Fabrication and characterization of single-crystal metal-assisted chemically etched rough Si nanowires for lithium-ion battery anodes

Silicon nanowires were fabricated by a metal assisted chemical (MAC) etching process and routes toward ohmic contacting of substrates for Li-ion battery anode application were developed. Si nanowire layers are comprised of wires that are single crystal with rough outer surfaces. The nanowires are epitaxial with the underlying Si(100) substrate, maintain equivalent doping density and crystal orientation, and are coated with a stoichiometric SiO2. Electrical backside contacting using an In-Ga eutectic allows low-resistance ohmic contacts to low-doped nanowire electrodes for electrochemical testing

Porous to non-porous transition in the morphology of metal assisted etched silicon nanowires

A single step metal assisted etching (MAE) process, utilizing metal ion-containing HF solutions in the absence of an external oxidant, has been developed to generate heterostructured Si nanowires with controllable porous (isotropically etched) and non-porous (anisotropically etched) segments. Detailed characterisation of both the porous and non-porous sections of the Si nanowires was provided by transmission electron microscopy studies, enabling the mechanism of nanowire roughening to be ascertained. The versatility of the MAE method for producing heterostructured Si nanowires with varied and controllable textures is discussed in detail

The influence of carrier density and doping type on lithium insertion and extraction processes at silicon surfaces

The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. A rate-dependent redox process influenced by the surface region electronic density, which influences the magnitude of cyclic voltammetry current is found at Si(100) surface regions during Li insertion and extraction. At p-type Si(100) surface regions, a thin, uniform film forms at lower currents, while also showing a consistently high (>70%) Coulombic efficiency for Li extraction. The p-type Si(100) surface region does not undergo crack formation after deintercalation and the amorphization was demonstrated using transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity

Detection of ultra-low protein concentrations with the simplest possible field effect transistor

Silicon nanowire (Si NW) sensors have attracted great attention due to their ability to provide fast, low-cost, label-free, real-time detection of chemical and biological species. Usually configured as field effect transistors (FETs), they have already demonstrated remarkable sensitivity with high selectivity (through appropriate functionalisation) towards a large number of analytes in both liquid and gas phases. Despite these excellent results, Si NW FET sensors have not yet been successfully employed to detect single molecules of either a chemical or biological target species. Here we show that sensors based on silicon junctionless nanowire transistors (JNTs), the simplest possible transistors, are capable of detecting the protein streptavidin at a concentration as low as 580 zM closely approaching the single molecule level. This ultrahigh detection sensitivity is due to the intrinsic advantages of junctionless devices over conventional FETs. Apart from their superior functionality, JNTs are much easier to fabricate by standard microelectronic processes than transistors containing p–n junctions. The ability of JNT sensors to detect ultra-low concentrations (in the zeptomolar range) of target species, and their potential for low-cost mass production, will permit their deployment in numerous environments, including life sciences, biotechnology, medicine, pharmacology, product safety, environmental monitoring and security

Electrical characterization of high performance, liquid gated vertically stacked SiNW-based 3D FET for biosensing applications

A 3D vertically stacked silicon nanowire (SiNW) field effect transistor featuring a high density array of fully depleted channels gated by a backgate and one or two symmetrical platinum side-gates through a liquid has been electrically characterized for their implementation into a robust biosensing system. The structures have also been characterized electrically under vacuum when completely surrounded by a thick oxide layer. When fully suspended, the SiNWs may be surrounded by a conformal high-κ gate dielectric (HfO2) or silicon dioxide. The high density array of nanowires (up to 7 or 8 × 20 SiNWs in the vertical and horizontal direction, respectively) provides for high drive currents (1.3 mA/μm, normalized to an average NW diameter of 30 nm at VSG = 3 V, and Vd = 50 mV, for a standard structure with 7 × 10 NWs stacked) and high chances of biomolecule interaction and detection. The use of silicon on insulator substrates with a low doped device layer significantly reduces leakage currents for excellent Ion/Ioff ratios >106 of particular importance for low power applications. When the nanowires are submerged in a liquid, they feature a gate all around architecture with improved electrostatics that provides steep subthreshold slopes (SS 10 μS) while allowing for the entire surface area of the nanowire to be available for biomolecule sensing. The fabricated devices have small SiNW diameters (down to dNW ∼ 15–30 nm) in order to be fully depleted and provide also high surface to volume ratios for high sensitivities

Self-seeded growth of germanium nanowires: coalescence and ostwald ripening

We report the controlled self-seeded growth of highly crystalline Ge nanowires, in the absence of conventional metal seed catalysts, using a variety of oligosilylgermane precursors and mixtures of germane and silane compounds (Ge:Si ratios between 1:4 and 1:1). The nanowires produced were encased in an amorphous shell of material derived from the precursors, which acted to isolate the Ge seed particles from which the nanowires were nucleated. The mode diameter and size distribution of the nanowires were found to increase as the growth temperature and Ge content in the precursors increased. Specifically, a model was developed to describe the main stages of self-seeded Ge nanowire growth (nucleation, coalescence, and Ostwald ripening) from the oligosilylgermane precursors and, in conjunction with TEM analysis, a mechanism of growth was proposed

Containing the catalysts: diameter controlled Ge nanowire growth

Sub-20 nm diameter Ge nanowires with narrow size distributions were grown from Ag nanoparticle seeds in a supercritical fluid (SCF) growth process. The mean Ge nanowire diameter and size distribution was shown to be dependent upon Ag nanoparticle coalescence, using both spin-coating and a block copolymer (BCP) templating method for particle deposition. The introduction of a metal assisted etching (MAE) processing step in order to "sink" the Ag seeds into the growth substrate, prior to nanowire growth, was shown to dramatically decrease the mean nanowire diameter from 27.7 to 14.4 nm and to narrow the diameter distributions from 22.2 to 6.8 nm. Hence, our BCP-MAE approach is a viable route for controlling the diameters of semiconductor nanowires whilst also ensuring a narrow size distribution. The MAE step in the process was found to have no detrimental effect on the length or crystalline quality of the Ge nanowires synthesised

Semiconductor nanostructures for antireflection coatings, transparent contacts, junctionless thermoelectrics and Li-ion batteries

Porous semiconductors structured top-down by electrochemical means, and from bottom-up growth of arrays and arrangements of nanoscale structures, are shown to be amenable to a range of useful thermal, optical, electrical and electrochemical properties. This paper summarises recent investigations of the electrochemical, electrical, optical, thermal and structural properties of porous semiconductors such as Si, In2O3, SnO2 and ITO, and dispersions, arrays and arrangements of nanoscale structures of each of these materials. We summarize the property-inspired application of such structurally engineered arrangements and morphologies of these materials for antireflection coatings, broadband absorbers, transparent contacts to LEDs that improve transmission, electrical contact and external quantum efficiency. Additionally the possibility of thermoelectric performance through structure-mediated variation in thermal resistance and phonon scattering without a p-n junction is shown through phonon engineering in roughened nanowires. Lastly, we show that bulk crystals and nanowires of p- and n-type doped Si are promising for use as anodes in Li-ion batteries

Synthesis & characterisation of group IV semiconducting nanowires

Semiconductor nanowires, particularly group 14 semiconductor nanowires, have been the subject of intensive research in the recent past. They have been demonstrated to provide an effective, versatile route towards the continued miniaturisation and improvement of microelectronics. This thesis aims to highlight some novel ways of fabricating and controlling various aspects of the growth of Si and Ge nanowires. Chapter 1 highlights the primary technique used for the growth of nanowires in this study, namely, supercritical fluid (SCF) growth reactions. The advantages (and disadvantages) of this technique for the growth of Si and Ge nanowires are highlighted, citing numerous examples from the past ten years. The many variables involved in this technique are discussed along with the resultant characteristics of nanowires produced (diameter, doping, orientation etc.). Chapter 2 outlines the experimental methodologies used in this thesis. The analytical techniques used for the structural characterisation of nanowires produced are also described as well as the techniques used for the chemical analysis of various surface terminations. Chapter 3 describes the controlled self-seeded growth of highly crystalline Ge nanowires, in the absence of conventional metal seed catalysts, using a variety of oligosilylgermane precursors and mixtures of germane and silane compounds. A model is presented which describes the main stages of self-seeded Ge nanowire growth (nucleation, coalescence and Ostwald ripening) from the oligosilylgermane precursors and in conjunction with TEM analysis, a mechanism of growth is proposed. Chapter 4 introduces the metal assisted etching (MAE) of Si substrates to produce Si nanowires. A single step metal-assisted etch (MAE) process, utilising metal ion-containing HF solutions in the absence of an external oxidant, was developed to generate heterostructured Si nanowires with controllable porous (isotropically etched) and non-porous (anisotropically etched) segments. In Chapter 5 the bottom-up growth of Ge nanowires, similar to that described in Chapter 3, and the top down etching of Si, described in Chapter 4, are combined. The introduction of a MAE processing step in order to “sink” the Ag seeds into the growth substrate, prior to nanowire growth, is shown to dramatically decrease the mean nanowire diameters and to narrow the diameter distributions. Finally, in Chapter 6, the biotin – streptavidin interaction was explored for the purposes of developing a novel Si junctionless nanowire transistor (JNT) sensor

Fabrication and characterization of single-crystal metal-assisted chemically etched rough Si nanowires for lithium-ion battery anodes

Silicon nanowires were fabricated by a metal assisted chemical (MAC) etching process and routes toward ohmic contacting of substrates for Li-ion battery anode application were developed. Si nanowire layers are comprised of wires that are single crystal with rough outer surfaces. The nanowires are epitaxial with the underlying Si(100) substrate, maintain equivalent doping density and crystal orientation, and are coated with a stoichiometric SiO2. Electrical backside contacting using an In-Ga eutectic allows low-resistance ohmic contacts to low-doped nanowire electrodes for electrochemical testing