An analysis on synthesizing large scales of one-dimensional silicon nano-structures by simple evaporation of sulfur-contained powders

The growth mechanism for synthesizing large scales of one-dimensional silicon nano-structures (silicon nano-wires (SiNWs) or silicon oxide nano-wires (SiO₂-NWs)) by a simple evaporation of sulfur-contained powders on silicon wafer is discussed. A novel sulfide-assisted mechanism referring to oxygen-assisted mechanism is proposed. Amongst this simple method, sulfide or pure sulfur can both assist the formation of SiNWs. The growth is fast and some SiNWs are easily oxidized to be amorphous structure of SiO₂-NWs under the low-vacuum system. The simple method suggests a useful route to achieve plenty of one-dimensional silicon nano-structures for further research.     

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.     

Selective formation of silicon nanowires on pre-patterned substrates

In this paper, the selective growth of silicon nanowires (SiNWs) was studied. With the aid of photolithography, the vertically aligned silicon nanowires were selectively formed on the patterned substrates via an electroless metal deposition (EMD) method under normal conditions (room temperature, 1 atm). Low-pressure chemical vapor deposition (LPCVD) silicon nitride was used as the masking layer for SiNWs preparation. The scanning electron microscope was used to examine the etching results. Both the patterned and the unpatterned silicon substrates were used for study. The results indicated that the growth rates of the SiNWs upon the patterned and the unpatterned substrates are different. For the patterned substrates, the growth rate of SiNWs is dependent upon the pattern shape. The influence of length-to-width ratio for the rectangular-shaped patterns was studied. It is concluded that by designing the proper length-to-width ratio, the nanowires with different lengths can be fabricated simultaneously on the same substrate.     

ON THE STUDY OF SILICON NANO-WIRES SELF-ASSEMBLED AS PARTICLES

Two different types of Silicon nano-wires (SiNWs) have been observed by scanning and transmission electron microscopy. One are of free standing SiNWs deposited uniformly on the surface of silicon substrates, and the other are self-assembled into special shaped particles. These SiNWs were synthesized by thermal evaporation of SiO amorphous powders without any metal catalysts in the temperature range of 900-1250℃. Growth history reveals that the self-assembled SiNWs are formed by original nucleation from the surface of amorphous SiO_{x particle matrices through phase separation and silicon precipitation followed by further growth through oxide-assisted vapor-solid reactions. The above results provide a solid experimental support for the oxide-assisted growth model of SiNWs.}     

Formation of Si nanowires by the electrochemical reduction of porous Ni/SiO2 blocks in molten CaCl2

Silicon nanowires (SiNWs) were prepared by the electrochemical reduction of solid Ni/SiO₂ blocks in molten CaCl₂ at 1173 K. The SiNWs have diameter distributions ranging from 80 to 350 nm, and the nickel–silicon droplets are found on the tips of the nanowires. The growth mechanism of SiNWs was investigated, which confirmed that the nano-sized nickel–silicon droplets formed at the Ni/SiO₂/CaCl₂ three-phase interline. The droplets lead to the oriented growth of SiNWs. Formation of nano-sized nickel–silicon droplets suggests that this method could be a potential way to produce nano-sized metal silicides.     

Silicon nano-wires fabricated by a novel thermal evaporation of zinc sulfide

Silicon nano-wires (SiNWs) with diameter of 30 nm and length of tens of micrometers on silicon wafers were synthesized by a novel thermal evaporation of zinc sulfide. After thermal evaporation at 1080°C for 1 h, crystalline SiNWs were produced. It was found that the tip of SiNWs contained sulfur, while the other places of SiNWs did not. It is considered that the decomposition of SiS resulted in the formation of SiNWs. On the basis of the facts, a sulfide-assisted growth model of SiNWs was suggested.     

Raman spectroscopy for study of interplay between phonon confinement and Fano effect in silicon nanowires

A combined effect of doping (type and species) and size on Raman scattering from silicon (Si) nanowires (NWs) has been presented here to study interplay between quantum confinement and Fano effects. The SiNWs prepared from low doping Si wafers show only confinement effect, as evident from the asymmetry in the Raman line‐shape, irrespective of the doping type. On the other hand SiNWs prepared from wafer with high doping shows the presence of electron–phonon interaction in addition to the phonon confinement effect as revealed from the presence of asymmetry and antiresonence in the corresponding Raman spectra. This combined effect induces an extra asymmetry in the lower energy side of Raman peak for n‐type SiNWs whereas the asymmetry flips from lower energy side to the higher energy side of the Raman peak in p‐type SiNWs. Such an interplay can be represented by considering a general Fano‐Raman line‐shape equation to take care of the combined effect in SiNWs. Copyright © 2015 John Wiley & Sons, Ltd.     

The effect of differently sized Ag catalysts on the fabrication of a silicon nanowire array using Ag-assisted electroless etching

A simple and low cost method to generate single-crystalline, well-aligned silicon nanowires (SiNWs) of large area, using Ag-assisted electroless etching, is presented and the effect of differently sized Ag catalysts on the fabrication of SiNWs arrays is investigated. The experimental results show that the size of the Ag catalysts can be controlled by adjusting the pre-deposition time in the AgNO₃/HF solution. The optimum pre-deposition time for the fabrication of a SiNWs array is 3 min (about 162.04 ± 38.53 nm Ag catalyst size). Ag catalysts with smaller sizes were formed in a shorter pre-deposition time (0.5 min), which induced the formation of silicon holes. In contrast, a large amount of Ag dendrites were formed on the silicon substrate, after a longer pre-deposition time (4 min). The existence of these Ag dendrites is disadvantageous to the fabrication of SiNWs. Therefore, a proper pre-deposition time for the Ag catalyst is beneficial to the formation of SiNWs.SiNWs were synthesized in the H₂O₂/HF solution system for different periods of time, using Ag-assisted electroless etching (pre-deposition of the Ag catalyst for 3 min). The length of the SiNWs increases linearly with immersion time. From TEM, SAED and HRTEM analysis, the axial orientation of the SiNWs is identified to be along the [001] direction, which is the same as that of the initial Si wafer. The use of HF may induce Si–H_x bonds onto the SiNW array surface. Overall, the Ag-assisted electroless etching technique has advantages, such as low temperature, operation without the need for high energy and the lack of a need for catalysts or dopants.     

Aligned silicon nanowires with fine‐tunable tilting angles by metal‐assisted chemical etching on off‐cut wafers

The morphology control of aligned silicon nanowires (SiNWs) is highly desirable as SiNWs demonstrated high prospect in a variety of applications. Besides the control over length, shape and distribution of aligned SiNWs, the fine‐tuning of tilting angles thereof also attracted intense interest. Up to now, only several discrete tilting angles have been reported. In this Letter, the ability to fine‐tune the tilting angle of SiNWs is demonstrated and the range that can be achieved is identified. Our technique employs the anisotropic characteristic of the etching process using custom‐produced off‐cut Si wafers of various orientations as substrates. With this technique, a uniquely favoured etching direction can result and the tilting angle can be precisely controlled. Tilted SiNWs with tilting angles from 0° to 50° relative to the wafer normal were obtained. The mechanism of the tilting angle manipulation is also discussed. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Influence of B<Subscript>2</Subscript>H<Subscript>6</Subscript> on the Growth of Silicon Nanowire

The un-doped and boron-doped silicon nanowires (SiNWs) were grown via vapor–liquid–solid (VLS) mechanism by low pressure chemical deposition (LPCVD). The diameters of un-doped and boron-doped SiNWs varied from 18.5 to 75.3 nm and 26.6 to 66.1 nm, respectively. The critical growth temperature of boron-doped SiNWs is 10°C lower than that of un-doped ones and the diameters of the boron-doped SiNWs is always larger than that of the un-doped ones under different growth temperatures. This is because that the introduction of diborane enhanced the dissociation of SiH₄ which determines the growth process of SiNW. A growth process of silicon nanowire is proposed to describe the influence of B₂H₆.     

Oxide-assisted growth of silicon nanowires by carbothermal evaporation

Silicon nanowires (SiNWs) have successfully been synthesized by carbothermal evaporation method. By ramping-up the furnace system at 20 °C min⁻¹ to 1100 °C for 6 h, the vertically aligned coexist with crooked SiNWs were achieved on the silicon substrate located at 12 cm from source material. The processing parameters such as temperature, heating rate, duration, substrate position and location are very important to produce SiNWs. Morphology and chemical composition of deposited products were investigated by field-emission scanning electron microscopy (FESEM) equipped with energy dispersive X-ray analysis (EDX). The existence of small sphere silicon oxide capped nanowires suggested that the formation of SiNWs was governed by oxide-assisted growth (OAG) mechanism.     

Preparation and surface modification of silicon nanowires under normal conditions

Preparation and surface modification of silicon nanowires (SiNWs) grown by the metal catalyzed solution method under normal conditions (room temperature, 1 atm) had been studied in this paper. Firstly, SiNWs using a simple solution method via electroless metal deposition (EMD) of silver under room temperature, standard pressure had been prepared. The influence of the growth parameters such as solution concentration, etching time on the SiNWs formation had been studied. Secondly, the surface modification of SiNWs with platinum and copper had been investigated. The results indicated that the SiNWs modified with Pt and Cu showed different surface morphologies. Pt modification on SiNWs presented in the form of nanoparticles, whereas Cu modification in the form of membrane. Therefore, the Pt modified SiNWs have more vast surface-to-bulk ratio than the unmodified ones, and SiNWs modified with copper nanoparticles will lead to the smaller surface-to-bulk ratio. So the platinum-modified SiNWs have a promising application in sensors’ field.     

Sulfide-assisted growth of silicon nano-wires by thermal evaporation of sulfur powders

Silicon nanowires (SiNWs) with a diameter of 20 nm were synthesized by the thermal evaporation of sulfur powders on silicon wafers. The source of the SiNWs came from the silicon substrates. It is considered that the generated SiS compound assisted the formation of SiNWs. Finally, the Raman shift of SiNWs was discussed.     

Synthesis and optical properties of silicon nanowires grown by different methods

We review our recent results on the growth and characterization of silicon nanowires (SiNWs). Vapour-phase deposition techniques are considered, including chemical vapour deposition (CVD), plasma-enhanced chemical vapour deposition (PECVD), high-temperature annealing, and thermal evaporation. We present complementary approaches to SiNW production. We investigate the low-temperature (down to 300 °C) selective nucleation of SiNWs by Au-catalysed CVD and PECVD. Bulk production of SiNWs is obtained by thermal-vapour deposition from Si/SiO powders in a high-temperature furnace. In this case, SiNWs grow either by condensing on Au catalyst films, or by self-condensation of the vapour in a lower-temperature region of the furnace. Finally, we also achieve controlled growth by thermolysis of nanopatterned, multi-layered Si/Au thin-film precursors. The as-produced wires are compared in terms of yield, structural quality, and optical properties. Raman and photoluminescence spectra of SiNWs are discussed. PACS 81.15.Gh; 73.21.-b; 73.21.Hb; 71.20.Mq; 78.30.-j     

The development of an inspection system for defects in silicon crystal growth

This study presents an inspection system to detect the growth defects of silicon crystals that comprise a CCD camera, an LED light source, and power modulation. The defects on multicrystalline silicon can be observed clearly while the silicon wafer were irradiated by the red LED light at a small lighting angle (i.e., 20–30°). However, the growth defects on monocrystalline silicon wafer were difficult to observe because of it low image intensity. And then, the growth defects image was significantly enhanced when the wafer was illuminated by a white LED (WLED) and rotated at a specific angle (i.e., 23°). The experimental results showed that the WLED illumination system made the growth defects more easily observable than did other LED sources (i.e., red, blue, and green LEDs). In addition, the proposed inspection system can be used for on-line fast detection for quality control of monocrystalline silicon wafer.     

Effects of silicon nanowires length on solar cells photovoltaic properties

Silicon nanowires (SiNWs) were produced by an electroless method on FZ-Si (100) wafer, in HF/AgNO₃ solution. The influence of etching time and temperature on SiNWs morphology were studied using FESEM images. Optical properties were also investigated by optical absorption spectroscopy and low-temperature photoluminescence at 4.2?K. Considering their role as active regions, photovoltaic properties of SiNWs solar cells were studied for their different lengths. Photovoltaic measurements were taken in 1 sun condition under AM 1.5 illumination supplied by a solar simulator. Measurements indicated a reduction in efficiency as SiNWs length increased, which might be attributed to increased dangling states on nanowires surfaces.     

The effects of surface modification on the electrical properties of p–n+ junction silicon nanowires grown by an aqueous electroless etching method

Although the aqueous electroless etching (AEE) method has received significant attention for the fabrication of silicon nanowires (SiNWs) due to its simplicity and effectiveness, SiNWs grown via the AEE method have a drawback in that their surface roughness is considerably high. Thus, we fabricated surface-modified p–n ⁺ junction SiNWs grown by AEE, wherein the surface roughness was reduced by a sequential processes of oxide growth using the rapid thermal oxidation (RTO) cycling process and oxide removal with a hydrofluoric acid solution. High-resolution transmission electron microscopy analysis confirmed that the surface roughness of the modified SiNWs was significantly decreased compared with that of the as-fabricated SiNWs. After RTO treatment, the wettability of the SiNWs had dramatically changed from superhydrophilic to superhydrophobic, which can be attributed to the formation of siloxane groups on the native oxide/SiNW surfaces and the effect of the nanoscale structure. Due to the enhancement in surface carrier mobility, the current density of the surface-modified p–n ⁺ junction SiNWs was approximately 6.3-fold greater than that of the as-fabricated sample at a forward bias of 4 V. Meanwhile, the photocurrent density of the surface-modified p–n ⁺ junction SiNWs was considerably decreased as a result of the decreases in the light absorption area, light absorption volume, and light scattering.     

Single-crystal Al-catalyzed Si nanowires grown via hedgehog-shaped Al-Si aggregates

Single-crystal, Al-catalyzed Si nanowires (SiNWs) were grown under atmospheric pressure using the dimpled feature of Al metal that remained after the removal of an anodic aluminum oxide (AAO) template directly formed on a Si substrate. During the H₂ preannealing prior to growth, the dimpled surface morphology of the remaining Al changed as the Al formed agglomerations with each other and subsequently formed Al-Si alloy islands on the silicon surface. Silicon nanowires were found to only grow on these islands, resulting in the final hedgehog-shaped morphology. The amount of Al agglomeration which controlled the overall size of the alloy islands was determined by varying the H₂/Ar flow ratio during preannealing. High-density growth of SiNWs was observed at a lower ratio of the H₂/Ar flow rates.     

Au5Si2/Si Heterojunction Nanowires Formed by Combining SiO Evaporation with Vapour--Liquid--Solid Mechanism

Crystalline AusSi2/Si heterojunetion nanowires （AusSi2/SiNWs） are obtained by thermal evaporating SiO pow- ders on thick gold-coated silicon substrates in a low vacuum system. Structure analysis of the produced AusSh/Si heterojunetions is performed by employing a transmission electron microscope （TEM） and a selected area electric diffraetometer. The chemical compositions axe studied by a energy-dispersive x-ray spectroscope attached to the TEM. A two-step growth model is proposed to describe the formation of the AusSi2/SiNWs. During the first step, crystalline SiNWs are formed via a growth mechanism combining the oxide-assisted growth process with the vapour-liquid-solid model at relatively high temperature. In the second step, the temperature decreases and one segment of the preformed SiNWs reacts with the remnant Au to form single crystalline AusSi2 nanowires by a solid-liquid-solid process. The present work should be useful for the future synthesis and research of high-quality gold silicide nanowires and microelectronic devices based on the nanowires.     

Microstructural characterization of Li insertion in individual silicon nanowires

The lithiation and delithiation process of silicon nanowire arrays (SiNWs) on silicon substrates has been studied with high-resolution electron microscopy. The composition of lithiated SiNWs was revealed, consisting of the unreacted crystalline silicon core and the reacted amorphous Li–Si shell. In particular, the Li–Si shell was comprised of a mixture of amorphous silicon oxide and crystalline silicon, leading to hindrance during Li–Si alloying/dealloying upon cycling.