Growth of Semiconductor and Semiconducting Oxides Nanowires by Vacuum Evaporation Methods

Abstract

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.