Fabrication and field emission properties of multi-walled carbon nanotube/silicon nanowire array

Silicon nanowire (SiNW) arrays were fabricated on silicon wafers by the metal-assisted chemical etching method. Varied average diameters of SiNW arrays were realized through further treatment in a mixed agent of HF and HNO₃ of certain concentrations. After the treatment, there were more than 93% SiNWs with diameters smaller than 100 nm. The tip of each SiNW was subsequently wrapped with multi-walled carbon nanotubes (MWCNTs) with chemical vapor deposition method. The as-fabricated MWCNT/SiNW arrays were fabricated into electric field emitters, with turn-on field of 2.0 V/μm (current density: 10 μA/cm²), much lower than that of SiNW array (5.0 V/μm). The turn-on electric field of MWCNT/SiNW array decreased with the decreasing of the average diameter of SiNWs, indicating the performance of the field emission is relative to the morphology of SiNWs. As the SiNW array is uniform in height and easy to fabricate, the MWCNT/SiNW array shows potential applications in flat electric display.     

碱溶液修饰硅纳米线阵列绒面

提出用碱溶液修饰硅纳米线阵列制作太阳能绒面的方法。实验中首先采用金属催化化学腐蚀法在Si(100)基底上制备了定向排列的硅纳米线阵列,然后将纳米线阵列浸入碱溶液中进行修饰,修饰时间分别为10,30,50,60,90s。通过扫描电子显微镜(SEM)对硅纳米线阵列进行形貌分析,采用太阳能测试系统附带的积分球测量纳米线阵列绒面结构的反射光谱。通过测量和分析发现硅纳线阵列在碱溶液中修饰30s时表面分布均匀,在400～1000nm波段的综合反射率低于4%。结果表明碱溶液修饰纳米线阵列的方法能够有效分散束状硅纳米线阵列,明显降低绒面的反射率,并且初步分析了碱溶液修饰硅纳米线阵列的分散机理。     

Fabrication of silver-coated silicon nanowire arrays for surface-enhanced Raman scattering by galvanic displacement processes

Silver-coated silicon nanowire (SiNW) arrays were prepared utilizing galvanic displacement processes consisting of three steps: galvanic displacement deposition of silver particles using a HF-AgNO₃ or NH₄F-AgNO₃ aqueous solution; formation of SiNW arrays by a silver-assisted chemical etching process conducted in the HF-H₂O₂ aqueous solution; deposition of silver particles on the SiNW arrays from the NH₄F-AgNO₃ aqueous solution. The effects of the morphology of pre-deposited silver particles and deposition solution on the formation of silver-coated SiNW arrays were discussed. Surface-enhanced Raman scattering (SERS) performances have been studied using Rhodamine 6G (R6G) probe molecules on the silver-coated SiNW substrates.     

High-resolution analytical electron microscopy of catalytically etched silicon nanowires

We report on the characterization of hexagonally ordered, vertically aligned silicon nanowires (SiNW) by means of analytical transmission electron microscopy. Combining colloidal lithography, plasma etching, and catalytic wet etching arrays of SiNW of a sub-50 nm diameter with an aspect ratio of up to 10 could be fabricated. Scanning transmission electron microscopy has been applied in order to investigate the morphology, the internal structure, and the composition of the catalytically etched SiNW. The analysis yielded a single-crystalline porous structure composed of crystalline silicon, amorphous silicon, and SiO _x with x≤2.     

Sulfur-doped black silicon formed by metal-assist chemical etching and ion implanting

We fabricated sulfur-doped black silicon by metal-assist chemical etching (MCE) and ion implanting. The morphologies of silicon nanowire (SiNW) arrays and the concentration of sulfur in black silicon were analyzed by scanning electron microscope (SEM). Sulfur-doped black silicon shows higher absorption in entire 0.3–2.5 μm wavelength range as compared to undoped SiNW arrays and flat silicon. The changes in the absorption spectra of black silicon with different etching durations and annealing temperature are also shown. Upon annealing, the absorption decreases significantly in 2–2.5 μm wavelength region. The novel results clearly indicate that sulfur implanting could produce below band gap absorption in the silicon substrate.     

碱液修饰对硅纳米线阵列电池光谱响应的影响

采用金属催化化学腐蚀法在p型(100)硅基底上制备了硅纳米阵列,然后用碱溶液对纳米线阵列进行修饰。分别研究了碱液修饰对硅纳米线阵列形貌、光电性质的影响。研究表明: 与绒面及纳米线阵列相比,碱修饰30 s硅纳米线阵列的表面分散均匀,反射率降低;光谱响应度显著提高,并且出现最大量子效率对应波长红移现象。最后,详细讨论了碱液修饰硅纳米线阵列电池对光谱响应的影响机制。     

Formation of aligned silicon nanowire on silicon by electroless etching in HF solution

It was demonstrated that the etching in HF-based aqueous solution containing AgNO₃ and Na₂S₂O₈ as oxidizing agents or by Au-assisted electroless etching in HF/H₂O₂ solution at 50 °C yields films composed of aligned Si nanowire (SiNW). SiNW of diameters ∼10 nm were formed. The morphology and the photoluminescence (PL) of the etched layer as a function of etching solution composition were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence. It was demonstrated that the morphology and the photoluminescence of the etched layers strongly depends on the type of etching solution. Finally, a discussion on the formation process of the silicon nanowires is presented.     

Effects of silver and gold catalytic activities on the structural and optical properties of silicon nanowires

The metal-assisted chemical etching of silicon in an aqueous solution of hydrofluoric acid and hydrogen peroxide is established for the fabrication of large area, uniform silicon nanowire (SiNW) arrays. In this study, silver (Ag) and gold (Au) are considered as catalysts and the effect of different catalysts with various thicknesses on the structural and optical properties of the fabricated SiNWs is investigated. The morphology of deposited catalysts on the silicon wafer is characterized by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is shown that the morphology of the fabricated silicon nanostructures remarkably depends upon the catalyst layer thickness, and the catalyst etching time directly affects the structural and optical properties of the synthesized SiNWs. FESEM images show a linear increment of the nanowire length versus time, whereas the etching rate for the Au-etched SiNWs was lower than the Ag-etched ones. Strong light scattering in SiNWs caused the total reflection to decrease in the range of visible light, and this decrement was higher for the Ag-etched SiNW sample, with a longer length than the Au-etched one. A broadband visible photoluminescence (PL) with different peak positions is observed for the Au- and Ag-etched samples. The synthesized optically active SiNWs can be considered as a promising candidate for a new generation of nano-scale opto-electronic devices.     

Interface modification and trap-type transformation in Al-doped CdO/Si-nanowire arrays/p-type Si devices by nanowire surface passivation

The present work reports the fabrication and detailed electrical properties of Al-doped CdO/Si-nanowire (SiNW) arrays/p-type Si Schottky diodes with and without SiNW surface passivation. It is shown that the interfacial trap states influence the electronic conduction through the device. The experimental results demonstrate that the effects of the dangling bonds at the SiNW surface and Si vacancies at the SiO_x/SiNW interface which can be changed by the Si–O bonding on the energy barrier lowering and the charge transport property. The induced dominance transformation from electron traps to hole traps in the SiNWs by controlling the passivation treatment time is found in this study.     

Effect of temperature and silicon resistivity on the elaboration of silicon nanowires by electroless etching

The morphology of silicon nanowire (SiNW) layers formed by Ag-assisted electroless etching in HF/H₂O₂ solution was studied. Prior to the etching, the Ag nanoparticles were deposited on p-type Si(1 0 0) wafers by electroless metal deposition (EMD) in HF/AgNO₃ solution at room temperature. The effect of etching temperature and silicon resistivity on the formation process of nanowires was studied. The secondary ion mass spectra (SIMS) technique is used to study the penetration of silver in the etched layers. The morphology of etched layers was investigated by scanning electron microscope (SEM).     

Fabrication of large-scale periodic silicon nanopillar arrays for 2D nanomold using modified nanosphere lithography

We present a fabrication procedure that can form large-scale periodic silicon nanopillar arrays for 2D nanomold which determines the feature size of nanoimprint lithography, using modified nanosphere lithography. The size of silicon nanopillars can be easily controlled by an etching and oxidation process. The period and density of nanopillar arrays are determined by the initial diameter of polystyrene (PS) spheres. In our experiment, the smallest nanopillar has a full width half maximum (FWHM) of approximately 50 nm, and the density of silicon pillar is ∼10⁹/cm². Using this approach, it is possible to fabricate 2D nanoimprint lithography mask with 50 nm resolution.     

Morphology control and electron field emission properties of high-ordered Si nanoarrays fabricated by modified nanosphere lithography

High-ordered silicon nanoarrays were prepared using direct nanosphere lithography combined with thermal oxidation. Atomic force microscope (AFM) images of the silicon arrays show that the patterns of polystyrene (PS) template are well transferred to the silicon surface. The size and morphology of the nanoarrays can be controlled effectively by varying the plasma-therm reactive ion etching (RIE) or thermal oxidation parameters. The field emission studies revealed that the typical turn-on field was about 7-8 V/μm with emission current reached 1 μA/cm². It is also found that the field emission current is highly dependent on the morphology of these Si nanoarrays.     

Formation of aligned silicon-nanowire on silicon in aqueous HF/(AgNO3 + Na2S2O8) solution

Highly oriented silicon nanowire (SiNW) layer was fabricated by etching Si substrate in HF/(AgNO₃ + Na₂S₂O₈) solution at 50 °C. The morphology and the photoluminescence (PL) of the etched layer as a function of Na₂S₂O₈ concentration were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). It was demonstrated that the morphology of the etched layers depends on the Na₂S₂O₈ concentration. Room-temperature photoluminescence (PL) from etched layer was observed. It was found that the utilisation of Na₂S₂O₈ decreases PL peak intensity. Finally, a discussion on the formation process of the silicon nanowires is presented.     

Field emission from patterned SnO2 nanostructures

A simple and reliable method has been developed for synthesizing finely patterned tin dioxide (SnO₂) nanostructure arrays on silicon substrates. A patterned Au catalyst film was prepared on the silicon wafer by radio frequency (RF) magnetron sputtering and photolithographic patterning processes. The patterned SnO₂ nanostructures arrays, a unit area is of ∼500 μm × 200 μm, were synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized SnO₂ nanostructures were characterized by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The mechanism of formation of SnO₂ nanostructures was also discussed. The measurement of field emission (FE) revealed that the as-synthesized SnO₂ nanorods, nanowires and nanoparticles arrays have a lower turn-on field of 2.6, 3.2 and 3.9 V/μm, respectively, at the current density of 0.1 μA/cm². This approach must have a wide variety of applications such as fabrications of micro-optical components and micropatterned oxide thin films used in FE-based flat panel displays, sensor arrays and so on.     

硅纳米线阵列的光学特性

在常温常压条件下,采用改进的金属催化化学腐蚀方法在n型单晶硅片(100)上制备了大面积垂直于硅衬底、直径均匀、排列整齐的硅纳米线阵列。分析了样品的表面形貌和反射谱,纳米线直径为10~50 nm。在腐蚀时间分别为15,30,60 m in时,纳米线长度分别为9,17,34μm。样品的减反射性能优异,在300~1 000nm波段,得到了2.4%的反射率。初步分析了纳米线阵列的减反射机制和不同腐蚀时间样品的反射率差异。     

Synthesis, morphology and random laser action of ZnO nanostructures

Three-dimensional (3-D) ZnO random-wall nanostructures and one-dimensional (1-D) ZnO nanorods were prepared on silicon substrates by a simple solid-vapour phase thermal sublimation technique. Optical pumped random lasing has been observed in the ZnO random-wall arrays with a threshold intensity of 0.38 MW/cm² in the emission wavelength from 380 to 395 nm. The optical gain was attributed to the closed-loop scattering and light amplification of the ZnO random-wall. The experimental result suggests that the morphology of nanostructure is the key factor to effect random lasing.     

A model for growth directional features in silicon nanowires

Long silicon nanowires (SiNWs) grown by laser ablation or by thermal evaporation of monoxide source materials are primarily oriented in the <112> direction, and some in the <110> direction, but rarely in the <100> or <111> directions. We propose a model to explain these SiNW growth directional features. The model consists of two parts. Part one is concerned with mechanism-based criteria and part two with applying these criteria to explain the experimental results. Four criteria are considered: (i) the stability of a Si atom occupying a surface site; (ii) the Si {111} surface stability in the presence of oxygen; (iii) the stepped Si {111} surface layer lateral growth process; and (iv) the effect of dislocations in providing perpetuating {111} steps to facilitate SiNW growth. Analyses of SiNW growth in accordance with these criteria showed that <112> and <110> are the preferred SiNW growth directions, and that <111> and <100> are not. Received: 12 November 2001 / Accepted: 20 November 2001 / Published online: 23 January 2002     

Electrochemical albumin sensing based on silicon nanowires modified by gold nanoparticles

Si nanowires (SiNWs) were modified by Au nanoparticles (AuNPs) using a self-assembled monolayer of aminopropyltriethoxysilane (APTES) and used for direct sensing of the bovine serum albumin (BSA). It was shown that repeated thermal treatment of the sensor greatly enhanced the reliability of the SiNW sensor by increasing the electrical conductivity largely from carbonization of the APTES molecules and from bringing the AuNPs in intimate contact with the SiNW surface. The AuNP-modified SiNW array sensor was able to detect 1-7 μM of BSA. The sensor exhibited a good sensitivity over the tested concentration range and linear behavior. It is expected that the proposed label-free biosensor can be further developed to selectively detect and quantify biomolecules other than BSA.     

分子动力学研究表面缺陷对硅纳米线杨氏模量的影响

硅纳米线因受量子尺寸效应与表面效应的影响而具有奇特的力、电及其耦合特性,成为了纳米电子器件的核心构件.然而在硅纳米线的制备过程中,表面产生缺陷不可避免.因此本文采用分子动力学方法着重研究了表面缺陷浓度对不同横截面形状(正方形、六角形和三角形)的[110]晶向和[111]晶向硅纳米线杨氏模量的影响.研究结果表明,当硅纳米线仅有单一表面缺陷时,不同晶向硅纳米线的杨氏模量均随表面缺陷浓度增加而迅速单调减小.当表面缺陷浓度为10%时,杨氏模量的减小幅度在10%-20%之间,减小幅度的差异与硅纳米线的晶向以及横截面形状密切相关.当存在多个表面缺陷时,杨氏模量随着缺陷浓度的增加表现出了不同程度的波动趋势.三角形截面硅纳米线的杨氏模量波动幅度最大,正方形截面的波动较小,即表面缺陷分布的不同对正方形截面硅纳米线的杨氏模量影响较小,这表明表面缺陷的影响与其分布及硅纳米线的横截面形状密切相关.通过与实验结果对比,本文的研究结果揭示了表面缺陷是导致硅纳米线杨氏模量实验值变小的重要因素,因此在表征硅纳米线的力学性能时,需要考虑表面缺陷的影响.     

Silicon nanowires for sequence-specific DNA sensing: device fabrication and simulation

Highly sensitive, sequence-specific and label-free DNA sensors were demonstrated by monitoring the electronic conductance of silicon nanowires (SiNWs) with chemically bonded single-stranded (ss) DNA or peptide nucleic acid (PNA) probe molecules. For a 12-mer oligonucleotide, tens of pM of target ss-DNA in solution was recognized when the complementary DNA oligonucleotide probe was attached to the SiNW surfaces. In contrast, ss-DNA samples of ×1000 concentration with a single-base mismatch produce only a weak signal due to nonspecific binding. In order to gain a physical understanding of the change in conductance of the SiNWs with the attachment of the DNA targets and the probes, process and device simulations of the two-dimensional cross sections of the SiNWs were performed. The simulations explained the width dependence of the SiNW conductance and provided understanding to improve the sensor performance. PACS 85.35.-p; 87.83.+a; 07.07.Df