized ZnO nanowires can be tailored into a spherical shape. Transmission electron microscopy revealed that the spherical tip is a single-crystalline piece connected to the body of the ZnO nanowire, and that the center of the sphere is hollow. The growth mechanism of the hollow ZnO nanospheres is proposed to involve laser-induced ZnO evaporation immediately followed by re-nucleation in a temperature gradient environment. The laser-irradiated ZnO nanowire array shows hydrophobic properties while the original ZnO nanowire array shows hydrophilicity. The as-grown ZnO nanowire arrays with hollow spherical tips can serve as templates to grow ZnO nanowire arrays with very fine tips, which may be a good candidate material for use in field emission and scanning probe microscopy.      

Optical properties of black silicon prepared by wet etching

In this paper, the optical properties of black silicon have been studied. The black silicon samples were fabricated by alkaline etching and metal assisted etching. The micro-columns and nanopores on the silicon surface were obtained in KOH and Au-induced HF/H₂O₂ solution, respectively. The height and diameter of micro-columns prepared by KOH etching is about 470?nm and 2?μm. In the Au-induced HF/H₂O₂ etching, the metallic nuclei behave as a cathode and their surrounding area acts as an anode, resulting in nanopores with diameters ranging from 80 to 120?nm. These microstructures formed in the etching process directly affect the optical properties of black silicon such as reflectance, transmittance and absorptance. According to the measurement of integrating sphere detector, the absorptance of the black silicon produced by wet etching remains roughly 90% from 250 to 1,000?nm wavelength, which is almost 150% of the absorptance of conventional silicon. However, the reflectance of black silicon is less than 13% and the transmittance is less than 4%.     

Aligned 1D silicon nanostructure arrays by plasma etching

High-density aligned arrays made of one-dimensional (1D) silicon nanostructures, including nanocone, nanorod, and nanowire, are fabricated by plasma etching in a hot-filament chemical vapor deposition apparatus using the gas mixture of hydrogen, nitrogen and methane. The silicon nanocones are crystalline structure and have a uniform apex angle of about 22°. The cones can be coated in situ with an about 3 nm thick amorphous carbon film by increasing the methane concentration in source gases. With gradually decreasing the plasma intensity, the morphologies of the silicon nanostructures evolve along the nanocone–nanorod–nanowire route, and the nanowire becomes amorphous structure. The model for fabrication process of silicon nanostructures with different morphologies will also be suggested.