Preparation of high-purity straight silicon nanowires by molten salt electrolysis

Silicon nanowires of high purity and regular morphology are of prime importance to ensure high specific capacities of lithium-ion batteries and reproducible electrode assembly process.Using nickel formate as a metal catalyst precursor,straight silicon nanowires(65–150 nm in diameter)were directly prepared by electrolysis from the Ni/SiO2 porous pellets with 0.8 wt%nickel content in molten CaCl2 at 900℃.Benefiting from their straight appearance and high purity,the silicon nanowires therefore offered an initial coulombic efficiency of 90.53% and specific capacity of 3377 m Ah/g.In addition,the silicon nanowire/carbon composite exhibited excellent cycle performance,retaining 90.38%of the initial capacity after 100 cycles.Whilst further study on the charge storage performance is still ongoing,these preliminary results demonstrate that nickel formate is an efficient and effective metal catalyst precursor for catalytic preparation of high purity straight silicon nanowires via the molten salt electrolysis,which is suitable for large-scale production.

Thermal stability of silicon nanowires:atomistic simulation study

Using the Stillinger Weber （SW） potential model,we investigate the thermal stability of pristine silicon nanowires based on classical molecular dynamics （MD） simulations.We explore the structural evolutions and the Lindemann indices of silicon nanowires at different temperatures in order to unveil atomic-level melting behaviour of silicon nanowires.The simulation results show that silicon nanowires with surface reconstructions have higher thermal stability than those without surface reconstructions,and that silicon nanowires with perpendicular dimmer rows on the two （100） surfaces have somewhat higher thermal stability than nanowires with parallel dimmer rows on the two （100） surfaces.Futher-more,the melting temperature of silicon nanowires increases as their diameter increases and reaches a saturation value close to the melting temperature of bulk silicon. The value of the Lindemann index for melting silicon nanowires is 0.037.

Ultra-Low Breakdown Voltage of Field Ionization in Atmospheric Air Based on Silicon Nanowires

Classic field ionization requires extremely high positive electric fields, of the order of a few million volts per centimeter. Here we show that field ionization can occur at dramatically lower fields on the electrode of silicon nanowires （SiNWs） with dense surface states and large field enhancement factor. A field ionization structure using SiNWs as the anode has been investigated, in which the SiNWs were fabricated by improved chemical etching process. At room temperature and atmospheric pressure, breakdown of the air is reproducible with a fixed anode-to-cathode distance of 0.5 μm. The breakdown voltage is -38 V, low enough to be achieved by a batterypowered unit. Two reasons can be given for the low breakdown voltage. First, the gas discharge departs from the Paschen＇s law and the breakdown voltage decreases sharply as the gap distance falls in μm range. The other reason is the large electric field enhancement factor （β） and the high density of surface defects, which cause a highly non-uniform electric field for field emission to occur.

Ultra-low thermal conductivity of roughened silicon nanowires:Role of phonon-surface bond order imperfection scattering

The ultra-low thermal conductivity of roughened silicon nanowires(SiNWs)can not be explained by the classical phonon-surface scattering mechanism.Although there have been several efforts at developing theories of phonon-surface scattering to interpret it,but the underlying reason is still debatable.We consider that the bond order loss and correlative bond hardening on the surface of roughened SiNWs will deeply influence the thermal transport because of their ultra-high surface-to-volume ratio.By combining this mechanism with the phonon Boltzmann transport equation,we explicate that the suppression of high-frequency phonons results in the obvious reduction of thermal conductivity of roughened SiNWs.Moreover,we verify that the roughness amplitude has more remarkable influence on thermal conductivity of SiNWs than the roughness correlation length,and the surface-to-volume ratio is a nearly universal gauge for thermal conductivity of roughened SiNWs.

Surface effects on the thermal conductivity of silicon nanowires

Thermal transport in silicon nanowires(SiNWs)has recently attracted considerable attention due to their potential applications in energy harvesting and generation and thermal management.The adjustment of the thermal conductivity of SiNWs through surface effects is a topic worthy of focus.In this paper,we briefly review the recent progress made in this field through theoretical calculations and experiments.We come to the conclusion that surface engineering methods are feasible and effective methods for adjusting nanoscale thermal transport and may foster further advancements in this field.

Stable Superwetting Surface Prepared with Tilted Silicon Nanowires

Large-scale uniform nanostructured surface with superwettability is crucial in both fundamental research and engineering applications.A facile and controllable approach was employed to fabricate a superwetting tilted silicon nanowires(TSNWs) surface through metal-assisted chemical etching and modification with low-surface-energy material.The contact angle(CA) measurements of the nanostructured surface show a large range from the superhydrophilicity(the CA approximate to 0°) to superhydrophobicity(the CA up to 160°).The surface becomes antiadhesion to water upon nanostructuring with a measured sliding angle(a) close to 0°.Moreover,the fluorinated TSNWs surface exhibits excellent stability and durability because strong chemical bonding has been formed on the surface.

Vacancy effect on the doping of silicon nanowires:A first-principles study

The influence of vacancy defect on the doping of silicon nanowires is systematically studied by the first-principles calculations. The atomic structures and electronic properties of vacancies and vacancy-boron （vacancy-phosphor） com- plexes in H-passivated silicon nanowire with a diameter of 2.3 nm are explored. The results of geometry optimization indicate that a central vacancy can exist stably, while the vacancy at the edge of the nanowire undergoes a local surface reconstruction, which results in the extradition of the vacancy out of the nanowire. Total-energy calculations indicate that the central vacancy tends to form a vacancy-dopant defect pair. Further analysis shows that n-type doping efficiency is strongly inhibited by the unintentional vacancy defect. In contrast, the vacancy defect has little effect on p-type doping. Our results suggest that the vacancy defect should be avoided during the growth and the fabrication of devices.

Simulation of Chirped Pulse Propagation in Silicon Nanowires: Shape and Spectrum Analysis

In this paper, we simulate the propagation of chirped pulses in silicon nanowires by solving the nonlinear Schrodinger equation (NLSE) using the split-step Fourier (SSF) method. The simulations are performed both for the pulse shape (time domain) and for the pulse spectrum (frequency domain), and various linear and nonlinear effects changing the shape and the spectrum of the pulse are analyzed. Owing to the high nonlinear coefficient and a very small effective-mode area, the required length for observing nonlinear effects in nanowires is much shorter than that of conventional optical fibers. The impacts of loss, nonlinear effects, second- and third-order dispersion coefficients and the chirp parameter on pulse propagation along the nanowire are investigated. The results show that the sign and the value of the chirp parameter have important role in pulse propagation so that in the anomalous dispersion regime, the compression occurs for the up- chirped pulses, whereas the broadening takes place for the down-chirped pulses. The opposite situation happens for up- and down-chirped pulses propagating in the normal dispersion regime.

Integration of silicon nanowires in solar cell structure for efficiencyenhancement: A review

Silicon nanowires (SiNWs) are a one-dimensional semiconductor, which shows promising applications indistinct areas such as photocatalysis, lithium-ion batteries, gas sensors, medical diagnostics, drug delivery,and solar cell. From an implementation point of view, SiNWs are fabricated using either a topdownor bottom-up approach, and SiNWs are both optically and electronically active. SiNWs enhancesthe efficiency of the solar cell due to better electronic, optical, and physical properties that can becontrolled by tuning the physical dimensions of SiNWs. The SiNWs shows an inherent capability to beutilized in radial or coaxial p-n junction solar cells, to stipulate orthogonal photon absorption, antireflection,and enhanced carrier collection. This paper reviews property-control of SiNWs, theirvarious types of incorporation in a solar cell, and the reasons behind enhanced efficiency.

Kinetically-Induced Hexagonality in Chemically Grown Silicon Nanowires

Various silicon crystal structures with different atomic arrangements from that of diamond have been observed in chemically synthesized nanowires.The structures are typified by mixed stacking mismatches of closely packed Si dimers.Instead of viewing them as defects,we define the concept of hexagonality and describe these structures as Si polymorphs.The small transverse dimensions of a nanowire make this approach meaningful.Unique among the polymorphs are cubic symmetry diamond and hexagonal symmetry wurtzite structures.Electron diffraction studies conducted with Au as an internal reference unambiguously confirm the existence of the hexagonal symmetry Si nanowires.Cohesive energy calculations suggest that the wurtzite polymorph is the least stable and the diamond polymorph is the most stable.Cohesive energies of intermediate polymorphs follow a linear trend with respect to their structural hexagonality.We identify the driving force in the polymorph formations as the growth kinetics.Fast longitudinal elongation during the growth freezes stacking mismatches and thus leads to a variety of Si polymorphs.The results are expected to shed new light on the importance of growth kinetics in nanomaterial syntheses and may open up ways to produce structures that are uncommon in bulk materials.

Ammonia sensing using arrays of silicon nanowires and graphene

Ammonia （NH3） is a toxic gas released in different industrial, agricultural and natural processes. It is also a biomarker for some diseases. These require NH3 sensors for health and safety reasons. To boost the sensitiv- ity of solid-state sensors, the effective sensing area should be increased. Two methods are explored and compared using an evaporating pool of 0.5 mL NH4OH （28% NH3）. In the first method an array of Si nanowires （Si NWA） is obtained via metal-assisted-electrochemical etching to increase the effective surface area. In the second method CVD graphene is suspended on top of the Si nanowires to act as a sensing layer. Both the effective surface area as well as the density of surface traps influences the amplitude of the response. The effective surface area of Si NWAs is 100 × larger than that of suspended graphene for the same top surface area, leading to a larger response in amp- litude by a factor of -7 notwithstanding a higher trap density in suspended graphene. The use of Si NWAs in- creases the response rate for both Si NWAs as well as the suspended graphene due to more effective NH3 diffu- sion processes.

Preparation and Characterization of Amorphous Silicon Oxide Nanowires

Large-scale amorphous silicon nanowires (SiNWs) with a diameter about 100 nm and a length of dozens of micrometers on silicon wafers were synthesized by thermal evaporation of silicon monoxide (SiO). Scanning electron microscope (SEM) and transmission electron microscope (TEM) observations show that the silicon nanowires are smooth. Selected area electron diffraction (SAED) shows that the silicon nanowires are amorphous and en-ergy-dispersive X-ray spectroscopy (EDS) indicates that the nanowires have the composition of Si and O elements in an atomic ratio of 1:2,their composition approximates that of SiO2. SiO is considered to be used as a Si sources to produce SiNWs. We conclude that the growth mechanism is closely related to the defect structure and silicon monoxide followed by growth through an oxide-assisted vapor-solid reaction.

Enhanced growth of crystalline-amorphous core-shell silicon nanowires by catalytic thermal CVD using in situ generated tin catalyst

In this work,we prepared silicon nanowires(Si NWs) on both fluorine-doped SnO 2(FTO) coated glass substrate and common glass substrate by catalytic thermal chemical vapor deposition(CVD) using indium film as the catalyst.It is confirmed that indium can catalyze the growth of Si NWs.More importantly,we found that tin generated in situ from the reduction of SnO 2 by indium can act as catalyst,which greatly enhances the growth of Si NWs on FTO substrate.The obtained Si NWs have a uniform crystalline-amorphous core-shell structure that is formed via vapor-liquid-solid and vapor-solid growth of silicon sequentially.This work provides a strategy to prepare Si NWs in high yield by catalytic thermal CVD using the low melting point metal catalysts.

Boosting electrocatalytic selectivity in carbon dioxide reduction:The fundamental role of dispersing gold nanoparticles on silicon nanowires

Carbon dioxide electrochemical reduction(CO_(2)RR)has been recognized as an efficient way to mitigate CO_(2)emissions and alleviate the pressure on global warming and associated environmental consequences.Gold(Au)is reported as stable and active electrocatalysts to convert CO_(2)to CO at low overpotential due to its moderate adsorption strength of^(*)COOH and^(*)CO.The request for improved catalytic performance,however,is motivated by current unsatisfied catalytic selectivity because of the side hydrogen evolution reaction.In this context,the design of Au based binary catalysts that can boost CO selectivity is of great interest.In the present work,we report that Au nanoparticles can be feasibly dispersed and anchored on silicon nanowires to form Au-Si binary nanomaterials.The Au-Si may stably drive CO_(2)RR with a CO Faraday efficiency of 95.6%at−0.6 V vs.RHE in 0.5 mol/L KHCO_(3)solution.Such selectivity outperforms Au particles by up to 61%.Controlled experiments illustrate that such catalytic enhancement can chiefly be ascribed to electronic effects of binary catalysts.Theoretical calculations reveal that spontaneously produced silicon oxide may not only inhibit hydrogen evolution reaction,but also stabilize the key intermediate^(*)COOH in CO formation.

Wafer-level site-controlled growth of silicon nanowires by Cu pattern dewetting

An approach for the wafer-level synthesis of size- and site-controlled amorphous silicon nanowires （α-SiNWs） is presented in this paper. Microscale Cu pattern arrays are precisely defined on SiO2 films with the help of photolithography and wet etching. Due to dewetting, Cu atoms shrink to the center of patterns during the annealing process, and react with the SiO2 film to open a diffusion channel for Si atoms to the substrate, α-SiNWs finally grow at the center of Cu patterns, and can be tuned by varying critical factors such as Cu pattern volume, SiO2 thickness, and annealing time. This offers a simple way to synthesize and accurately position a SiNW array on a large area.

A comparative electrochemical investigation of silicon nanowires formation via metal-catalyzed electroless etching

In this study, the electrochemical behavior of monocrystalline bare Si and Ag-coated Si in hydrofluoric acid （HF） solutions with and without hydrogen peroxide （H202） was systematically tested with an electrochemical technique. By analyzing the po- larization curves, the corrosion processes were quantified and the etchants which govern the formation of silicon nanowires （SiNWs） were determined. It was discovered that both H202 and Ag enhanced the reduction reactions, irrespective of the con- ductivity type and doping concentration of Si. It is believed that the formation of SiNWs via Metal-Catalyzed Electroless Etching is a process controlled by cathodic reduction reactions.

Growth of silicon nanowires in aqueous solution under atmospheric pressure

A new method for growing silicon nanowires is presented. They were grown in an aqueous solution at a temperature of 85℃ under atmospheric pressure by using sodium methylsiliconate as a water-soluble silicon precursor. The structure, morphology, and composition of the as-grown nanowires were characterized by scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectrometry. It was also confirmed by X-ray powder diffraction and Raman spectroscopy that the silicon nanowire has a hexagonal structure. It was possible to grow the crystalline silicon nanowires at low temperature under atmospheric pressure because potassium iodide, which was used as a gold etchant, sufficiently increased the surface energy and reactivity of gold as a metal catalyst for the reaction of the Si precursor even at low temperature.

Modulating the thermal conductivity of silicon nanowires via surface amorphization

We perform non-equilibrium molecular dynamics calculations to study the heat transport in crystalline-core amorphous-shell silicon nanowires(SiNWs).It is found that the thermal conductivity of the core-shell SiNWs is closely related to the cross-sectional area ratio of amorphous shell.Through shell amorphization,an 80%reduction in thermal conductivity compared to crystalline SiNWs with the same size can be achieved,due to the non-propagating heat diffusion in the amorphous region.In contrast to the strong temperature-dependent thermal conductivity of crystalline SiNWs,the core-shell SiNWs only show weak temperature dependence.In addition,an empirical relation is proposed to accurately predict the thermal conductivity of the core-shell SiNWs based on the rule of mixture.The present work demonstrates that SiNWs with an amorphized shell are promising candidates for thermoelectric applications.

Enhanced photocatalytic activities of silicon nanowires/graphene oxide nanocomposite:Effect of etching parameters

Homogeneous and vertically aligned silicon nanowires(SiNWs)were successfully fabricated using silver assisted chemical etching technique.The prepared samples were characterized using scanning electron microscopy,transmission electron microscopy and atomic force microscopy.Photocatalytic degradation properties of graphene oxide(GO)modified SiNWs have been investigated.We found that the SiNWs morphology depends on etching time and etchant composition.The SiNWs length could be tuned from 1 to 42μm,respectively when varying the etching time from 5 to 30 min.The etchant concentration was found to accelerate the etching process;doubling the concentrations increases the length of the SiNWs by a factor of two for fixed etching time.Changes in bundle morphology were also studied as function of etching parameters.The SiNWs diameter was found to be independent of etching time or etchant composition while the size of the SiNWs bundle increases with increasing etching time and etchant concentration.The addition of GO was found to improve significantly the photocatalytic activity of SiNWs.A strong correlation between etching parameters and photocatalysis efficiency has been observed,mainly for SiNWs prepared at optimum etching time and etchant concentrations of 10 min and 4:1:8.A degradation of92%was obtained which further improved to 96%by addition of hydrogen peroxide.Only degradation efficiency of 16%and 31%has been observed for bare Si and GO/bare Si samples respectively.The obtained results demonstrate that the developed SiNWs/GO composite exhibits excellent photocatalytic performance and could be used as potential platform for the degradation of organic pollutants.

Multi-time scale photoelectric behavior in facile fabricated transparent and flexible silicon nanowires aerogel membrane

In recent years,transparent and flexible materials have been widely pursued in electronics and optoelectronics fields for usage as planar electrodes,energy conversion components and sensing units.As the most widely applied semiconductor material,the related progress in silicon is of great significance although with large difficulty.Herein,we report a one-step method to achieve flexible and transparent silicon nanowires aerogel membrane.A competitive carrier kinetics involving interfacial trapped carriers and the valence electrons transition is demonstrated,according to the photoelectric performance of a sandwiched graphene/silicon nanowires membrane/AI device,i.e.,rapidly positive photoresponse dominated by laser excited^ee-carriers generation(〜500 ms)and subsequent slow negative photocurrent evolution due to laser heating involved multi-levels process(>10 s).These results contribute to fabrication of silicon nanowire self-assembly structures and also the exploration of their optoelectrical properties in flexible and transparent devices.