Effect of electroless etching parameters on the growth and reflection properties of silicon nanowires

Vertically aligned silicon nanowire (Si NW) arrays have been fabricated over large areas using an electroless etching (EE) method, which involves etching of silicon wafers in a silver nitrate and hydrofluoric acid based solution. A detailed parametric study determining the relationship between nanowire morphology and time, temperature, solution concentration and starting wafer characteristics (doping type, resistivity, crystallographic orientation) is presented. The as-fabricated Si NW arrays were analyzed by field emission scanning electron microscope (FE-SEM) and a linear dependency of nanowire length to both temperature and time was obtained and the change in the growth rate of Si NWs at increased etching durations was shown. Furthermore, the effects of EE parameters on the optical reflectivity of the Si NWs were investigated in this study. Reflectivity measurements show that the 42.8% reflectivity of the starting silicon wafer drops to 1.3%, recorded for 10 μm long Si NW arrays. The remarkable decrease in optical reflectivity indicates that Si NWs have a great potential to be utilized in radial or coaxial p-n heterojunction solar cells that could provide orthogonal photon absorption and enhanced carrier collection.     

Photocurrent polarization anisotropy of randomly oriented nanowire networks

While the polarization sensitivity of single or aligned NW ensembles is well-known, this article reports on the existence of residual photocurrent polarization sensitivities in random NW networks. In these studies, CdSe and CdTe NWs were deposited onto glass substrates and contacted with Au electrodes separated by 30-110 microm gaps. SEM and AFM images of resulting devices show isotropically distributed NWs between the electrodes. Complementary high resolution TEM micrographs reveal component NWs to be highly crystalline with diameters between 10 and 20 nm and with lengths ranging from 1 to 10 microm. When illuminated with visible (linearly polarized) light, such random NW networks exhibit significant photocurrent anisotropies rho = 0.25 (sigma = 0.04) [rho = 0.22 (sigma = 0.04)] for CdSe (CdTe) NWs. Corresponding bandwidth measurements yield device polarization sensitivities up to 100 Hz. Additional studies have investigated the effects of varying the electrode potential, gap width, and spatial excitation profile. These experiments suggest electrode orientation as the determining factor behind the polarization sensitivity of NW devices. A simple geometric model has been developed to qualitatively explain the phenomenon. The main conclusion from these studies, however, is that polarization sensitive devices can be made from random NW networks without the need to align component wires.     

Layer-by-layer assembly of nanowires for three-dimensional, multifunctional electronics

We report a general approach for three-dimensional (3D) multifunctional electronics based on the layer-by-layer assembly of nanowire (NW) building blocks. Using germanium/silicon (Ge/Si) core/shell NWs as a representative example, ten vertically stacked layers of multi-NW field-effect transistors (FETs) were fabricated. Transport measurements demonstrate that the Ge/Si NW FETs have reproducible high-performance device characteristics within a given device layer, that the FET characteristics are not affected by sequential stacking, and importantly, that uniform performance is achieved in sequential layers 1 through 10 of the 3D structure. Five-layer single-NW FET structures were also prepared by printing Ge/Si NWs from lower density growth substrates, and transport measurements showed similar high-performance characteristics for the FETs in layers 1 and 5. In addition, 3D multifunctional circuitry was demonstrated on plastic substrates with sequential layers of inverter logical gates and floating gate memory elements. Notably, electrical characterization studies show stable writing and erasing of the NW floating gate memory elements and demonstrate signal inversion with larger than unity gain for frequencies up to at least 50 MHz. The ability to assemble reproducibly sequential layers of distinct types of NW-based devices coupled with the breadth of NW building blocks should enable the assembly of increasing complex multilayer and multifunctional 3D electronics in the future.     

p-Type ZnO nanowire arrays

Well-aligned ZnO nanowire (NW) arrays with durable and reproducible p-type conductivity were synthesized on alpha-sapphire substrates by using N2O as a dopant source via vapor-liquid-solid growth. The nitrogen-doped ZnO NWs are single-crystalline and grown predominantly along the [110] direction, in contrast to the [001] direction of undoped ZnO NWs. Electrical transport measurements reveal that the nondoped ZnO NWs exhibit n-type conductivity, whereas the nitrogen-doped ZnO NWs show compensated highly resistive n-type and finally p-type conductivity upon increasing N2O ratio in the reaction atmosphere. The electrical properties of p-type ZnO NWs are stable and reproducible with a hole concentration of (1-2) x 10(18) cm(-3) and a field-effect mobility of 10-17 cm2 V(-2) s(-1). Surface adsorptions have a significant effect on the transport properties of NWs. Temperature-dependent PL spectra of N-doped ZnO NWs show acceptor-bound-exciton emission, which corroborates the p-type conductivity. The realization of p-type ZnO NWs with durable and controlled transport properties is important for fabrication of nanoscale electronic and optoelectronic devices.     

An ordered Si nanowire with NiSi2 tip arrays as excellent field emitters

A method was developed to grow ordered silicon nanowire with NiSi(2) tip arrays by reacting nickel thin films on silica-coated ordered Si nanowire (NW) arrays. The coating of thin silica shell on Si NW arrays has the effect of limiting the diffusion of nickel during the silicidation process to achieve the single crystalline NiSi(2) NWs. In the meantime, it relieves the distortion of the NWs caused by the strain associated with formation of NiSi(2) to maintain the straightness of the nanowire and the ordering of the arrays. Other nickel silicide phases such as Ni(2)Si and NiSi were obtained if the silicidation processes were conducted on the ordered Si NWs without a thin silica shell. Excellent field emission properties were found for NiSi(2)/Si NW arrays with a turn on field of 0.82 V μm(-1) and a threshold field of 1.39 V μm(-1). The field enhancement factor was calculated to be about 2440. The stability test showed a fluctuation of about 7% with an applied field of 2.6 V μm(-1) for a period of 24 h. The excellent field emission characteristics are attributed to the well-aligned and highly ordered arrangement of the single crystalline NiSi(2)/Si heterostructure field emitters. In contrast to other growth methods, the present growth of ordered nickel silicide/Si NWs on silicon is compatible with silicon nanoelectronics device processes, and also provides a facile route to grow other well-aligned metal silicide NW arrays. The advantages will facilitate its applications as field emission devices.     

An advanced fabrication method of highly ordered ZnO nanowire arrays on silicon substrates by atomic layer deposition

In this work, the controlled fabrication of highly ordered ZnO nanowire (NW) arrays on silicon substrates is reported. Si NWs fabricated by a combination of phase shift lithography and etching are used as a template and are subsequently substituted by ZnO NWs with a dry-etching technique and atomic layer deposition. This fabrication technique allows the vertical ZnO NWs to be fabricated on 4 in Si wafers. Room temperature photoluminescence and micro-photoluminescence are used to observe the optical properties of the atomic layer deposition (ALD) based ZnO NWs. The sharp UV luminescence observed from the ALD ZnO NWs is unexpected for the polycrystalline nanostructure. Surprisingly, the defect related luminescence is much decreased compared to an ALD ZnO film deposited at the same time ona plane substrate. Electrical characterization was carried out by using nanomanipulators. With the p-type Si substrate and the n-type ZnO NWs the nanodevices represent p–n NW diodes.The nanowire diodes show a very high breakthrough potential which implies that the ALD ZnO NWs can be used for future electronic applications.     

Lateral self-aligned p-type In2O3 nanowire arrays epitaxially grown on Si substrates

Lateral orientated growth of In2O3 nanowire (NW) and nanorod (NR) arrays has been achieved by a vapor transport and condensation method on (001) and (111) surfaces of Si substrates. The single crystalline In2O3 NWs and NRs were grown along [211] in parallel to the Si +/-[110] and lying in the substrate plane. The electrical measurements show that the In2O3 NWs are p-type semiconductor. By N+ doping, the resistivity of the In2O3 NWs has been tuned. The lateral self-aligned In2O3 NW and NR arrays on Si can offer some unique advantages for fabricating parallel nanodevices that can be integrated directly with silicon technology.     

Wafer-scale assembly of highly ordered semiconductor nanowire arrays by contact printing

Controlled and uniform assembly of "bottom-up" nanowire (NW) materials with high scalability presents one of the significant bottleneck challenges facing the integration of nanowires for electronic applications. Here, we demonstrate wafer-scale assembly of highly ordered, dense, and regular arrays of NWs with high uniformity and reproducibility through a simple contact printing process. The assembled NW pitch is shown to be readily modulated through the surface chemical treatment of the receiver substrate, with the highest density approaching approximately 8 NW/mum, approximately 95% directional alignment, and wafer-scale uniformity. Such fine control in the assembly is attained by applying a lubricant during the contact printing process which significantly minimizes the NW-NW mechanical interactions, therefore enabling well-controlled transfer of nanowires through surface chemical binding interactions. Furthermore, we demonstrate that our printing approach enables large-scale integration of NW arrays for various device structures on both rigid silicon and flexible plastic substrates, with a controlled semiconductor channel width ranging from a single NW ( approximately 10 nm) up to approximately 250 microm, consisting of a parallel array of over 1250 NWs and delivering over 1 mA of ON current.     

Bent Polytypic ZnSe and CdSe Nanowires Probed by Photoluminescence

Nanowires (NWs) have witnessed tremendous development over the past two decades owing to their varying potential applications. Semiconductor NWs often contain stacking faults due to the presence of coexisting phases, which frequently hampers their use. Herein, it is investigated how stacking faults affect the optical properties of bent ZnSe and CdSe NWs, which are synthesized using the vapor transport method. Polytypic zinc blende–wurtzite structures are produced for both these NWs by altering the growth conditions. The NWs are bent by the mechanical buckling of poly(dimethylsilioxane), and micro‐photoluminescence (PL) spectra were then collected for individual NWs with various bending strains (0–2%). The PL measurements show peak broadening and red shifts of the near‐band‐edge emission as the bending strain increases, indicating that the bandgap decreases with increasing the bending strain. Remarkably, the bandgap decrease is more significant for the polytypic NWs than for the single phase NWs. This work provides insights into flexible electronic devices of 1D nanostructures by engineering the polytypic structures.     

ZnO nanowire/TiO2 nanoparticle photoanodes prepared by the ultrasonic irradiation assisted dip-coating method

Hybrid ZnO/TiO₂ photoanodes for dye-sensitized solar cells were prepared by combining ZnO nanowire (NW) arrays and TiO₂ nanoparticles (NPs) with the assistance of the ultrasonic irradiation assisted dip-coating method. Results show that the ultrasonic irradiation was an efficient way to promote the gap filling of TiO₂ NPs in the interstices of ZnO NWs. Hybrid ZnO NW/TiO₂ NP electrodes prepared with ultrasonic treatment exhibited better gap filling efficiency and higher visible absorptance. The overall conversion efficiency of the hybrid electrode was 0.79%, representing 35% improvement compared with that of the traditional one (0.58%). The enlarged surface area and improved attachments of TiO₂ NPs onto the walls of ZnO NWs induced by the application of ultrasonic irradiation may be the underlying reason. Electrochemical impedance spectroscopy measurements indicated that hybrid electrodes combined the advantages of improved electron transport along the ZnO NWs and increased surface area provided by infiltrated TiO₂ NPs, both of which are responsible for the improved cell efficiency.     

Partial conversion reaction of ZnO nanowires to ZnSe by a simple selenization method and their photocatalytic activities

A simple novel synthetic method for preparing ZnSe/ZnO heterostructured nanowire (NW) arrays via the selenization of ZnO NWs is reported. A hydrothermally grown ZnO NWs array on a glass substrate was reacted with selenium vapor to generate a 20–30 nm of zincblend ZnSe nanoparticles (NPs) on wurtzite ZnO NWs. A growth mechanism was proposed based on SEM, XRD, and TEM analysis to explain the partial chemical conversion of ZnO NW surfaces into ZnSe NPs. This mechanism is applicable to the synthesis of other chalcogenide compounds. The as-synthesized ZnSe/ZnO heterojunctions showed enhanced UV–visible light absorption properties. The materials exhibited excellent photocatalytic activity toward the decomposition of an organic dye compared to the bare ZnO due to enhanced light absorption and the type-II cascade band structure.     

Electrochemical properties of GaN nanowire electrodes--influence of doping and control by external bias

We report on the electrochemical characteristics of GaN nanowire (NW) ensembles grown by plasma-assisted molecular beam epitaxy on Si111 substrates and on the influence of Si and Mg doping. The NW electrochemical properties in terms of surface capacitance (C(S)), surface resistance (R(S)) are extracted from electrochemical impedance spectra. While Mg doping of GaN NWs does not cause a significant variation of these quantities, an increase of the Si concentration leads to an increase of C(S) and a simultaneous decrease of R(S), indicating the presence of charge carriers in the NWs. According to the extracted values for R(S) and C(S) the NWs are classified into resistive and conductive. For conductive NWs charge transfer to a ferricyanide redox couple in the electrolyte is demonstrated and the ensemble average of the flatband voltage was determined. Variation of the lateral surface potential due to application of an external bias via the electrolyte is demonstrated.     

Sulfur passivation and contact methods for GaAs nanowire solar cells

The effect of sulfur passivation on core-shell p-n junction GaAs nanowire (NW) solar cells has been investigated. Devices of two types were investigated, consisting of indium tin oxide contact dots or opaque Au finger electrodes. Lateral carrier transport from the NWs to the contact fingers was achieved via a p-doped GaAs surface conduction layer. NWs between the opaque contact fingers had sidewall surfaces exposed for passivation by sulfur. The relative cell efficiency increased by 19% upon passivation. The contribution of the thin film grown between the NWs to the total cell efficiency was estimated by removing the NWs using a sonication procedure. Mechanisms of carrier transport and photovoltaic effects are discussed on the basis of spatially resolved laser scanning measurements.     

Field effect transistor from individual trigonal Se nanowire

Trigonal Se nanowires (NWs) were fabricated through a high-yield chemical solution process. The morphology and structural characterization of the Se NWs were investigated using transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and x-ray diffraction (XRD). The results indicated that the Se NWs grow along the crystallographic c-axis, the direction of which is parallel to the helical chains of Se atoms. Single Se NW field effect transistor (FET) devices were prepared through photolithographic patterning. The device performance shows that the Se NWs are p-type semiconductors displaying mobility up to 30?cm(2)?V(-1)?s(-1). This finding on the Se NW FETs has broad implications and provides very useful fundamental information necessary for future applications in the fabrication of high-quality NW FETs and other electronic devices.     

Semi-transparent,flexible, and electrically conductive silicon mesh by capillarity-driven welding of vapor-liquid-solid-grown nanowires over large areas

Bottom-up synthesis of semiconductor nanowires (NWs) by the vapor-liquid-solid (VLS) mechanism has enabled diverse technological applications for these nanomaterials. Unlike metallic NWs, however, it has been challenging to form large-area interconnected NW networks. Here, we generate centimeter-scale meshes of mechanically and electrically interconnected Si NWs by sequentially growing, collapsing, and joining the NWs using a capillarity-driven welding mechanism. We fabricate meshes from VLS-grown NWs ranging in diameter from 20 to 100 nm and find that the meshes are three-dimensional with a thickness ranging from ~ 1 to ~ 10 microns depending on the NW diameter. Optical extinction measurements reveal that the networks are semi-transparent with a color that depends on the absorption and scattering characteristics of individual NWs. Moreover, active voltage contrast imaging of both centimeter- and micron-scale meshes reveals widespread electrical connectivity. Using a sacrificial layer, we demonstrate that the mesh can be liberated from the growth substrate, yielding a highly flexible and transparent film. Electrical transport measurements both on the growth substrate and on liberated, flexible films reveal electrical conduction across a centimeter scale with a sheet resistance of ~ 160–180 kΩ/square that does not change significantly upon bending. Given the ability to encode complex functionality in semiconductor NWs through the VLS process, we believe these meshes of networked NWs could find application as neuromorphic memory, electrode scaffolds, and bioelectronic interfaces.

     

Femtosecond laser irradiation induced heterojunctions between carbon nanofibers and silver nanowires for a flexible strain sensor

We report the direct joining of carbon nanofibers(CNFs)to silver nanowire(Ag NWs)by controlled irradiation with femtosecond(fs)laser pulses.Two separate types of nano-junction dependent on joint geometry,laser fluence and irradiation time are identified in irradiated mixtures.In one type of junction,the tip of an Ag NW is melted and flows to form a bond with an adjacent CNF.The second type of junction occurs without significant heating of the Ag NW and involves the softening and flow of carbon in the CNF in response to the transfer of plasmonic energy from the Ag NW into the CNF.Bonding in a T-type joint configuration can be of either kind depending on the relative orientation of the incident optical field and the long axis of the Ag NW.FDTD simulations were used to explore this effect for different joint geometries and laser polarization.The electrical properties of a heterojunction involving a single Ag NW-CNF structure have been measured,and it is found that the junction resistance can be reduced by six orders of magnitude after laser joining.Finally,we have investigated the properties of a strain sensor based on an Ag NW-CNF hybrid nanowire network and find that this device can exhibit high sensitivity.This sensitivity occurs as nano-junctions induced by fs laser irradiation greatly reduces the initial resistance.This laser-based technique for direct nanojoining of CNF and Ag NWs may enable the design of robust nanowire structures for application in a variety of new devices.     

Direct gravure printing of silicon nanowires using entropic attraction forces

The development of a method for large-scale printing of nanowire (NW) arrays onto a desired substrate is crucial for fabricating high-performance NW-based electronics. Here, the alignment of highly ordered and dense silicon (Si) NW arrays at anisotropically etched micro-engraved structures is demonstrated using a simple evaporation process. During evaporation, entropic attraction combined with the internal flow of the NW solution induced the alignment of NWs at the corners of pre-defined structures, and the assembly characteristics of the NWs were highly dependent on the polarity of the NW solutions. After complete evaporation, the aligned NW arrays are subsequently transferred onto a flexible substrate with 95% selectivity using a direct gravure printing technique. As a proof-of-concept, flexible back-gated NW field-effect transistors (FETs) are fabricated. The fabricated FETs have an effective hole mobility of 17.1 cm(2) ·V(-1) ·s(-1) and an on/off ratio of ~2.6 × 10(5) .     

Sub-100 nm Si nanowire and nano-sheet array formation by MacEtch using a non-lithographic InAs nanowire mask

We report a non-lithographical method for the fabrication of ultra-thin silicon (Si) nanowire (NW) and nano-sheet arrays through metal-assisted-chemical-etching (MacEtch) with gold (Au). The mask used for metal patterning is a vertical InAs NW array grown on a Si substrate via catalyst-free, strain-induced, one-dimensional heteroepitaxy. Depending on the Au evaporation angle, the shape and size of the InAs NWs are transferred to Si by Au-MacEtch as is (NWs) or in its projection (nano-sheets). The Si NWs formed have diameters in the range of ～25-95 nm, and aspect ratios as high as 250 in only 5 min etch time. The formation process is entirely free of organic chemicals, ensuring pristine Au-Si interfaces, which is one of the most critical requirements for high yield and reproducible MacEtch.     

Development of ultra-high density silicon nanowire arrays for electronics applications

This article reviews our recent progress on ultra-high density nanowires (NWs) array-based electronics. The superlattice nanowire pattern transfer (SNAP) method is utilized to produce aligned, ultra-high density Si NW arrays. We fi rst cover processing and materials issues related to achieving bulk-like conductivity characteristics from 10 20 nm wide Si NWs. We then discuss Si NW-based fi eld-effect transistors (FETs). These NWs & NW FETs provide terrifi c building blocks for various electronic circuits with applications to memory, energy conversion, fundamental physics, logic, and others. We focus our discussion on complementary symmetry NW logic circuitry, since that provides the most demanding metrics for guiding nanofabrication. Issues such as controlling the density and spatial distribution of both p-and n-type dopants within NW arrays are discussed, as are general methods for achieving Ohmic contacts to both p-and n-type NWs. These various materials and nanofabrication advances are brought together to demonstrate energy effi cient, complementary symmetry NW logic circuits.     

Highly efficient visible light photocatalysis of novel CuS/ZnO heterostructure nanowire arrays

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu(2)S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.