The effect of flux angle, substrate temperature and deposition rate on obliquely deposited germanium (Ge) films has been investigated. By carrying out deposition with the vapor flux inclined at 87° to the substrate normal at substrate temperatures of 250°C or 300°C, it may be possible to obtain isolated Ge nanowires. The Ge nanowires are crystalline as shown by Raman Spectroscopy. / Singapore-MIT Alliance (SMA)

No description available.

In order to completely assess the potential of semiconductor nanowires for multifunctional applications such as flexible electronics, nanoelectromechanical systems (NEMS), and composites, a full characterization of their properties must be obtained. While many of their physical properties have been well studied, explorations of mechanical, electromechanical, and optical properties of semiconductor nanowires remain relatively sparse in the literature. Two major hurdles to the elucidation of these properties are: (1) the development of experimental techniques which are capable of mechanical and electromechanical measurements coupled with detailed structural analysis, and (2) the synthesis of high quality nanowires with the high yields necessary to produce the quantities needed for composite fabrication. These issues are addressed in this dissertation by utilizing the supercritical fluid-liquid-solid (SFLS) synthesis method to produce germanium (Ge) nanowire specimens for mechanical and electromechanical measurements coupled with high-resolution transmission electron microscopy (HRTEM). In addition, excellent dispersibility and large quantities allow for optical measurements of dispersions and composites. Ge cantilever nanoelectromechanical resonators were fabricated and induced into resonance. From the frequency response, the Young's modulus of the nanowires was determined to be insensitive to diameter and on par with the literature values for bulk Ge. The mechanical quality factors of the resonators were found to decrease with decreasing diameter. The data indicate that energy dissipation from the oscillating cantilevers occurs predominantly via surface losses. The mechanical strengths of individual Ge nanowires were measured by in situ nanomanipulation in a scanning electron microscope (SEM). The nanowires were found to tolerate diameter-dependent flexural strains more than two orders of magnitude higher than bulk Ge. Corresponding bending strengths were in agreement with the ideal strength of a perfect Ge crystal, indicative of a reduced presence of extended defects. The nanowires also exhibited plastic deformation at room temperature, becoming amorphous at the point of maximum strain. The optical absorbance spectra of Ge nanowires were measured and found to exhibit spectra markedly different from bulk Ge. Simulations using a discrete dipole approximation (DDA) model suggest that the difference in light absorption results from light trapping within the nanowires. / text

Nanomaterials are widely investigated by researches and because of their unique properties they have been utilized in many different devices. Nanowires are one of these materials which show deviated mechanical, chemical, physical and optical, properties from their bulk counterparts. These deviations in properties of the nanowires are based on both their high surface to volume ratio and quantum confinement effect. Lately optical properties of nanowires have received great attention as they also exhibit good light sensitivity. Germanium is a semiconductor, which has been used widely as an active material in infrared light detectors. Due to excellent light detection of germanium its nanostructures have also been widely studied in optoelectronic devices. Germanium nanowires have been used in many devices such as field effect transistors, diodes, field emitters and photodetectors. Synthesis of high quality and high aspect ratio germanium nanowires could make important contributions to these devices. There are several synthesis methods for germanium nanowires. These are electrochemical etching, solvothermal, supercritical v fluidic, laser ablation, chemical vapor deposition and vapor transport methods. Among these methods, high quality, single crystalline, defect free germanium nanowires using accessible solid powder precursors could be synthesized with vapor transport method. In the first part of this thesis, germanium nanowire growth with vapor transport method is investigated. One of the most advantageous features of this method is using solid powder precursors instead of toxic gases. Until now, three different kinds of solid germanium precursors have been reported in vapor transport method, all of them are investigated and the resulting nanowires are compared in this thesis. Vapor transport method enables high control over the morphology of the nanowires. The most important parameters which affect the morphology of the nanowires are temperature, pressure and precursor type. Therefore, a detailed parametric study is provided based on these parameters and their effect on the final diameter of the nanowires is determined. The as &ndash / synthesized nanowires contain a very thick oxide layer on their surface. Therefore, oxide removal with acid etching is also investigated in this thesis. In the second part of this thesis, utilization of the germanium nanowire networks in fully transparent, flexible and network enhanced photodetectors is investigated. In order to obtain a germanium nanowire network, the as-synthesized nanowires are transferred from growth substrate to the device substrate by sonication and vacuum filtration. Silver nanowires and single walled carbon nanotubes are used as fully transparent electrodes. Both rigid and flexible photodetectors are fabricated and their current-voltage characteristics and photoresponse behaviors with different germanium nanowire densities are determined.

Ce mémoire présente une étude de la synthèse par la méthode Vapeur-Liquide-Solide (VLS) de nanofils de silicium et de germanium par Epitaxie par Jets Moléculaires ainsi que de l'effet de la présence de manganèse sur leur croissance. La croissance des nanofils est fortement modifiée par la présence de manganèse. Les nanofils de silicium élaborés sous un faible flux de manganèse présentent des propriétés morphologiques et structurales remarquables. La présence de manganèse modifie le diamètre d'équilibre des gouttes AuSi utilisées pour la croissance par voie VLS et permet l'élaboration de nanofils de silicium de longueurs élevées et de faibles diamètres. De plus, leur qualité cristalline est considérablement améliorée par rapport aux nanofils de silicium formés sans apport de manganèse. Dans ce mémoire nous proposons quelques explications à ce phénomène. Dans le cas des nanofils de germanium, l'incorporation de manganèse n'a pu être obtenue par codépôt. Aussi, (i) le dopage par implantation ionique de nanofils de germanium et (ii) la fonctionnalisation de nanofils de germanium par la formation d'hétérostructures type cœur/coquille Ge/GeMn ont été considérés : - les mesures d'aimantation effectuées sur des nanofils de germanium implantés au manganèse démontrent l'existence de propriétés ferromagnétiques avec des températures de Curie supérieures à 400K. Il s'agit d'un résultat très prometteur en vue d'applications utilisant des nanofils de germanium ferromagnétiques à température ambiante ; - pour accéder aux propriétés magnétiques des nanofils de germanium fonctionnalisés par dépôt de GeMn, nous avons mis au point une procédure de prises de contacts adaptée à la mesure de leurs propriétés de magnétotransport. Les caractéristiques électriques de ces dispositifs montrent que les propriétés de transport sont dominées par la présence de la couche coquille de GeMn, surtout à basse température. Des mesures de magnétotransport effectuées à 100K indiquent l'existence d'effets de magnétorésistance liés aux propriétés ferromagnétiques des nanofils de Ge ainsi fonctionnalisés. / This thesis presents a study of the Vapour-Liquid-Solid (VLS) synthesis of silicon and germanium nanowires by Molecular Beam Epitaxy and the effect of the presence of manganese on the growth properties. The presence of manganese strongly modifies the growth of nanowires and observed behaviours are very different for AuSi and AuGe systems. Silicon nanowires grown in the presence of manganese exhibit very interesting morphological and structural properties. The presence of manganese modifies AuSi droplets' diameter and allows manufacturing long nanowires with relatively small diameters. Moreover, the crystalline quality is dramatically improved as compared to that of silicon nanowires grown without manganese. In this manuscript we propose some explanation for the growth phenomena. In the case of germanium nanowires, manganese incorporation could not be obtained by concomitant deposition of germanium and manganese. Consequently, (i) the doping of germanium nanowires by ion implantation as well as (ii) germanium nanowires functionalization by core/shell Ge/GeMn heterostructures formation were considered: - magnetization measurements performed on implanted germanium nanowires demonstrate ferromagnetic properties with Curie temperatures above 400K. This result is very promising for the processing of devices using room-temperature ferromagnetic germanium nanowires ; - in order to access Ge/GeMn nanowires magnetic properties, we processed samples to probe nanowires magnetotransport properties. Electrical resistivities of devices show that transport properties are dominated by GeMn shell layer even more at low temperature. Magnetotransport measurements done at 100K indicate magnetoresistance effects linked with nanowires ferromagnetic properties.

Germanium (Ge) is the most compatible semiconductor material with silicon-based complementary metal-oxide semiconductor technology, which has higher electron and hole mobility than Si, leading to enhanced device performance. In addition, semiconductor nanowires (NWs) have attracted significant attention as promising candidates for next-generation nanoscale devices. Due to their unique geometry and physical properties, NWs show excellent optical and electrical properties such as quantum size effects, enhanced light absorption, and high biological and chemical sensitivity. Furthermore, high response to light irradiation is one of the most significant properties of semiconductor NWs, which makes them excellent candidates for photodetectors. Hence, Ge NWs are promising high-mobility nanostructures for optoelectronic devices. Despite constant improvement in the performance of single NW-based devices, determining their electrical properties remains challenging. Here, a symmetric six-contact Hall bar configuration is developed for top-down fabricated highly doped Ge NWs with different widths down to 30 nm, which simultaneously facilitates Hall effect and four-probe resistance measurements. Furthermore, accurate control of doping and fabrication of metal contacts on n-type doped Ge NWs with low resistance and linear characteristics remain significant challenges in Ge-based devices. Therefore, a combined approach is reported to fabricate Ohmic contacts on n-type doped Ge NWs using ion implantation and rear-side flash lamp annealing. This approach allows the fabrication of axial p–n junctions along the single NWs with different widths. The fabricated devices demonstrated rectifying characteristics in dark conditions. The photoresponse of the axial p–n junction photodetectors was investigated under three different illumination wavelengths of 637 nm, 785 nm, and 1550 nm. Moreover, the fabricated axial p–n junction photodetector demonstrated a high-frequency response up to 1 MHz at zero bias.

Recently, there has been a growing interest in semiconductor and semiconducting oxide nanowires for applications in electronics, energy conversion, energy storage and optoelectronic devices such as field effect transistors, solar cells, Li- ion batteries, gas sensors, light emitting diodes, field emission displays etc. Semiconductor and semiconducting oxide nanowires have been synthesized widely by different vapor transport methods. However, conditions like high growth temperature, low vacuum, carrier gases for the growth of nanowires, limit the applicability of the processes for the growth of nanowires on a large scale for different applications. In this thesis work, studies have been made on the growth of semiconductor and semiconducting oxide nanowires at a relatively lower substrate temperature (< 500 °C), in a high vacuum (1× 10-5 mbar), without employing any carrier gas, by electron beam and resistive thermal evaporation processes. The morphology, microstructure, and composition of the nanowires have been investigated using analytical techniques such as SEM, EDX, XRD, XPS, and TEM. The optical properties of the films such as reflectance, transmittance in the UV-visible and near IR region were studied using a spectrophotometer. Germanium nanowires were grown at a relatively lower substrate temperature of 380-450 °C on Si substrates by electron beam evaporation (EBE) process using a Au-assisted Vapor-Liquid-Solid mechanism. High purity Ge was evaporated in a high vacuum of 1× 10-5 mbar, and gold catalyst coated substrates maintained at a temperature of 380-450 °C resulted in the growth of germanium nanowires via Au-catalyzed VLS growth. The influence of deposition parameters such as the growth temperature, Ge evaporation rate, growth duration, and gold catalyst layer thickness has been investigated. The structural, morphological and compositional studies have shown that the grown nanowires were single-crystalline in nature and free from impurities. The growth mechanism of Germanium nanowires by EBE has been discussed. Studies were also made on Silicon nanowire growth with Indium and Bismuth as catalysts by electron beam evaporation. For the first time, silicon nanowires were grown with alternative catalysts by the e-beam evaporation method. The use of alternative catalysts such as Indium and Bismuth results in the decrease of nanowire growth temperature compared to Au catalyzed Si nanowire growth. The doping of the silicon nanowires is possible with an alternative catalyst. The second part of the thesis concerns the growth of oxide semiconductors such as SnO2, Sn doped Indium oxide (ITO) nanowires by the electron beam evaporation method. For the first time, SnO2 nanowires were grown with a Au-assisted VLS mechanism by the electron beam evaporation method at a low substrate temperature of 450 °C. SEM, XRD, XPS, TEM, EDS studies on the grown nanowires showed that they were single crystalline in nature and free of impurities. The influence of deposition parameters such as the growth temperature, oxygen partial pressure, evaporation rate of Sn, and the growth duration has been investigated. Studies were also done on the application of SnO2 nanowire films for UV light detection. ITO nanowires were grown via a self-catalytic VLS growth mechanism by electron beam evaporation without the use of any catalyst at a low substrate temperature of 250-400 °C. The influence of deposition parameters such as the growth temperature, oxygen partial pressure, evaporation rate of ITO, and growth duration has been investigated. Preliminary studies have been done on the application of ITO nanowire films for transparent conducting coatings as well as for antireflection coatings. The final part of the work is on the Au-assisted and self catalytic growth of SnO2 and In2O3 nanowires on Si substrates by resistive thermal evaporation. For the first time, SnO2 nanowires were grown with a Au-assisted VLS mechanism by the resistive thermal evaporation method at a low substrate temperature of 450 °C. SEM, XRD, XPS, TEM, and EDS studies on the grown nanowires showed that they were single crystalline in nature and free of impurities. Studies were also made on the application of SnO2 nanowire films for methanol sensing. The self-catalytic growth of SnO2 and In2O3 nanowires were deposited in high vacuum (5×10-5 mbar) by thermal evaporation using a modified evaporation source and a substrate arrangement. With this arrangement, branched SnO2 and In2O3 nanowires were grown on a Si substrate. The influence of deposition parameters such as the applied current to the evaporation boat, and oxygen partial pressure has been investigated. The growth mechanism behind the formation of the branched nanowires as well as nanowires has been explained on the basis of a self-catalytic vapor-liquid-solid growth mechanism. The highlight of this thesis work is employing e-beam evaporation and resistive thermal evaporation methods for nanowire growth at low substrate temperatures of ~ 300-500 °C. The grown nanowires were tested for applications such as gas sensing, transparent conducting coatings, UV light detection and antireflection coating etc. The thesis is divided into nine chapters and each of its content is briefly described below. Chapter 1 In this chapter, a brief introduction is given on nanomaterials and their applications. This chapter also gives an overview of the different techniques and different growth mechanisms used for nanowires growth. A brief overview of the applications of semiconductors and semiconductor oxide nanowires synthesized is also presented. Chapter 2 Different experimental techniques employed for the growth of Si, Ge, SnO2, In2O3, ITO nanowires have been described in detail in this chapter. Further, the details of the different techniques employed for the characterization of the grown nanowires were also presented. Chapter 3 In this chapter, studies on the growth of Germanium nanowires by electron beam evaporation (EBE) are given. The influence of deposition parameters such as growth temperature, evaporation rate of germanium, growth duration, and catalyst layer thickness was investigated. The morphology, structure, and composition of the nanowires were investigated by XRD, SEM, and TEM. The VLS growth mechanism has been discussed for the formation of the germanium nanowires by EBE using Au as a catalyst. Chapter 4 This chapter discusses the growth of Si nanowires with Indium and Bismuth as an alternate to Au-catalyst by electron beam evaporation. The influence of deposition parameters such as growth temperature, Si evaporation rate, growth duration, and catalyst layer thickness has been investigated. The grown nanowires were characterized using XRD, SEM, TEM and HRTEM. The Silicon nanowires growth mechanism has been discussed. Chapter 5 This chapter discusses the Au-catalyzed VLS growth of SnO2 nanowires by the electron beam evaporation method as well as Antimony doped SnO2 nanowires by co-evaporation method at a low substrate temperature of 450 °C. The grown nanowires were characterized using XRD, SEM, TEM, STEM, Elemental mapping, HRTEM, and XPS. The effect of deposition parameters such as oxygen partial pressure, growth temperature, catalyst layer thickness, evaporation rate of Sn, and the growth duration of nanowires were investigated. The SnO2 nanowires growth mechanism has been explained. Preliminary studies were made on the possible use of pure SnO2 and doped SnO2 nanowire films for UV light detection. SnO2 nanowire growth on different substrates such as stainless steel foil (SS), carbon nanosheets films, and graphene oxide films were studied. SnO2 nanowire growth on different substrates, especially SS foil will be useful for Li-ion battery applications. Chapter 6 This chapter discusses the self catalyzed VLS growth of Sn doped Indium oxide (ITO) nanowires by the electron beam evaporation method at a low temperature of 250-400 °C. The grown nanowires were characterized using XRD, SEM, TEM, STEM, HRTEM, and XPS. The effect of deposition parameters such as oxygen partial pressure, growth temperature, evaporation rate of ITO, and the growth duration of the nanowires were investigated. Preliminary studies were also made on the possible use of self-catalyzed ITO nanowire films for transparent conducting oxides and antireflection coatings. ITO nanowire growth on different and large area substrates such as stainless steel foil (SS), and Glass was done successfully. ITO nanowire growth on different substrates, especially large area glass substrates will be useful for optoelectronic devices. Chapter 7 In this chapter, studies on the growth of SnO2 nanowires by a cost-effective resistive thermal evaporation method at a relatively lower substrate temperature of 450 °C are presented. The grown nanowires were characterized using XRD, SEM, TEM, HRTEM, and XPS. Preliminary studies were done on the possible use of SnO2 nanowire films for methanol sensing. Chapter 8 This chapter discusses the self-catalytic growth of SnO2 and In2O3 nanowires by resistive thermal evaporation. The nanowires of SnO2 and In2O3 were grown at low temperatures by resistive thermal evaporation using a modified source and substrate arrangement. In this arrangement, branched SnO2 nanowires, and In2O3 nanowires growth was observed. The grown nanowires were characterized using XRD, SEM, TEM, HRTEM, and XPS. The possible growth mechanism for branched nanowires growth has been explained. Chapter 9 The significant results obtained in the present thesis work have been summarized in this chapter.