Characterization of silicon nanowires grown on silicon, stainless steel and indium tin oxide substrates

Silicon nanowires (SiNWs) have been grown on crystalline silicon (Si), indium tin oxide (ITO) and stainless steel (SS) substrates using a gold catalyst coating with a thickness of 200 nm via pulsed plasma-enhanced chemical vapor deposition (PPECVD). Their morphological, mineralogical and surface characteristics have been investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis. SiNWs growth is accompanied by oxidation, thus yielding partially (SiO _x ) and fully oxidized (SiO₂) Si sheaths. The mean diameters of these SiNWs range from 140 to 185 nm. Si with (111) and (220) planes exists in SiNWs grown on all three substrates while Si with a (311) plane is detected only for Si and ITO substrates. Computational simulation using density functional theory (DFT) has also been conducted to supplement the experimental Raman analyses for crystalline Si and SiO₂. XPS results reveal that ca. 30 % of the SiNWs have been oxidized for all substrates. The results presented in this paper can be used to aid selection of appropriate substrates for SiNW growth, depending on specific applications.     

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 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.     

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     

Effects of gas pressure on the synthesis and photoluminescence properties of Si nanowires in VHF-PECVD method

Silicon nanowires (SiNWs) were grown on an Au-coated Si(111) substrate at various gas pressures by very high frequency plasma enhanced chemical vapor deposition via the vapor–liquid–solid mechanism. The synthesized SiNWs were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy and photoluminescence (PL). The SiNWs were sharp needle-shaped and possessed highly crystalline core and oxide amorphous shell. As the gas pressure increases from 70 mtorr to 85 mtorr, the average diameter of the SiNWs decreases from 250 nm to 70 nm. Furthermore, the density of the nanowires increases with the gas pressure. The PL spectra revealed a peak at about 400 nm and a broadband emission at about 700 nm.     

纳米压印多孔硅模板的研究

纳米压印模板通常采用极紫外光刻、聚焦离子束光刻和电子束光刻等传统光刻技术制备,成本较高.寻找一种简单、低成本的纳米压印模板制备方法以提升纳米压印光刻技术的应用成为研究的重点与难点.本文以多孔氧化铝为母模板,采用纳米压印光刻技术对纳米多孔硅模板的制备进行了研究.在硅基表面成功制备出纳米多孔阵列结构,孔间距为350—560 nm,孔径在170—480 nm,孔深为200 nm.在激发波长为514 nm时,拉曼光谱的测试结果表明,相对于单面抛光的硅片,纳米多孔结构的硅模板拉曼光强有了约12倍左右的提升,对提升硅基光电器件的应用具有重要的意义.最后,利用多孔硅模板作为纳米压印母模板,通过热压印技术,成功制备出了聚合物纳米柱软模板.     

Silicon nanowires synthesized by vapor–liquid–solid growth on excimer laser annealed thin gold film

The fabrication of Si nanowires has been demonstrated using excimer laser annealed thin gold film as the catalyst and vapor–liquid–solid (VLS) growth. Au nanoparticles with mean diameters of 12, 13 and 15 nm were formed by excimer laser annealing (ELA) of Au film with thickness of 2.5, 5 and 10 nm, respectively. The results show that the silicon nanowires (SiNWs) with desired diameter can be obtained by controlling the Au film thickness and laser power density.     

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.     

Growth and use of metal nanocrystal assemblies on high-density silicon nanowires formed by chemical vapor deposition

In this paper, we describe the growth and potential application of metal nanocrystal assemblies on metal-catalyzed, CVD-grown silicon nanowires (SiNWs). The nanowires are decorated by chemical assembly of closely spaced (1–5 nm) Ag (30–100 nm diameter) and Au (5–25 nm diameter) nanocrystals formed from solutions of AgNO₃ and NaAuCl₄·2H₂O, respectively. The formation and growth of metal nanocrystals is believed to involve the galvanic reduction of metal ions from solution and the subsequent oxidation of available Si-hydride sites on the surfaces of the nanowires. A native oxide layer suppresses formation of metal nanocrystals; adding HF to the ionic solutions significantly increases the density of nanocrystals on the surfaces of the nanowires. The nanocrystals coating the nanowires were characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction. Ag nanocrystals on the nanowires afford sensitive detection of Rhodamine 6G (R6G) molecules in the 100 picomolar–micromolar range by surface enhanced Raman spectroscopy. In addition, Au nanocrystals formed on selected surfaces of a substrate of arbitrary shape can serve as effective nuclei for localized nanowire growth. PACS 81.07.b; 81.15.Gh     

Synthesis and analysis of silicon nanowire below Si-Au eutectic temperatures using very high frequency plasma enhanced chemical vapor deposition

Silicon nanowires (SiNWs) were synthesized from pure silane precursor gas and Au nanoparticles catalyst at below Au-Si eutectic temperature. The SiNWs were grown onto Si (1 1 1) substrates using very high frequency plasma enhanced chemical vapor deposition via a vapor-solid-solid mechanism at temperatures ranging from 363 to 230 °C. The morphology of the synthesized SiNWs was characterized by means of field emission scanning electron microscope equipped with energy dispersive X-ray, high resolution transmission electron microscopy, X-ray diffraction technique and Raman spectroscope. Results demonstrated that the SiNWs can be grown at the temperature as low as 250 °C. In addition, it was revealed that the grown wires were silicon-crystallized.     

Silicon nano-wires fabricated by thermal evaporation of silicon wafer

Thin silicon nano-wires (SiNWs) with a diameter of 10–20 nm were fabricated by a simple thermal evaporation of silicon wafer at 1523 K. The gold produced by an electrochemical method was covered on the wafer surface as catalyst. It was found that the SiNWs are amorphous and its Raman peak shifted down maybe due to the effect of laser heating and quantum confinement. Finally, a temperature gradient growth model is suggested to explain the growth direction of SiNWs.     

Coherent anti-Stokes Raman scattering in silicon nanowire ensembles

In this letter, we, for the first time, report on coherent anti-Stokes Raman scattering (CARS) spectroscopy of an ensemble of silicon nanowires (SiNWs) formed by wet chemical etching of crystalline silicon with a mask of silver nanoparticles. The fabricated SiNWs have diameter ranged from 30 to 200 nm and demonstrate both visible and infrared photolumine cence (PL) and spontaneous Raman signal, with their intensities depending on presence of silver nanoparticles in SiNWs. The efficiency of CARS in SiNW ensembles is found to be significantly higher than that in crystalline silicon. The results of CARS and PL measurements are explained in terms of resonant excitation of the electron states attributed to silicon nanoparticles.     

Impurity doping in silicon nanowires synthesized by laser ablation

Boron (B) or phosphorus (P) doped silicon nanowires (SiNWs) were synthesized by laser ablation. Local vibrational modes of B were observed in B-doped SiNWs by micro-Raman scattering measurements at room temperature. Fano broadening due to a coupling between the discrete optical phonon and a continuum of interband hole excitations was also observed in the Si optical phonon peak for B-doped SiNWs. An electron spin resonance signal due to conduction electrons was observed only for P-doped SiNWs. These results prove that B and P atoms were doped in substitutional sites of the crystalline Si core of SiNWs during laser ablation and electrically activated in the sites.     

一种新方法制备硅/聚(3, 4-乙撑二氧噻吩)核/壳纳米线阵列杂化太阳能电池

采用气相聚合法制备了有机/无机杂化的硅/聚3, 4-乙撑二氧噻吩核/壳纳米线阵列(SiNWs/PEDOT)太阳能电池. 相对平面结构Si/PEDOT太阳能电池, SiNWs/PEDOT太阳能电池的能量转换效率提升了7倍, 达到3.23%.对比分析反射光谱、I-V曲线及外量子效率的实验结果, 发现SiNWs/PEDOT太阳能电池性能改进的主要原因可归结为: 气相聚合法能够有效地制备出SiNWs/PEDOT电池的核/壳纳米线阵列结构, 使得器件具有高光捕获、高比结面积和高电荷收集效率. 关键词： Si/PEDOT核/壳纳米线结构 太阳能电池 气相聚合     

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.     

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.     

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.     

Growth parameters and shape specific synthesis of silicon nanowires by the VLS method

In this paper the effect of varying temperature, pressure and chemical precursors on the vapour–liquid–solid (VLS) growth of silicon nanowires (Si NWs) have been investigated. Some aspects of nucleation and growth mechanisms are discussed. Control on Si NW morphology by varying the choice of gaseous precursor (silane or dichlorosilane) at elevated temperatures is reported.     

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.