Дисертації з теми "INDIUM EVAPORATION"

Hybrid pixel detectors are widely used in many fields, including military, environment, industry and medical treatment. When integrating such a detector, a vertical connection technique called flip-chip bonding is almost the only way to realize the high-density interconnection between each pixel detector to the read-out chip. Such bonding can offer high-density I/O and a short interconnect distance, which can make the resulting device show excellent performance. Electro deposition is a promising approach to enable a low cost and high yield bump bonding process, compared with conventional sputtering or evaporation which is currently utilized for small-scale production. Due to that, Indium bumping process using electroplating is selected, as a result of which indium bump arrays with a pitch of 220 μm and a diameter of 30 μm have been fabricated using a standard silicon wafer processing. UBM (under bump metallization) for indium bumping was Ti/Ni (300 Å/ 2000 Å). It helps to increase adhesion between the wafer and the bumps and also serves as an excellent diffusion barrier both at room temperature and at 200°C. The indium is electroplated, using an indium sulfamate plating bath, and then formed into bumps through a reflow process. The reflow is made on a 200°C hot plate with a continuous flow of nitrogen over the wafer. During the reflow the indium is melted and forms into bumps due to surface tension. All the corresponding procedural processing steps and results are incorporated in this paper.

In2Se3 thin films with different thicknesses have been deposited by thermal evaporation method on glass substrate under vacuum pressure of 10-6 Torr. Structural Properties of these films were studied by different analytical techniques. X- ray diffraction revealed as deposited films have amorphous nature and annealing effect enhanced crystalline structure. Structural studies by XRD results showed the polycrystalline nature of the films. The Full Width at Half Maximum (FWHM) values were observed from the XRD pattern and used to evaluate the microstructural parameters like crystallite size, strain, dislocation density. The optical absorption spectra of In2Se3 films were studied in the wavelength region of 250–2500 nm. The optical properties show that the band gap (Eg) values vary from 2.5 to 3.34 eV as an-nealing temperature varies from 150 to 350C. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35133

Les détecteurs infrarouges InSb sont composés d'un circuit intégré Si et d'une matrice InSb qui sont connectés électriquement et mécaniquement par des billes de soudure en indium, préalablement déposées sur une métallisation. La jonction établie entre ces deux substrats est sollicitée thermomécaniquement à chaque utilisation à la température de l'azote liquide. Cette sollicitation thermomécanique est propice à la fatigue limitant la durée de vie du détecteur. Ce travail de thèse a pour objet l'amélioration des métallurgies de la métallisation et de la soudure au vu de la tenue en cyclage thermique de composants assemblés. L'effet des conditions de dépôt sur la microstructure, les propriétés électrique et de diffusion de la barrière de diffusion est évalué pour les métaux réfractaires suivants : alliage tungstène-titane (WTi) et tantale (Ta). L'élaboration par voie physique conduit à l'apparition inopinée d'une phase métastable néfaste, qui peut cependant être contrôlée par l'intermédiaire d'une sous couche. Un alliage indium-argent (eutectique) est déposé par évaporation qui permet de diminuer la température de fusion, et par conséquent les contraintes résiduelles du composant. L'effet de l'élément d'alliage Ag est évalué au vu de la résistance de contact et de la tenue mécanique de l'assemblage. Les résultats ont montré que la métallurgie est affectée par la méthode de fabrication, qui conditionne la tenue thermomécanique du composant optoélectronique
InSb based infra-red (IR) detectors are constituted by a Si integrated circuit and an InSb matrix which are electrically and mechanically connected thanks to solder balls in pure indium deposited on underbump metallic layers (UBM). IR detectors are cooled down to liquid nitrogen for each use. This thermomechanical solicitation affects the device reliability. The thesis purpose is to improve the UBM and solder metallurgies taking into account thermal cycling behavior of industrial components. The effect of deposition conditions on the diffusion barrier microstructure, electrical properties and diffusion efficiency is estimated for several refractory metals : tungsten-titanium alloy (WTi) and tantalum (Ta). The physical vapor deposition yield unexpected and harmful metastable phase formation, which can be controlled using a sub-layer. An indium-silver eutectic alloy is deposited by evaporation which allows to reduce the melting temperature and hence residual stresses within the component. The effect of Ag alloying is estimated by both the contact resistance and mechanical shear resistance. Results emphasize that the metallurgy is affected by the deposition technique, which impinges on IR detectors thermomechanical behavior

Thin film solar cells of Copper Indium Telluride and Cadmium Sulfide junctions were fabricated on plain ITO glass slides and also on those coated with intrinsic Tin Oxide. CdS was deposited through chemical bath deposition and CIT by electrodeposition. Both compounds were subjected to annealing at temperatures between 350°C and 500°C which produced more uniform film thicknesses and larger grain sizes. The CIT/ CdS junction was characterized after performing XRD and spectral absorption of individual compounds. Studies were also made on CdS / CdTe solar cells with respect to effect of annealing temperatures on open circuit voltages. NP acid etch, the most important process to make the surface of CdTe tellurium rich, was also studied in terms of open circuit voltages. Thermally evaporated CdS of four different thicknesses was deposited on Tin Oxide coated ITO and inferences were drawn as to what thickness of CdS yields better results.

Ce travail concerne l'étude d'un élément Hall de performances intéressantes, et réalisé en technologie couche mince. L'analyse bibliographique nous a conduit à privilégier l'antimoniure d'indium. L'ouvrage, après examen critique des techniques de fabrication de couches minces composées, présente la nouvelle méthode que nous avons développée ainsi que les procédés mis en oeuvre pour optimiser les caractéristiques structurelles des couches. Les résultats expérimentaux concernant l'analyse structurelle, les procédures de recuit et le comportement électrique en présence de champ magnétique des couches de InSb sont présentés. Les perspectives d'avenir sont évoquées en conclusion

Thesis (M.S. in Meteorology)--Naval Postgraduate School, September 2007.
Thesis Advisor(s): Murphree, James T. ; Frederickson, Paul A. "September 2007." Description based on title screen as viewed on October 25, 2007. Includes bibliographical references (p. 129-134). Also available in print.

Thesis (Ph.D.)--University of Delaware, 2007.
Principal faculty advisor: Babatunde Ogunnaike, Dept. of Chemical Engineering, and Robert W. Birkmire, Dept. of Materials Science & Engineering. Includes bibliographical references.

1-Microevaporation - Microfluidics is the branch of fluid mechanics dedicated to the study of flows in the channel withdimensions between 1 micron and 100 micron. The object of this chapter is to illustrate the basicprinciples and possible applications of microfluidic chip, called microevaporator. In the first part ofthe chapter, we present a detailed description of the physics of microevaporators using analyticalarguments, and describe some applications. In the second part of the chapter, we present theexperimental protocol of engineering of micro evaporator and different type of microfluidics device.2- On-chip microspectroscopy - The object of this chapter is to illustrate a method to measure absorption spectra during theprocess of growth of our materials in our microfluidic tools. The aim is to make an opticalcharacterization of our micro materials and to carry-out a spatio-temporal study of kineticproperties of our dispersion under study. This instrumental chapter presents the theoretical basis !of the method we used.3-Role of colloidal stability in the growth of micromaterials - We used combined microspectroscopy and videomicroscopy to follow the nucleation and growth ofmaterials made of core-shell Ag@SiO2 NPs in micro evaporators.!We evidence that the growth is actually not always possible, and instead precipitation may occurduring the concentration process. This event is governed by the concentration of dispersion in thereservoir and we assume that its origin come from ionic species that are concentrated all togetherwith the NPs and may alter the colloidal stability en route towards high concentration. 4-Microfluidic-induced growth and shape-up of three-dimensional extended arrays of denselypacked nano particles - In this chapter I present in details microfluidic evaporation experiments to engineer various denselypacked 3D arrays of NPs.5-Bulk metamaterials assembled by microfluidic evaporation - In this chapter I introduced the technique we used (microspot ellipsometry) in close collaborationswith V.Kravets and A.Grigorenko(University of Manchester) and with A.Aradian, P.Barois, A.Baron,K.Ehrhardt(CRPP, Pessac) to characterized the solids made of densely packed NPs. I describe theconstraints that emerge from the coupling between the small size of our materials and the opticalrequirements, the analysis and interpretation of the ellipsometry experiments show that for thematerial with high volume fraction of metal exists the strong electrical coupling between the NPsand the materials display an extremely high refraction index in the near infra-red regime.

Differentes methodes de calcul des proprietes optiques des couches minces optiques a profil d'indice continu sont presentees. Dans le cas des filtres rugates, l'utilisation de methodes analytiques a notamment permis un calcul des enveloppes des spectres ainsi que l'optimisation du profil d'indice. Un nouveau systeme de coevaporation sous vide a ete developpe pour realiser des filtres a profil d'indice continu. Des couches minces homogenes de zns, znse, mgf#2, ainsi que de zns-mgf#2 et de znfe-mgf#2 de differentes compositions ont ete realisees. Il apparait que le zns presente un probleme de condensation lorsqu'il est codepose avec du mgf#2, meme sur substrat froid. Le znse ne presente pas ce probleme lorsque celui-ci est majoritaire dans un melange realise a froid. Des filtres rugates a profil d'indice sinusoidal, comportant jusqu'a 20 periodes, ont ete realises en znse-mgf#2 depose sur substrat froid. Leurs spectres de reflexion et de transmission sont conformes aux simulations numeriques. Un atout important des filtres rugates par rapport aux multicouches a par ailleurs ete mis en evidence: les faibles contraintes dans les couches de melanges znse-mgf#2 et dans les filtres realises devraient autoriser la realisation de films epais, ce qui est une necessite pour la realisation de miroirs de faible largeur de bande

L'étude chimiqueet isotonique des éléments dissous des eaux ce pluie, de l'eau du sol et des eaux souterraines permet la mise en évidence des caractères principaux da cycle hvdrique .sur une île *volcanique tropicale à climat contrasté comme ta Réunion. Ia variation des teneurs chimiques dans les pluies montre une influence marquée de la présence marine qui evolue avec le relief, La repartition des teneurs isotopiques des précipitations montre une distribution similaire en situation normale et fortement perturbée lors de Ia forte dépression tropicale Clotilda où ses teneurs sont très appauvries. Cette variation naturelle des teneurs, dueaux pluies à forte ascendance, constitue un signl que l'on s'est efforcé de retrouver dans l'eau des profils de sol* et dans les points d'eau. L'examen des teneurs des eaux dans îes sols montre, qu'en bas de pente, dans le secteur aride de l'île, se produit une évaporation irréductible alimentée par les nappes libres. dans les haut, sur les versants, Il se produit une infiltration que l'on a pu également quantifier. Les analyses chimiques et isotopiques des eaux souterraines montrent une minéralisarion globale est bien représentée,loin de l'océan, par la minéralisabbn carbonatée essentiellement d'origine orogénique. La composîtion cationique, des eaux reflète-les compositions chimiques des roches qu'elles ont lessivées. D'autre part, les circulations souterraines ne suivent pas obligatoirement la pente générale du volcan. Les aqurifères côtiers montrent une bydrochimie où l'influence marinie prédomine mais où apparait un pôle de mélange avec des teneurs chloruréé et sulfaté. L'analyse-des isotopes du carbone et des sulfates a permis de mettre en évidence -.me influence non négligeable de la culture de la canne à sucre avec des temps de transit des aquifêres probablement inférieurs à 35 ans. Les aquifères de ia côte ouest sont peu protégés de la pollution de bas de versant et toute mise en valeur de cette côte devra tenir compte de la sensibilité des aquitères aux sources de pollution.

碩士
長庚大學
光電工程研究所
102
In the thesis we investigate the characteristics of Chalcopyrite CuInSe2 (CIS) absorber layers by using evaporated selenization method. This method is a two step process: (i) deposition of stacked metallic bilayers of indium and copper by evaporation, (ii) selenization of the precursor layers in a closed quartz box by the furnace. Chalcopyrite is well known to form a stable phase at significant deviations from stoichiometry ranging from copper poor ([Cu]/[In]<1) to copper rich ([Cu]/[In]>1). In today’s best CIS solar cells, the composition is in the range of [Cu]/[In]≒0.9. In copper excess usually have CuxSe it suggested that CuxSe formation at the surface may be a limiting step for the CuInSe2 formation. The study is observed that the copper over indium([Cu][In]) ratio from 0.88~1.79 with CIS thin film. The XRD spectra indicate that the peak position of (112) direction in the CIS absorber layer will shift to higher angle when the copper rich. In order to understand the influence of various process parameters the depth-resolved XPS of the absorber layer is required. Binding energy of Cu 2p3/2 are increase with CuxSe. And having secondary phase the element of Se are existence in Se 3d5/2. By Chemical bath deposition (CBD), cadmium sulfide (CdS) is also studied in this thesis. IV measurement of [Cu]/[In]≒0.9 cell has a small leakage current. The efficiency of Al/ ZnO:Al /i-ZnO/ CdS/ CuInSe2/ Mo/ SLG solar cell is 4.62%, Voc=0.34 V, Jsc=29.1 (mA/cm2), FF=0.49.

The surface temperature is required to specifying the temperature of the evaporating Gold, Tin and Indium source using constant elements for turn off the refinement in the post-processing settings. The present work represents the modeling of nanoscale Gold, Tin & Indium films by computing the film thickness, mass deposited on the substrate and mass transfer rate on silicon substrates with time dependent model using BDF solver. Gold is deposited by thermal evaporation process 34-38 nm by evaporating at temperature of 2000 °K in the vacuum of 50 Pa. Mass of gold deposited for 60 sec is 5.8 x 10-6 kg with mass transfer rate of 9.9 x 10-8 kg/sec. The SEM micrographs shows the smooth and uniformly distributed nanoscale gold film on silicon and the average grain size of gold is 12-30 nm. The XRD analysis shows the polycrystalline face centered cubic (fcc) structure in preferential (111) plane. Tin and Indium is evaporated from a resistively heated evaporator source at a temperature of 1855 °K and 1485 °K respectively in a pressure (vacuum) of 100 Pa onto silicon surface held on a fixed surface. The film thickness varies between 144 nm to 165 nm for Tin and 160 nm to 183 nm for Indium across the sample after 60 sec of deposition, with radial symmetry about the midpoint of the source. The film thickness as well as mass deposited at a point increases linearly with time. Like gold mass deposited & mass transfer rate for tin and indium also computed from the flux arriving on the substrate. Since the angular distribution is of particular interest in this model, by increasing the integration resolution to a maximum value for ensuring the most accurate angular resolution when computing the flux. The SEM micrographs of Tin and Indium at different magnifications shows the 100nm to 1microns grain size along the grain boundaries. Similarly, XRD analysis with Kα (wavelength 1.541874) shows the peaks of intensity at different 2θ angles for different orientations of planes with polycrystalline structure. The XRD of tin shows tetragonal polycrystalline structure in preferential (101) plane while XRD for indium shows tetragonal bcc structure in preferential (103) plane for tin & indium thickness of 164 nm, 183 nm respectively. Deposited gold, tin & indium film thickness measured from Dektek surface profiler at different points on the substrate surface.

博士
國立交通大學
光電工程學系
100
Indium-tin-oxide (ITO) has been a useful material as transparent conductive electrodes for the last two decades. Both solar cells and light-emitting-diodes benefit from the property of ITO to improve the conversion efficiency or light extraction, respectively. In this work, we developed a growth method to deposit ITO nanostructures, including the nano-columns, nanowhiskers, and nanorods. These nanostructures were applied for the GaAs-based, Si-based, and polymer-based solar cells, to reduce the surface reflectance or increase carrier collection. We further investigated the growth mechanism of ITO nanostructures which was dominated by the tin-induced self-catalytic vapor-liquid-solid (VLS) and the vapor-solid (VS) growth mechanism. The growth process could be divided into three steps: (1) nucleation, (2) column growth, and (3) side branch growth. We show evidence of the initial droplets formation to confirm the existence of the liquid phase. The core-shell structure had been observed in the TEM image of ITO nanorods, and hence the EDX analysis demonstrated higher concentration of tin in the shell than that in the core. The shell layer could absorb ITO vapor during the growth of ITO nanowhiskers. After investigation of the growth mechanism of ITO nanostructures, the applications had been discussed. First, we deposited the oriented ITO nano-columns on GaAs-based solar cell to provide broadband antireflection. Therefore, the conversion efficiency of the ITO nano-columns GaAs-based solar cell increased by 28% compared to a cell without any AR treatment. Next, we deposited the ITO nanowhiskers on the micro groove textured Si-based solar cell to combine the nano-and micro-textured antireflective coating. The compound antireflective structures increased light harvesting in the near-infrared. The conversion efficiency of the combined antireflective coated Si-based solar cell achieved 17.2%, compared to 16.1% of the conventional Si based solar. Finally, the ITO nanorods were prepared on ITO glass which functioned as three-dimensional (3D) nanoelectrode. The nano-electrode increased the hole collection efficiency for the organic solar cell. Compared to the organic solar cell with a flat electrode, the conversion efficiency and lifetime of the ITO nano-electrode organic solar cell increased by 10%, and 100%, respectively. We then conclude the growth and photovoltaic applications of the ITO nanostructures and provide future outlooks.

碩士
國立虎尾科技大學
光電與材料科技研究所
95
Abstract ITO is the most popular material for transparent electrical conduction film of commercial applications. There are several applications based on its excellent properties such as good conductivity, high transmittance rate for visible light, high absorbability for ultraviolet region and good chemical stability. This thesis studies the e-beam vaporized ITO thin film on glass substrate. The optical and electrical properties were studies with several process parameters such as the flow rate of oxygen, growth temperature, e-beam accelerated voltage. Systematic studies for the ITO related process parameters in the e-beam technology were well done in this thesis. With well controlled ITO film with process parameters optimized in the thesis, sheet resistance as low as 9.8(Ω/□) and high transparency as 95% with wavelength 470nm can both be achieved.

碩士
明新科技大學
化學工程與材料科技系碩士班
101
Transparent conductive electrodes with high transmittance and low resistance to optoelectronic device have gradually been widely used，such as touch panel、solar call、liquid crystal displays、with the rapid expansion of these product markets、the growth transparent conductive electrode rapidly increase in demand.Wherein the Indium tin oxide (Indium Tin Oxide; ITO) plays the important role of the conductive electrodes in a plane display. ITO film having a low resistance, and have a high transmittance in the visible range, the method of the preparation of indium tin oxide, mainly by sputtering method and electron beam deposition method, wherein the electron beam deposition method does not cause the surface of the elementinjury, and therefore subject to widespread attention. In this study, using an electron beam deposition method a growing Indium tin oxide thin film on the sodaline glass. Study their structural, electrical and optical properties of the thin film micro different deposition thickness, substrate temperature, spot oxygen flow and subsequent heat process.Using X-ray diffraction analyzer crystalline; Scanning electron microscope to observe the surface morphology of the sample; UV / VIS / NIR spectrometer transmittance ; sheet resistance of the four-point probe studies; Hall effectThe measurement to obtain the carrier concentration and the mobility of the thin film. The interpretation of the results, indium tin oxide film at a substrate temperature of 200 oC growth ITO film 100 nm thin film growth leads to 8 sccm O2 annealing at 300 ℃ in the 550nm transmittance of 98%, you can get a better quality factor of 0.055Ω-1, the experimental results using an electron beam vapor deposition by appropriate annealing the transparent conductive film of low resistance and high transmittance can be obtained.

碩士
國防大學理工學院
電子工程碩士班
100
In this thesis, the copper indium selenide (CuInSe2) absorber layer was prepared by two step methods. In the first step, the metal precursor of copper and indium stacked layers was deposited by evaporator sequentially. In the second step, the precursor was selenized by heating the selenium powder in a closed quartz box to form a chalcopyrite structure of CuInSe2 thin films. Three types of metal precursors, copper-rich, stoichiometric and copper-poor, were deposited by changing the deposited thickness of copper and indium. To examine the metal alloy property, the stable phase of Cu11In9 is formed when the annealing temperature is higher than 175°C. After selenization, the CuInSe2 thin films with copper-poor exhibit small particle size, low carrier concentration and large resistance in comparison with that of stoichiometric and copper-rich. The optical bandgaps of CuInSe2 thin film with copper-rich, stoichiometric and copper-poor, which is characterized by light transmission and reflection, are 0.99, 0.97 and 1.18eV, respectively. The solar efficiency of CuInSe2 absorber layer with copper-rich, stoichiometric and copper-poor is 0.16%, 2.09% and 0.04%, respectively. It is noted that large leakage current resulted in very low efficiency in copper-rich and copper-poor films due to high conductivity and large roughness, respectively. In addition, cadmium sulfide (CdS) is also studied in this thesis. Chemical bath deposition (CBD) was used to deposit CdS thin films. The deposited CdS films exhibit a cubic structure, the sulfur-to-cadmium ratio of 0.64 and a resistance of 108Ω. The deposited rates of CdS films are different in glass substrate and Mo-coated on glass substrate. The CdS films have a significant influence on the solar efficiency depending on whether the CdS films completely cover the CuInSe2 surface or not.

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.

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.

碩士
長庚大學
化工與材料工程學系
99
In this study, the Cu-In-Ga-Se (CIGS) semiconductor thin films were deposited on glass substrates and indium-tin-oxide (ITO) coated glass substrates using selenization of co-evaporated Cu-In-Ga metal alloys . The effect of the Cu/(In+Ga) and Ga /(In+Ga) molar ratio in Cu-In-Ga metal alloys on the structural, optical and electrical properties of CIGS thin film were investigated. X-ray diffraction pattern of samples ( XRD ) revealed that samples in this study were chalcopyrite CIGS phase. Energy dispersive analysis of X-ray ( EDAX ) showed that compositions of CuIn 1-x Ga x Se 2 thin film were the function of the Cu-In-Ga molar ratio in metal alloys. The thickness of samples were in the range of 1.8 ~ 4 µm. The direct energy band gap of samples varied from 1.28~ 1.50 eV, depending on Cu/(In+Ga) and Ga/(In+Ga) molar ratios in samples. Maximum photocurrent density of samples reached to 0.24 mA/cm 2 in the solution containing S 2- and SO 3 2- ions. The carrier concentration of samples varied from 2.86 × 10 18 ~ 3.82 × 10 12 cm -3 using Hall measurement. The resistivity of samples decreased with an increase in Cu/(In+Ga) molar ratio in samples. The conduction type of CuIn 1-x Ga x Se 2 thin films are all p-type. Glass/Mo/CIGS/CdS/IZO/AZO/Ag solar cell gaved V OC of 0.238 V, J SC of 0.134 mA/cm 2 , FF of 0.220, and conversion efficiency of 0.01 %.

Droplet evaporation is ubiquitous to multitude of applications such as microfluidics, surface patterning and ink-jet printing. In many of the process like food processing tiny concentrations of suspended particles may alter the behavior of an evaporating droplet remarkably, leading to partially viscous and partially elastic dynamical characteristics. This, in turn, may lead to some striking mechanical instabilities, such as buckling and rupture. In this thesis, we provide a comprehensive physical description of the vaporization, self-assembly, agglomeration and buckling kinetics of sessile nanofluid droplet pinned on a hydrophobic substrate in various configurations. We have deciphered five distinct regimes of droplet lifecycle. Regime I-III consists of evaporation induced preferential agglomeration that leads to the formation of unique dome shaped inhomogeneous shell with stratified varying density liquid core. Regime IV involves capillary pressure initiated shell buckling and stress induced shell rupture. Regime V marks rupture induced cavity inception and growth. We provide a regime map explaining the droplet morphology and buckling characteristics for droplets evaporating on various substrates. Specifically, we find that final droplet volume and radius of curvature at buckling onset are universal functions of particle concentration. Furthermore, flow characteristics inside the heated and unheated droplets are investigated and found to be driven by the buoyancy effects. Velocity magnitudes are observed to increase by an order at higher temperatures with self-similar flow profiles. With an increase in the surface temperature, droplets exhibit buckling from multiple sites over a larger sector in the top half of the droplet. In addition, irrespective of the initial nanoparticle concentration and substrate temperature, hydrophobicity and roughness, growth of daughter cavity (subsequent to buckling) inside the droplet is found to be controlled by the solvent evaporation rate from the droplet periphery. The results are of great significance to a plethora of applications like DNA deposition and nanofabrication. In the next part of the thesis, we deploy the droplet in a rectangular channel. The rich physics governing the universality in the underlying dynamics remains grossly elusive. Here, we bring out hitherto unexplored universal features of the evaporation dynamics of a sessile droplet entrapped in a 3D confined fluidic environment. Increment in channel length delays the completion of the evaporation process and leads to unique spatio-temporal evaporation flux and internal flow. We show, through extensive set of experiments and theoretical formulations, that the evaporationtimescale for such a droplet can be represented by a unique function of the initial conditions. Moreover, using same theoretical considerations, we are able to trace and universally merge the volume evolution history of the droplets along with evaporation lifetimes, irrespective of the extent of confinement. These results are explained in the light of increase in vapor concentration inside the channel due to greater accumulation of water vapor on account of increased channel length. We have formulated a theoretical framework which introduces two key parameters namely an enhanced concentration of the vapor field in the vicinity of the confined droplet and a corresponding accumulation lengthscale over which the accumulated vapor relaxes to the ambient concentration. Lastly, we report the effect of confinement on particle agglomeration and buckling dynamics. Compared to unconfined scenario, we report non-intuitive suppression of rupturing beyond a critical confinement. We attribute this to confinement-induced dramatic alteration in the evaporating flux, leading to distinctive spatio-temporal characteristics of the internal flow leading to preferential particle transport and subsequent morphological transitions. We present a regime map quantifying buckling & non-buckling pathways. These results may turn out to be of profound importance towards achieving desired morphological features of a colloidal droplet, by aptly tuning the confinement space, initial particle concentration, as well as the initial droplet volume. These findings may have implications in designing functionalized droplet evaporation devices for emerging engineering and biomedical applications.

Droplet evaporation is ubiquitous to multitude of applications such as microfluidics, surface patterning and ink-jet printing. In many of the process like food processing tiny concentrations of suspended particles may alter the behavior of an evaporating droplet remarkably, leading to partially viscous and partially elastic dynamical characteristics. This, in turn, may lead to some striking mechanical instabilities, such as buckling and rupture. In this thesis, we provide a comprehensive physical description of the vaporization, self-assembly, agglomeration and buckling kinetics of sessile nanofluid droplet pinned on a hydrophobic substrate in various configurations. We have deciphered five distinct regimes of droplet lifecycle. Regime I-III consists of evaporation induced preferential agglomeration that leads to the formation of unique dome shaped inhomogeneous shell with stratified varying density liquid core. Regime IV involves capillary pressure initiated shell buckling and stress induced shell rupture. Regime V marks rupture induced cavity inception and growth. We provide a regime map explaining the droplet morphology and buckling characteristics for droplets evaporating on various substrates. Specifically, we find that final droplet volume and radius of curvature at buckling onset are universal functions of particle concentration. Furthermore, flow characteristics inside the heated and unheated droplets are investigated and found to be driven by the buoyancy effects. Velocity magnitudes are observed to increase by an order at higher temperatures with self-similar flow profiles. With an increase in the surface temperature, droplets exhibit buckling from multiple sites over a larger sector in the top half of the droplet. In addition, irrespective of the initial nanoparticle concentration and substrate temperature, hydrophobicity and roughness, growth of daughter cavity (subsequent to buckling) inside the droplet is found to be controlled by the solvent evaporation rate from the droplet periphery. The results are of great significance to a plethora of applications like DNA deposition and nanofabrication. In the next part of the thesis, we deploy the droplet in a rectangular channel. The rich physics governing the universality in the underlying dynamics remains grossly elusive. Here, we bring out hitherto unexplored universal features of the evaporation dynamics of a sessile droplet entrapped in a 3D confined fluidic environment. Increment in channel length delays the completion of the evaporation process and leads to unique spatio-temporal evaporation flux and internal flow. We show, through extensive set of experiments and theoretical formulations, that the evaporationtimescale for such a droplet can be represented by a unique function of the initial conditions. Moreover, using same theoretical considerations, we are able to trace and universally merge the volume evolution history of the droplets along with evaporation lifetimes, irrespective of the extent of confinement. These results are explained in the light of increase in vapor concentration inside the channel due to greater accumulation of water vapor on account of increased channel length. We have formulated a theoretical framework which introduces two key parameters namely an enhanced concentration of the vapor field in the vicinity of the confined droplet and a corresponding accumulation lengthscale over which the accumulated vapor relaxes to the ambient concentration. Lastly, we report the effect of confinement on particle agglomeration and buckling dynamics. Compared to unconfined scenario, we report non-intuitive suppression of rupturing beyond a critical confinement. We attribute this to confinement-induced dramatic alteration in the evaporating flux, leading to distinctive spatio-temporal characteristics of the internal flow leading to preferential particle transport and subsequent morphological transitions. We present a regime map quantifying buckling & non-buckling pathways. These results may turn out to be of profound importance towards achieving desired morphological features of a colloidal droplet, by aptly tuning the confinement space, initial particle concentration, as well as the initial droplet volume. These findings may have implications in designing functionalized droplet evaporation devices for emerging engineering and biomedical applications.

The exploitation of the soft x-ray/extreme ultra-violet (EUV) region of the electromagnetic spectrum is possible mainly due to the development of multilayer (ML) mirrors. This region of the electromagnetic spectrum offers great opportunities in both science and technology. The shorter wavelength allows one to see smaller features in microscopy and write finer features in lithography. High reflectivity with moderate spectral bandwidth at normal/near-normal incidence can be achieved in soft x-ray/ EUV spectral range using these ML mirrors, where natural crystals with the required large periodicity are not available. These MLs are generally artificial Bragg’s reflectors, which consist of alternative high and low density materials with periodicity in the nanometer range. The main advantages of ML optics stem from the tunability of layer thickness, composition, lateral gradient, and the gradient along the normal to the substrate; these can be tailored according to the desired wavelength regime. They have the great advantage of being adaptable to figured surfaces, enabling their use as reflective optics in these spectral regions, for focusing and imaging applications. Broadband reflectivity and wavelength tunability are also possible by using MLs with normal and lateral gradient, respectively. However, fabrication of these ML mirrors requires the capability to deposit uniform, ultra-thin (a few angstroms-thick) films of different materials with thickness control on the atomic scale. Thus, one requires a proper understanding of substrate surfaces, individual layers, chemical reactivity at interfaces and, finally, of the ML structures required for particular applications. The performance of these MLs is limited by (the lack of) contrast in optical constants of the two materials, interfacial roughness, the chemical reactivity of two materials and, finally, errors in the thickness of individual layers. Soft x-ray/extreme ultra-violet ML mirrors have found a wide range of applications in synchrotron radiation beam lines, materials science, astronomy, x-ray microscopy, x-ray laser, x-ray lithography, polarizers, and plasma diagnostics. The Indus–1 synchrotron radiation (SR) source is an operational 450 MeV machine, which produces radiation up to soft x-rays. Indus-2 is a 2.5 GeV machine, which has been commissioned recently to produce hard x-rays (E > 25 keV). The combination of Indus-1 and Indus-2 will cover a broad energy spectrum from IR to hard x-rays. Therefore, there is a significant need and opportunity to study MLs of different pairs of materials, with different parameters such as periodicity and optimum thickness of individual layers. The goal of the present thesis is to fabricate MLs for soft x-ray optics and to study their physics for application as polarizers in the wavelength range from 67 Å to 160 Å on the Indus-1 synchrotron source. To accomplish this task, a UHV electron beam evaporation system has been developed indigenously for the fabrication of MLs. Three different ML systems viz., Mo/Si, Fe/B4C and Mo/Y have been fabricated, and their surfaces and interfaces were investigated thoroughly for the polarizer application. X-ray reflectivity (XRR) has been used extensively in the investigations of these MLs. This is because XRR is a highly sensitive non-destructive technique for the characterization of buried interfaces, and gives microscopic information (at atomic resolution) over a macroscopic length scale (a few microns). Numerical analysis of XRR data has been carried out using computer programs. Depth-graded x-ray photoelectron spectroscopy (XPS) has been used for compositional analysis at interfaces for some of the ML structures, as a technique complementary to XRR. The performance of some of these MLs has been tested in the soft x-ray region, using the Indus-1 synchrotron radiation (SR) source. Prior to studying the MLs, a detailed study of the surfaces and interfaces of thin films, bi-layers, and tri-layers was carried out using XRR and the glancing incidence fluorescence technique. The discontinuous-to-continuous transition and the mode of film growth, which are vital to the optimization of layer thickness (basically for the high-atomic number or high-Z layer) in the ML structures, were also investigated using in situ sheet resistance measurement method. Indus-1 is a soft x-ray SR source that covers atomic absorption edges of many low-Z materials. The present work demonstrates the possibilities of characterizing low-Z thin films and multilayers using soft x-ray resonant reflectivity. In one case, we have shown for first time that soft x-ray resonant reflectivity can be employed as a non-destructive technique for the determination of interlayer composition. In a second study using the Indus-1 SR source, we have shown, by observing the effect of the anomalous optical constant on reflectivity pattern when photon energy is tuned across the atomic absorption edge of the constituent low-Z element, that soft x-ray resonant reflectivity is an element-specific technique. This thesis is organized into 7 chapters. A brief summary of individual chapters is presented below. Chapter 1 gives a brief general introduction to x-ray ML optics. This is followed by a discussion of the importance of the soft x-ray region of electromagnetic radiation. The optical properties of x-rays are reviewed and optical constants are calculated for some of the important materials used for x-ray MLs. The refractive index in the x-ray region being less than unity (except absorption edges), the consequent limitation of conventional transmission lenses is discussed. The limitation of glancing angle incidence optics is presented, motivating the need for ML optics, which is discussed along with a theoretically calculated reflectivity profile. The procedure for materials for the MLs for application in different spectral regions is discussed, along with a survey of literature related to the present thesis. The importance of the quality of surfaces and interfaces on the performance of ML structures has been shown through simulations. The applications of soft x-ray MLs are discussed with emphasis on polarization. This is followed by a review of different modes of growth of thin films. Finally, the scope of the present work is highlighted. Chapter 2 provides brief descriptions of the experimental techniques used in the present investigations and of the numerical methods employed for quantitative data analysis. The XRR technique is discussed elaborately because it has been used extensively. Detailed calculations of x-ray reflectivity from single surfaces, thin films and bi-layers are presented, along with simulated values. The effect of critical angle and Brewster’s angle is also discussed. Data analysis methods for computing x-ray reflectivity from multilayer structures, based on dynamical and kinematical models, have been discussed. The effect of roughness on XRR has been discussed based on the recursion formalism of dynamical theory. Simulations of XRR and experimental XRR data fitting are carried out using computer programs. The XRR experimental set up is also outlined. A theoretical background is given for the electrical measurements on thin films. This is followed by a brief overview of x-ray photoelectron spectroscopy (XPS) and interpretation of spectra. Finally, the glancing incidence x-ray fluorescence (GIXRF) technique is outlined. Chapter 3 describes in detail the ultra-high vacuum electron beam evaporation system developed in house especially for the fabrication of thin films and x-ray multilayer optics. At the outset, a brief overview of different deposition techniques commonly used for the fabrication of x-ray optical elements is presented. Design, fabrication, and assembly of different accessories are discussed. The control of thickness and uniformity of the films deposited has been checked through the experiments, whose results are provided. The results obtained for ML test structures are presented to show the capability of system in carrying out fabrication of high quality x-ray ML structures. Finally, the versatility of evaporation system incorporating in situ characterization facilities such as -situ electrical measurements for different substrate temperatures is illustrated. Chapter 4 presents a study of the growth of ultra-thin Mo films at different substrate temperatures using in situ sheet resistance measurements. First, a theoretical background is given on the different stages of island growth and on factors affecting thin film growth, followed by a discussion of the possible electrical conduction phenomena in continuous and discontinuous metal films. The nature of thin film growth and a detailed microscopic picture at different growth stages are derived from a modeling of sheet resistance data obtained in situ. The various conduction mechanisms have been identified in different stages of growth. In the island growth stage, the isotropic and anisotropic growth of Mo islands is identified from the model. In the insulator-metal transition region, experimentally determined values of critical exponent of conductivity agrees well with theoretically predicted values for a two-dimensional (2D) percolating system, revealing that Mo films on float glass substrate is predominantly a 2D structure. The minimum thickness for which Mo films becomes continuous is obtained as 1.8 nm and 2.2 nm for Mo deposited at substrate temperatures 300 K and 100 K, respectively. An amorphous-to- crystalline transition is also observed, and discussed. Chapter 5 covers the detailed study of the surfaces and interfaces studies in three different ML structures viz., Mo/Si, Fe/B4C and Mo/Y, meant for the polarizer application in the wavelength range of 67 Å to 160 Å. Multilayers with varying periodicity, varying number of layer pairs, and different ratios of high-Z layer thickness to the period, were fabricated using the electron beam system. Initially, a brief overview of the design aspects of ML structures is given, along with the theoretically calculated reflectivity at Brewster’s angle from the best material combinations. In Mo/Si MLs, the interlayer formed at the interfaces due to interdiffusion of the two elements is asymmetric in thickness, i.e., Mo-on-Si interlayer is thicker than the Si-on-Mo interlayer. To take account of these interlayers in XRR data fitting, a four layer model is considered. The effect of interlayers on reflectivity pattern was studied using simulations, and differences with respect to roughness are also discussed. The mechanism of formation of asymmetric interlayers is also discussed. The interlayer composition has determined using depth-graded XPS. The results reveal the formation of the MoSi2 composition at both the interfaces. The experimental results agree well with theoretical calculations based on solid-state amorphization reaction, which is a result of large heat of mixing. The effective heat of formation model reveals the formation of MoSi2 as the first phase. The soft x-ray reflectivity performance of the Mo/Si ML structure at Brewster’s angle is tested using Indus-1 synchrotron radiation (SR). Using XRR and GIXFR, a study of the surfaces and interfaces of bilayers of B4C-on-Fe and Fe-on- B4C, and tri-layers of Fe-B4C-Fe was carried out, with a systematic variation of Fe and B4C layer thicknesses. A sharp interface was observed in Fe-on-B4C, whereas a low density (w.r.t. Fe) interlayer is observed at the B4C-on-Fe interface. The interlayer properties fluctuates w.r.t. the bottom Fe layer thickness and is independent of the top B4C layer thickness. The nature of fluctuations has been discussed in detail. A study of the surfaces and interfaces of Fe/B4C MLs is described. Finally, a study of the surfaces and interfaces of bilayers, tri-layers, and MLs of the Mo/Y system is discussed in detail. Chapter 6 describes the application of soft x-ray resonant reflectivity for the characterization of low-Z thin films and interfaces in multilayer structures. Initially, a discussion of the energy dependence of atomic scattering factors and hence of optical constants is provided with simulations, with emphasis on the atomic absorption edge. Then, a brief overview of synchrotron radiation, with particular emphasis on the parameters of the Indus-1 synchrotron source is given. The possibilities of determining the composition of the buried interlayer with sub-nanometer scale sensitivity using soft x-ray resonant reflectivity are discussed. The methodology has been applied to study the Mo/Si interface both by simulations and by experiments on the Indus-1 SR, by tuning the photon energy to the Si L-absorption edge. Finally, direct evidence of elemental specificity of soft x-ray resonant reflectivity through the observation of the effect of anomalous optical constants on the reflectivity pattern is discussed. We demonstrate the method through simulations and experiments on the B4C material in B4C thin films and Fe/ B4C bi-layers, using Indus-1 SR tuned to the boron Kedge. Chapter 7 summarizes the main findings of the present work, and provides an outlook for further investigations in the field.

The exploitation of the soft x-ray/extreme ultra-violet (EUV) region of the electromagnetic spectrum is possible mainly due to the development of multilayer (ML) mirrors. This region of the electromagnetic spectrum offers great opportunities in both science and technology. The shorter wavelength allows one to see smaller features in microscopy and write finer features in lithography. High reflectivity with moderate spectral bandwidth at normal/near-normal incidence can be achieved in soft x-ray/ EUV spectral range using these ML mirrors, where natural crystals with the required large periodicity are not available. These MLs are generally artificial Bragg’s reflectors, which consist of alternative high and low density materials with periodicity in the nanometer range. The main advantages of ML optics stem from the tunability of layer thickness, composition, lateral gradient, and the gradient along the normal to the substrate; these can be tailored according to the desired wavelength regime. They have the great advantage of being adaptable to figured surfaces, enabling their use as reflective optics in these spectral regions, for focusing and imaging applications. Broadband reflectivity and wavelength tunability are also possible by using MLs with normal and lateral gradient, respectively. However, fabrication of these ML mirrors requires the capability to deposit uniform, ultra-thin (a few angstroms-thick) films of different materials with thickness control on the atomic scale. Thus, one requires a proper understanding of substrate surfaces, individual layers, chemical reactivity at interfaces and, finally, of the ML structures required for particular applications. The performance of these MLs is limited by (the lack of) contrast in optical constants of the two materials, interfacial roughness, the chemical reactivity of two materials and, finally, errors in the thickness of individual layers. Soft x-ray/extreme ultra-violet ML mirrors have found a wide range of applications in synchrotron radiation beam lines, materials science, astronomy, x-ray microscopy, x-ray laser, x-ray lithography, polarizers, and plasma diagnostics. The Indus–1 synchrotron radiation (SR) source is an operational 450 MeV machine, which produces radiation up to soft x-rays. Indus-2 is a 2.5 GeV machine, which has been commissioned recently to produce hard x-rays (E > 25 keV). The combination of Indus-1 and Indus-2 will cover a broad energy spectrum from IR to hard x-rays. Therefore, there is a significant need and opportunity to study MLs of different pairs of materials, with different parameters such as periodicity and optimum thickness of individual layers. The goal of the present thesis is to fabricate MLs for soft x-ray optics and to study their physics for application as polarizers in the wavelength range from 67 Å to 160 Å on the Indus-1 synchrotron source. To accomplish this task, a UHV electron beam evaporation system has been developed indigenously for the fabrication of MLs. Three different ML systems viz., Mo/Si, Fe/B4C and Mo/Y have been fabricated, and their surfaces and interfaces were investigated thoroughly for the polarizer application. X-ray reflectivity (XRR) has been used extensively in the investigations of these MLs. This is because XRR is a highly sensitive non-destructive technique for the characterization of buried interfaces, and gives microscopic information (at atomic resolution) over a macroscopic length scale (a few microns). Numerical analysis of XRR data has been carried out using computer programs. Depth-graded x-ray photoelectron spectroscopy (XPS) has been used for compositional analysis at interfaces for some of the ML structures, as a technique complementary to XRR. The performance of some of these MLs has been tested in the soft x-ray region, using the Indus-1 synchrotron radiation (SR) source. Prior to studying the MLs, a detailed study of the surfaces and interfaces of thin films, bi-layers, and tri-layers was carried out using XRR and the glancing incidence fluorescence technique. The discontinuous-to-continuous transition and the mode of film growth, which are vital to the optimization of layer thickness (basically for the high-atomic number or high-Z layer) in the ML structures, were also investigated using in situ sheet resistance measurement method. Indus-1 is a soft x-ray SR source that covers atomic absorption edges of many low-Z materials. The present work demonstrates the possibilities of characterizing low-Z thin films and multilayers using soft x-ray resonant reflectivity. In one case, we have shown for first time that soft x-ray resonant reflectivity can be employed as a non-destructive technique for the determination of interlayer composition. In a second study using the Indus-1 SR source, we have shown, by observing the effect of the anomalous optical constant on reflectivity pattern when photon energy is tuned across the atomic absorption edge of the constituent low-Z element, that soft x-ray resonant reflectivity is an element-specific technique. This thesis is organized into 7 chapters. A brief summary of individual chapters is presented below. Chapter 1 gives a brief general introduction to x-ray ML optics. This is followed by a discussion of the importance of the soft x-ray region of electromagnetic radiation. The optical properties of x-rays are reviewed and optical constants are calculated for some of the important materials used for x-ray MLs. The refractive index in the x-ray region being less than unity (except absorption edges), the consequent limitation of conventional transmission lenses is discussed. The limitation of glancing angle incidence optics is presented, motivating the need for ML optics, which is discussed along with a theoretically calculated reflectivity profile. The procedure for materials for the MLs for application in different spectral regions is discussed, along with a survey of literature related to the present thesis. The importance of the quality of surfaces and interfaces on the performance of ML structures has been shown through simulations. The applications of soft x-ray MLs are discussed with emphasis on polarization. This is followed by a review of different modes of growth of thin films. Finally, the scope of the present work is highlighted. Chapter 2 provides brief descriptions of the experimental techniques used in the present investigations and of the numerical methods employed for quantitative data analysis. The XRR technique is discussed elaborately because it has been used extensively. Detailed calculations of x-ray reflectivity from single surfaces, thin films and bi-layers are presented, along with simulated values. The effect of critical angle and Brewster’s angle is also discussed. Data analysis methods for computing x-ray reflectivity from multilayer structures, based on dynamical and kinematical models, have been discussed. The effect of roughness on XRR has been discussed based on the recursion formalism of dynamical theory. Simulations of XRR and experimental XRR data fitting are carried out using computer programs. The XRR experimental set up is also outlined. A theoretical background is given for the electrical measurements on thin films. This is followed by a brief overview of x-ray photoelectron spectroscopy (XPS) and interpretation of spectra. Finally, the glancing incidence x-ray fluorescence (GIXRF) technique is outlined. Chapter 3 describes in detail the ultra-high vacuum electron beam evaporation system developed in house especially for the fabrication of thin films and x-ray multilayer optics. At the outset, a brief overview of different deposition techniques commonly used for the fabrication of x-ray optical elements is presented. Design, fabrication, and assembly of different accessories are discussed. The control of thickness and uniformity of the films deposited has been checked through the experiments, whose results are provided. The results obtained for ML test structures are presented to show the capability of system in carrying out fabrication of high quality x-ray ML structures. Finally, the versatility of evaporation system incorporating in situ characterization facilities such as -situ electrical measurements for different substrate temperatures is illustrated. Chapter 4 presents a study of the growth of ultra-thin Mo films at different substrate temperatures using in situ sheet resistance measurements. First, a theoretical background is given on the different stages of island growth and on factors affecting thin film growth, followed by a discussion of the possible electrical conduction phenomena in continuous and discontinuous metal films. The nature of thin film growth and a detailed microscopic picture at different growth stages are derived from a modeling of sheet resistance data obtained in situ. The various conduction mechanisms have been identified in different stages of growth. In the island growth stage, the isotropic and anisotropic growth of Mo islands is identified from the model. In the insulator-metal transition region, experimentally determined values of critical exponent of conductivity agrees well with theoretically predicted values for a two-dimensional (2D) percolating system, revealing that Mo films on float glass substrate is predominantly a 2D structure. The minimum thickness for which Mo films becomes continuous is obtained as 1.8 nm and 2.2 nm for Mo deposited at substrate temperatures 300 K and 100 K, respectively. An amorphous-to- crystalline transition is also observed, and discussed. Chapter 5 covers the detailed study of the surfaces and interfaces studies in three different ML structures viz., Mo/Si, Fe/B4C and Mo/Y, meant for the polarizer application in the wavelength range of 67 Å to 160 Å. Multilayers with varying periodicity, varying number of layer pairs, and different ratios of high-Z layer thickness to the period, were fabricated using the electron beam system. Initially, a brief overview of the design aspects of ML structures is given, along with the theoretically calculated reflectivity at Brewster’s angle from the best material combinations. In Mo/Si MLs, the interlayer formed at the interfaces due to interdiffusion of the two elements is asymmetric in thickness, i.e., Mo-on-Si interlayer is thicker than the Si-on-Mo interlayer. To take account of these interlayers in XRR data fitting, a four layer model is considered. The effect of interlayers on reflectivity pattern was studied using simulations, and differences with respect to roughness are also discussed. The mechanism of formation of asymmetric interlayers is also discussed. The interlayer composition has determined using depth-graded XPS. The results reveal the formation of the MoSi2 composition at both the interfaces. The experimental results agree well with theoretical calculations based on solid-state amorphization reaction, which is a result of large heat of mixing. The effective heat of formation model reveals the formation of MoSi2 as the first phase. The soft x-ray reflectivity performance of the Mo/Si ML structure at Brewster’s angle is tested using Indus-1 synchrotron radiation (SR). Using XRR and GIXFR, a study of the surfaces and interfaces of bilayers of B4C-on-Fe and Fe-on- B4C, and tri-layers of Fe-B4C-Fe was carried out, with a systematic variation of Fe and B4C layer thicknesses. A sharp interface was observed in Fe-on-B4C, whereas a low density (w.r.t. Fe) interlayer is observed at the B4C-on-Fe interface. The interlayer properties fluctuates w.r.t. the bottom Fe layer thickness and is independent of the top B4C layer thickness. The nature of fluctuations has been discussed in detail. A study of the surfaces and interfaces of Fe/B4C MLs is described. Finally, a study of the surfaces and interfaces of bilayers, tri-layers, and MLs of the Mo/Y system is discussed in detail. Chapter 6 describes the application of soft x-ray resonant reflectivity for the characterization of low-Z thin films and interfaces in multilayer structures. Initially, a discussion of the energy dependence of atomic scattering factors and hence of optical constants is provided with simulations, with emphasis on the atomic absorption edge. Then, a brief overview of synchrotron radiation, with particular emphasis on the parameters of the Indus-1 synchrotron source is given. The possibilities of determining the composition of the buried interlayer with sub-nanometer scale sensitivity using soft x-ray resonant reflectivity are discussed. The methodology has been applied to study the Mo/Si interface both by simulations and by experiments on the Indus-1 SR, by tuning the photon energy to the Si L-absorption edge. Finally, direct evidence of elemental specificity of soft x-ray resonant reflectivity through the observation of the effect of anomalous optical constants on the reflectivity pattern is discussed. We demonstrate the method through simulations and experiments on the B4C material in B4C thin films and Fe/ B4C bi-layers, using Indus-1 SR tuned to the boron Kedge. Chapter 7 summarizes the main findings of the present work, and provides an outlook for further investigations in the field.