Synthesis of silicon nanowires using laser ablation method and their manipulation by electron beam

Size control of silicon nanowires (SiNWs) synthesized by laser ablation of a Si target with iron or nickel as catalysts were investigated by changing the synthesis parameters such as the content of catalyst in targets and laser power during synthesis. The diameter and length of SiNWs significantly depended on the synthesis parameters, i.e. the size of SiNWs can be controlled by the synthesis parameters. Manipulation of SiNWs was also performed during the observation of scanning electron microscope. By changing the degree of charge-up for free-standing adjacent intertwined SiNWs at an edge of Si substrate, the distance and speed of opening motion of them can be controlled. This motion is probably caused by the Coulomb repulsive interaction between them.     

Growth time-dependent density and surface evolution of silicon nanowires in a vapor-liquid-solid process

Single crystalline silicon nanowires (SiNWs) were grown on Si(100) substrate using a gold (Au)-catalyzed vapor-liquid-solid (VLS) approach. The dependence of the growth time (i.e., the time of exposure to the Si source) on the density and surface evolution of the grown SiNWs is considered. It was observed that the density of grown SiNWs on Si substrate increased with increasing growth time. The highest density (approximately 1.1 x 10(6) mm(-2)) was reached at 4 hr. Upon further exposure to the Si source, we observed that the density was maintained for up to 9 hr. We suggest that the increased Si chemical potential in Au-Si droplets with increased growth time enhanced the SiNW growth rate at the interfaces between Au-Si droplets and SiNWs, and enhanced the transition of the NWs from the existing Au-Si droplets onto Si substrate. This allows the SiNW density to increase with increased growth time of up to 4 hr. Moreover, we examined the influence of the growth time on surface evolution including Au diffusion, facet and taper formation, and vapor-solid (VS) growth of the SiNWs. To explain the behavior of the grown SiNWs in the VLS process, we propose a combined model using the VLS and VS growth mechanisms.     

Photoluminescence and optical limiting properties of silicon nanowires

Si nanowires (SiNWs) have been produced by thermal vaporization on Si(111) substrate without catalysts added. The grown SiNWs have been characterized by Raman scattering, SEM, XRD, and electron diffraction and shown to be highly crystalline with only little impurities such as amorphous Si and silicon oxides. Photoluminescence (PL) study has illustrated that the Si band-to-band gap increases from 1.1 eV for bulk Si to 1.56 eV for the as-grown SiNWs due to quantum confinement effect. A strong PL peak at 521 nm (2.37 eV) is attributed to the relaxation of the photon-induced self-trapped state in the form of surface Si-Si dimers, which may also play an important role in optical limiting of SiNWs with 532-nm nanosecond laser pulses. With the observation of optical limiting at 1064 nm, nonlinear scattering is believed to make a dominant contribution to the nonlinear response of SiNWs.     

Catalyst-free synthesis of silicon nanowires by oxidation and reduction process

A new process has been developed to grow silicon (Si) nanowires (NWs), and their growth mechanisms were explored and discussed. In this process, SiNWs were synthesized by simply oxidizing and then reducing Si wafers in a high temperature furnace. The process involves H₂, in an inert atmosphere, reacts with thermally grown SiO₂ on Si at 1100 °C enhancing the growth of SiNWs directly on Si wafers. High-resolution transmission electron microscopy studies show that the NWs consists of a crystalline core of ~25 nm in diameter and an amorphous oxide shell of ~2 nm in thickness, which was also supported by selected area electron diffraction patterns. The NWs synthesized exhibit a high aspect ratio of ~167 and room temperature phonon confinement effect. This simple and economical process to synthesize crystalline SiNWs opens up a new way for large scale applications.     

Significant enhancement of hole mobility in [110] silicon nanowires compared to electrons and bulk silicon

Utilizing sp3d5s* tight-binding band structure and wave functions for electrons and holes we show that acoustic phonon limited hole mobility in [110] grown silicon nanowires (SiNWs) is greater than electron mobility. The room temperature acoustically limited hole mobility for the SiNWs considered can be as high as 2500 cm2/V s, which is nearly three times larger than the bulk acoustically limited silicon hole mobility. It is also shown that the electron and hole mobility for [110] grown SiNWs exceed those of similar diameter [100] SiNWs, with nearly 2 orders of magnitude difference for hole mobility. Since small diameter SiNWs have been seen to grow primarily along the [110] direction, results strongly suggest that these SiNWs may be useful in future electronics. Our results are also relevant to recent experiments measuring SiNW mobility.     

Control of surface migration of gold particles on Si nanowires

On the surface of silicon nanowires (SiNWs) synthesized by gold (Au)-catalyzed chemical vapor deposition (CVD), Au particles 5-20 nm in diameter are formed if the growth conditions are within a specific range. We studied the mechanism of Au particle formation by growing SiNWs under different conditions, specifically by dynamically changing the growth parameters during the growth process. We show that insufficient supply of Si source to the Au-Si eutectic on top of the SiNWs enhances the migration of Au atoms on the surface of SiNWs in the form of Au-Si eutectic, which is precipitated on the surface as Au particles during cooling. We also show that using Au-Si eutectic on the surface of SiNWs as a catalyst enables one-step growth of branched SiNWs.     

Ultralow thermal conductivity of isotope-doped silicon nanowires

The thermal conductivity of silicon nanowires (SiNWs) is investigated by molecular dynamics (MD) simulation. It is found that the thermal conductivity of SiNWs can be reduced exponentially by isotopic defects at room temperature. The thermal conductivity reaches the minimum, which is about 27% of that of pure 28Si NW, when doped with 50% isotope atoms. The thermal conductivity of isotopic-superlattice structured SiNWs depends clearly on the period of superlattice. At a critical period of 1.09 nm, the thermal conductivity is only 25% of the value of pure Si NW. An anomalous enhancement of thermal conductivity is observed when the superlattice period is smaller than this critical length. The ultralow thermal conductivity of superlattice structured SiNWs is explained with phonon spectrum theory.     

New silicon architectures by gold-assisted chemical etching

Silicon nanowires (SiNWs) were produced by nanosphere lithography and metal assisted chemical etching. The combination of these methods allows the morphology and organization control of Si NWs on a large area. From the investigation of major parameters affecting the etching such as doping type, doping concentration of the substrate, we demonstrate the formation of new Si architectures consisting of organized Si NW arrays formed on a micro/mesoporous silicon layer with different thickness. These investigations will allow us to better understand the mechanism of Si etching to enable a wide range of applications such as molecular sensing, and for thermoelectric and photovoltaic devices.     

Use of phosphine as an n-type dopant source for vapor-liquid-solid growth of silicon nanowires

Phosphine (PH3) was investigated as an n-type dopant source for Au-catalyzed vapor-liquid-solid (VLS) growth of phosphorus-doped silicon nanowires (SiNWs). Transmission electron microscopy characterization revealed that the as-grown SiNWs were predominately single crystal even at high phosphorus concentrations. Four-point resistance and gate-dependent conductance measurements confirmed that electrically active phosphorus was incorporated into the SiNWs during VLS growth. A transition was observed from p-type conduction for nominally undoped SiNWs to n-type conduction upon the introduction of PH3 to the inlet gas. The resistivity of the n-type SiNWs decreased by approximately 3 orders of magnitude as the inlet PH3 to silane (SiH4) gas ratio was increased from 2 x 10(-5) to 2 x 10(-3). These results demonstrate that PH3 can be used to produce n-type SiNWs with properties that are suitable for electronic and optoelectronic device applications.     

Ion beam doping of silicon nanowires

We demonstrate n- and p-type field-effect transistors based on Si nanowires (SiNWs) implanted with P and B at fluences as high as 10(15) cm (-2). Contrary to what would happen in bulk Si for similar fluences, in SiNWs this only induces a limited amount of amorphization and structural disorder, as shown by electrical transport and Raman measurements. We demonstrate that a fully crystalline structure can be recovered by thermal annealing at 800 degrees C. For not-annealed, as-implanted NWs, we correlate the onset of amorphization with an increase of phonon confinement in the NW core. This is ion-dependent and detectable for P-implantation only. Hysteresis is observed following both P and B implantation.     

Forest of ultra thin silicon nanowires: realization of temperature and catalyst size

One of the most important progresses in the field of nano science and technology was partially due to the high surface to volume ratio of quasi one-dimensional silicon nanowires (SiNWs) with various applications in biological and chemical sensors, optoelectronic devices, catalysis, Li ion batteries and solar cells. In this study we have prepared a uniform forest of ultrathin SiNWs using plasma enhanced chemical vapor deposition method. Uniformly distributed SiNWs were obtained based on an Au layer containing gold nano-seeds with the average diameters ranging from 10 to 40 nm at various temperatures. The physicochemical properties of SiNWs were characterized using field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and high-resolution transmission electron microscopy. Microscopic assessments revealed that crystalline-amorphous core–shell SiNWs with different diameters and lengths ranging from 35 to 130 nm and ~?0.7 to 1.9 µm are formed during the vapor–liquid–solid mechanism, respectively. The XRD spectra show that the main lattice directions are Si(111), Si(220) and Si(311) which confirm crystalline structure of synthesized NWs. The PL spectrum reveal two distinct emission peaks at wavelengths of about 480 nm (blue range) and 690 nm (red range) as sharp and a broad peak, respectively.     

Controlled synthesis of millimeter-long silicon nanowires with uniform electronic properties

We report the nanocluster-catalyzed growth of ultralong and highly uniform single-crystalline silicon nanowires (SiNWs) with millimeter-scale lengths and aspect ratios up to approximately 100 000. The average SiNW growth rate using disilane (Si 2H 6) at 400 degrees C was 31 mum/min, while the growth rate determined for silane (SiH 4) reactant under similar growth conditions was 130 times lower. Transmission electron microscopy studies of millimeter-long SiNWs with diameters of 20-80 nm show that the nanowires grow preferentially along the 110 direction independent of diameter. In addition, ultralong SiNWs were used as building blocks to fabricate one-dimensional arrays of field-effect transistors (FETs) consisting of approximately 100 independent devices per nanowire. Significantly, electrical transport measurements demonstrated that the millimeter-long SiNWs had uniform electrical properties along the entire length of wires, and each device can behave as a reliable FET with an on-state current, threshold voltage, and transconductance values (average +/-1 standard deviation) of 1.8 +/- 0.3 muA, 6.0 +/- 1.1 V, 210 +/- 60 nS, respectively. Electronically uniform millimeter-long SiNWs were also functionalized with monoclonal antibody receptors and used to demonstrate multiplexed detection of cancer marker proteins with a single nanowire. The synthesis of structurally and electronically uniform ultralong SiNWs may open up new opportunities for integrated nanoelectronics and could serve as unique building blocks linking integrated structures from the nanometer through millimeter length scales.     

Ultrafast growth of single-crystalline Si nanowires

Silicon nanowires (SiNWs) have been catalytically synthesized by heat treatment of Si nanopowder at 980 °C. The SiNWs comprise crystalline Si nanoparticles interconnected with metal catalyst. The formation mechanism of nanowires generally depends on the presence of Fe catalysts in the synthesis process of solid–liquid–solid (SLS). Although gas phase of vapor–liquid–solid (VLS) method can be used to produce various of different nanowire materials, growth model based on the SLS mechanism by heat treatment is more ascendant for providing ultrafast growth of single-crystalline Si nanowires and controlling the diameter of them easily. The growth of single-crystalline SiNWs and morphology were discussed.     

Reversible electrowetting on superhydrophobic silicon nanowires

This paper reports for the first time on the reversible electrowetting of liquid droplets in air and oil environments on superhydrophobic silicon nanowires (SiNWs). The silicon nanowires were grown on Si/SiO2 substrates using the vapor-liquid-solid (VLS) mechanism, electrically insulated using 300 nm SiO2, and hydrophobized by coating with a fluoropolymer C4F8. The resulting surfaces displayed liquid contact angle (Theta) around 160 degrees for a saline solution (100 mM KCl) in air with almost no hysteresis. Electrowetting induced a maximum reversible decrease of the contact angle of 23 degrees at 150 VTRMS in air.     

Extended arrays of vertically aligned sub-10 nm diameter [100] Si nanowires by metal-assisted chemical etching

Large-area high density silicon nanowire (SiNW) arrays were fabricated by metal-assisted chemical etching of silicon, utilizing anodic aluminum oxide (AAO) as a patterning mask of a thin metallic film on a Si (100) substrate. Both the diameter of the pores in the AAO mask and the thickness of the metal film affected the diameter of SiNWs. The diameter of the SiNWs decreased with an increase of thickness of the metal film. Large-area SiNWs with average diameters of 20 nm down to 8 nm and wire densities as high as 10 (10) wires/cm (2) were accomplished. These SiNWs were single crystalline and vertically aligned to the (100) substrate. It was revealed by transmission electron microscopy that the SiNWs were of high crystalline quality and showed a smooth surface.     

Nanowire arrays in multicrystalline silicon thin films on glass: a promising material for research and applications in nanotechnology

Silicon nanowires (SiNW) were formed on large grained, electron-beam crystallized silicon (Si) thin films of only ～6 μm thickness on glass using nanosphere lithography (NSL) in combination with reactive ion etching (RIE). Electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) studies revealed outstanding structural properties of this nanomaterial. It could be shown that SiNWs with entirely predetermined shapes including lengths, diameters and spacings and straight side walls form independently of their crystalline orientation and arrange in ordered arrays on glass. Furthermore, for the first time grain boundaries could be observed in individual, straightly etched SiNWs. After heat treatment an electronic grade surface quality of the SiNWs could be shown by X-ray photoelectron spectroscopy (XPS). Integrating sphere measurements show that SiNW patterning of the multicrystalline Si (mc-Si) starting thin film on glass substantially increases absorption and reduces reflection, as being desired for an application in thin film photovoltaics (PV). The multicrystalline SiNWs directly mark a starting point for research not only in PV but also in other areas like nanoelectronics, surface functionalization, and nanomechanics.     

Pressure-induced orientation control of the growth of epitaxial silicon nanowires

Single crystal silicon nanowires (SiNWs) were synthesized with silane reactant using Au nanocluster-catalyzed one-dimensional growth. We have shown that under our experimental conditions, SiNWs grown epitaxially on Si(111) via the vapor-liquid-solid growth mechanism change their growth direction as a function of the total pressure. Structural characterization of a large number of samples shows that SiNWs synthesized at a total pressure of 3 mbar grow preferentially in the 111 direction, while the one at 15 mbar favors the 112 direction. Specifically by dynamically changing the system pressure during the growth process morphological changes of the NW growth directions along their length have been demonstrated.     

A wurtz-like reaction to silicon nanowires

Silicon nanowires have been successfully synthesized via wurtz-like reaction, using silicon tetrachloride and sodium in the presence of Co/Ni catalyzer at 500 °C In this process the sodium was used as reductant and flux. Transmission electron microscopy (TEM) shows that the nanowire cluster is about 10 nm in diameter and length up to several microns, and well aligned along their longitude direction. High-resolution transmission electron microscopy (HRTEM) images demonstrates that as-synthesized nanowires interlayer spacing are around 0.31 nm, corresponding well to the (111) lattice parameter of diamond-like crystalline silicon. Based on the experimental results, the possible wurtz reaction mechanism of the silicon nanowires (SiNWs) has been properly proposed.     

An effective three-dimensional surface-enhanced Raman scattering substrate based on oblique Si nanowire arrays decorated with Ag nanoparticles

Silicon nanowire arrays (SiNWAs) decorated with metallic nanoparticle heterostructures feature promising applications in surface-enhanced Raman scattering (SERS). However, the densely arranged SiNWAs are usually inconvenient for the following decoration of metallic nanoparticles, and only the top area of silicon nanowires (SiNWs) contributes to the SERS detection. To improve the utilization of the heterostructure, herein, oblique SiNWAs were grown separately, and Ag nanoparticles (AgNPs) were uniformly deposited by magnetron sputtering to get the three-dimensional (3D) SiNWAs decorated with AgNPs (AgNPs-SiNWAs) SERS substrate. The large open surfaces of oblique SiNWs would create more surface area available for the formation of hotspots and improve the adsorption and excitation of analyte molecules on the wire. The optimized AgNPs-SiNWAs substrate exhibits high sensitivity in detecting chemical molecule Rhodamine 6G, and the detection limit can reach 1 × 10^?10 M. More importantly, the substrate also can be used as an effective DNA sensor for label-free DNA detection.     

The oxidation characteristics of silicon nanowires grown with an au catalyst

In this study, we investigated the thermal oxidation of silicon nanowires (SiNWs) grown via the vapor-liquid-solid (VLS) method with an Au catalyst. We systematically analyzed the oxidation mechanism of the SiNWs in both the radial and axial directions and mapped the behavior of the Au atoms on the sidewall and at top of the wire as a function of oxidation time. After thermal oxidation at a temperature of 900 °C, two kinds of oxidation behavior in SiNWs were observed: one was conventional radial oxidation and the other was axial oxidation. In particular, the axial oxidation rate at the Si/Au interface increased dramatically compared with the radial oxidation rate, which can be explained by the reaction between the Si atoms precipitated from the Au tip and the O₂ gas injected in the area surrounding the Au tip. Additionally, we observed that the oxidation rate in the axial direction was inversely proportional to the wire diameter, which is related to the SiO₂ surrounding the Si wire. Moreover, the Au shape changed with respect to the wire diameter, suggesting that both the stress in the Au-Si alloy and the SiO₂ shell thickness of the wire critically affect the growth of SiO₂ on Au.