Site specific growth of metal catalyzed silica nanowires for biological and chemical sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050°C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1μg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

Molecular detection using metallic nanowires with quantized conductance

This thesis studies the adsorption of molecules with different binding strengths onto copper nanowires with prestabilized conductance values fabricated by an electrochemical method. Since the diameters of these wires are comparable to the wavelength of conduction electrons the conductance of the nanowires is quantized, and the adsorption of even a few molecules onto atomically thin wires changes the conductance from integer values to fractional ones. These changes are proportional to the binding strength of the adsorbed molecules. The decrease in conductance is hypothesized to be caused by the scattering of the conduction electrons by the adsorbed molecules. The sensitivity of molecular adsorption-induced conductance change can be used for the development of a chemical sensor. The stabilized copper nanowires obtained in this thesis may also be used for other purposes, such as interconnecting conductors between nanodevices and digital switches in functional nanoelectronic circuitry.

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Thin layers of indium tin oxide are widely used as transparent coatings and electrodes in solar energy cells, flat-panel displays, antireflection coatings, radiation protection and lithium-ion battery materials, because they have the characteristics of low resistivity, strong absorption at ultraviolet wavelengths, high transmission in the visible, high reflectivity in the far-infrared and strong attenuation in the microwave region. However, there is often a trade-off between electrical conductivity and transparency at visible wavelengths for indium tin oxide and other transparent conducting oxides. Here, we report the growth of layers of indium tin oxide nanowires that show optimum electronic and photonic properties and demonstrate their use as fully transparent top contacts in the visible to near-infrared region for light-emitting devices.

Resist-substrate interface tailoring for generating high density arrays of Ge and Bi2Se3 nanowires by electron beam lithography

The authors report a chemical process to remove the native oxide on Ge and Bi2Se3 crystals, thus facilitating high-resolution electron beam lithography (EBL) on their surfaces using a hydrogen silsesquioxane (HSQ) resist. HSQ offers the highest resolution of all the commercially available EBL resists. However, aqueous HSQ developers such as NaOH and tetramethylammonium hydroxide have thus far prevented the fabrication of high-resolution structures via the direct application of HSQ to Ge and Bi2Se3, due to the solubility of components of their respective native oxides in these strong aqueous bases. Here we provide a route to the generation of ordered, high-resolution, high-density Ge and Bi2Se3 nanostructures with potential applications in microelectronics, thermoelectric, and photonics devices.                         

AuxAg1-x alloy seeds: A way to control growth, morphology and defect formation in Ge nanowires

Germanium (Ge) nanowires are of current research interest for high speed nanoelectronic devices due to the lower band gap and high carrier mobility compatible with high K-dielectrics and larger excitonic Bohr radius ensuing a more pronounced quantum confinement effect [1-6]. A general way for the growth of Ge nanowires is to use liquid or a solid growth promoters in a bottom-up approach which allow control of the aspect ratio, diameter, and structure of 1D crystals via external parameters, such as precursor feedstock, temperature, operating pressure, precursor flow rate etc [3, 7-11]. The Solid-phase seeding is preferred for more control processing of the nanomaterials and potential suppression of the unintentional incorporation of high dopant concentrations in semiconductor nanowires and unrequired compositional tailing of the seed-nanowire interface [2, 5, 9, 12]. There are therefore distinct features of the solid phase seeding mechanism that potentially offer opportunities for the controlled processing of nanomaterials with new physical properties. A superior control over the growth kinetics of nanowires could be achieved by controlling the inherent growth constraints instead of external parameters which always account for instrumental inaccuracy. The high dopant concentrations in semiconductor nanowires can result from unintentional incorporation of atoms from the metal seed material, as described for the Al catalyzed VLS growth of Si nanowires [13] which can in turn be depressed by solid-phase seeding. In addition, the creation of very sharp interfaces between group IV semiconductor segments has been achieved by solid seeds [14], whereas the traditionally used liquid Au particles often leads to compositional tailing of the interface [15] . Korgel et al. also described the superior size retention of metal seeds in a SFSS nanowire growth process, when compared to a SFLS process using Au colloids [12]. Here in this work we have used silver and alloy seed particle with different compositions to manipulate the growth of nanowires in sub-eutectic regime. The solid seeding approach also gives an opportunity to influence the crystallinity of the nanowires independent of the substrate. Taking advantage of the readily formation of stacking faults in metal nanoparticles, lamellar twins in nanowires could be formed.

Characterization of resistivity of Sb2S3 semiconductor nanowires by conductive AFM and in-situ methods

Conductive AFM and in situ methods were used to determine contact resistance and resistivity of individual Sb2S3 nanowires. Nanowires were deposited on oxidized Si surface for in situ measurements and on Si surface with macroelectrodes for conductive AFM (C-AFM) measurements. Contact resistance was determined by measurement of I(V) characteristics at different distances from the nanowire contact with the macroelectrode and resistivity of nanowires was determined. Sb2S3 is a soft material with low adhesion force to the surface and therefore special precautions were taken during measurements.

Non-equilibrium induction of tin in germanium: towards direct bandgap Ge1-xSnx nanowires

The development of non-equilibrium group IV nanoscale alloys is critical to achieving new functionalities, such as the formation of a direct bandgap in a conventional indirect bandgap elemental semiconductor. Here, we describe the fabrication of uniform diameter, direct bandgap Ge1-xSnx alloy nanowires, with a Sn incorporation up to 9.2[thinsp]at.%, far in excess of the equilibrium solubility of Sn in bulk Ge, through a conventional catalytic bottom-up growth paradigm using noble metal and metal alloy catalysts. Metal alloy catalysts permitted a greater inclusion of Sn in Ge nanowires compared with conventional Au catalysts, when used during vapour-liquid-solid growth. The addition of an annealing step close to the Ge-Sn eutectic temperature (230[thinsp][deg]C) during cool-down, further facilitated the excessive dissolution of Sn in the nanowires. Sn was distributed throughout the Ge nanowire lattice with no metallic Sn segregation or precipitation at the surface or within the bulk of the nanowires. The non-equilibrium incorporation of Sn into the Ge nanowires can be understood in terms of a kinetic trapping model for impurity incorporation at the triple-phase boundary during growth.

Nanowires for 3d silicon interconnection – low temperature compliant nanowire-polymer film for z-axis interconnect

Semiconductor chip packaging has evolved from single chip packaging to 3D heterogeneous system integration using multichip stacking in a single module. One of the key challenges in 3D integration is the high density interconnects that need to be formed between the chips with through-silicon-vias (TSVs) and inter-chip interconnects. Anisotropic Conductive Film (ACF) technology is one of the low-temperature, fine-pitch interconnect method, which has been considered as a potential replacement for solder interconnects in line with continuous scaling of the interconnects in the IC industry. However, the conventional ACF materials are facing challenges to accommodate the reduced pad and pitch size due to the micro-size particles and the particle agglomeration issue. A new interconnect material - Nanowire Anisotropic Conductive Film (NW-ACF), composed of high density copper nanowires of ~ 200 nm diameter and 10-30 µm length that are vertically distributed in a polymeric template, is developed in this work to tackle the constrains of the conventional ACFs and serves as an inter-chip interconnect solution for potential three-dimensional (3D) applications.

Modifying germanium nanowires for future devices: an in situ TEM study

Germanium was of great interest in the 1950’s when it was used for the first transistor device. However, due to the water soluble and unstable oxide it was surpassed by silicon. Today, as device dimensions are shrinking the silicon oxide is no longer suitable due to gate leakage and other low-κ dielectrics such as Al2O3 and HfO2 are being used. Germanium (Ge) is a promising material to replace or integrate with silicon (Si) to continue the trend of Moore’s law. Germanium has better intrinsic mobilities than silicon and is also silicon fab compatible so it would be an ideal material choice to integrate into silicon-based technologies. The progression towards nanoelectronics requires a lot of in depth studies. Dynamic TEM studies allow observations of reactions to allow a better understanding of mechanisms and how an external stimulus may affect a material/structure. This thesis details in situ TEM experiments to investigate some essential processes for germanium nanowire (NW) integration into nanoelectronic devices; i.e. doping and Ohmic contact formation. Chapter 1 reviews recent advances in dynamic TEM studies on semiconductor (namely silicon and germanium) nanostructures. The areas included are nanowire/crystal growth, germanide/silicide formation, irradiation, electrical biasing, batteries and strain. Chapter 2 details the study of ion irradiation and the damage incurred in germanium nanowires. An experimental set-up is described to allow for concurrent observation in the TEM of a nanowire following sequential ion implantation steps. Grown nanowires were deposited on a FIB labelled SiN membrane grid which facilitated HRTEM imaging and facile navigation to a specific nanowire. Cross sections of irradiated nanowires were also performed to evaluate the damage across the nanowire diameter. Experiments were conducted at 30 kV and 5 kV ion energies to study the effect of beam energy on nanowires of varied diameters. The results on nanowires were also compared to the damage profile in bulk germanium with both 30 kV and 5 kV ion beam energies. Chapter 3 extends the work from chapter 2 whereby nanowires are annealed post ion irradiation. In situ thermal annealing experiments were conducted to observe the recrystallization of the nanowires. A method to promote solid phase epitaxial growth is investigated by irradiating only small areas of a nanowire to maintain a seed from which the epitaxial growth can initiate. It was also found that strain in the nanowire greatly effects defect formation and random nucleation and growth. To obtain full recovery of the crystal structure of a nanowire, a stable support which reduces strain in the nanowire is essential as well as containing a seed from which solid phase epitaxial growth can initiate. Chapter 4 details the study of nickel germanide formation in germanium nanostructures. Rows of EBL (electron beam lithography) defined Ni-capped germanium nanopillars were extracted in FIB cross sections and annealed in situ to observe the germanide formation. Chapter 5 summarizes the key conclusions of each chapter and discusses an outlook on the future of germanium nanowire studies to facilitate their future incorporation into nanodevices.

Diameter-driven crossover in resistive behaviour of heavily doped self-seeded germanium nanowires

The dependence of the resistivity with changing diameter of heavily-doped self-seeded germanium nanowires was studied for the diameter range 40 to 11 nm. The experimental data reveal an initial strong reduction of the resistivity with diameter decrease. At about 20 nm a region of slowly varying resistivity emerges with a peak feature around 14 nm. For diameters above 20 nm, nanowires were found to be describable by classical means. For smaller diameters a quantum-based approach was required where we employed the 1D Kubo–Greenwood framework and also revealed the dominant charge carriers to be heavy holes. For both regimes the theoretical results and experimental data agree qualitatively well assuming a spatial spreading of the free holes towards the nanowire centre upon diameter reduction.

The structural conversion from α-AgVO3 to β-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO3 nanowires (NWs) and their conversion to tunnel structured β-AgVO3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO3 to β-AgVO3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of β-AgVO3 NWs offers insight into the true β-AgVO3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the β-AgVO3 NWs have a core–shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO3 NWs core material. Electrochemical comparison of α-AgVO3 and β-AgVO3 NWs confirms that β-AgVO3 offers improved electrochemical performance. An ex situ structural characterization of β-AgVO3 NWs after the first galvanostatic discharge and charge offers new insight into the Li+ reaction mechanism for β-AgVO3. Ag+ between the van der Waals layers of the vanadium oxide is reduced during discharge and deposited as metallic Ag, the vacant sites are then occupied by Li+.

Piezo force microscopy and peakforce tuna measurements of III-V semiconductor nanowires

GaN, InP and GaAs nanowires were investigated for piezoelectric response. Nanowires and structures based on them can find wide applications in areas purposes such as nanogenarators, nanodrives, Solar cells and other perspective areas. Experemental measurements were carried out on AFM Bruker multimode 8 and data was handled with Nanoscope software. AFM techniques permitted not only to visualize the surface topography, but also to show distribution of piezoresponse and allowed to calculate its properties. The calculated values are in the same range as published by other authors.

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.

Site Specifc Growth of Metal Catalyzed Silica Nanowires for Biological and Chemical Sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050 ˚C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1µg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.