Two thin film materials - intermetallic and porous silicon thin films, have been studied in this thesis. The first part focuses on the hydrogen storage and electrochemical properties of single layer LaNi5-based thin films fabricated by magnetron sputtering. The aim is to enhance their performance in mini hydrogen storage systems, and their application as electrodes in thin film Ni-MH micro-batteries. Such LaNi5-based thin films were fabricated by magnetron puttering. Using X-ray diffraction (XRD), these thin films revealed a crystalline structure with uniform chemical composition. Using AFM, SEM and TEM, they were found to have a unique microstructure: (1) Nanopores of approximately 15-40 nm which could possibly act as hydrogen reservoir (2) A dense, defect free cross sectional region which would ultimately improve the efficiency and lifetime of the thin film electrodes used in thin film battery. The hydrogen absorption/desorption behaviour of these thin films were determined by volumetric method. The maximum hydrogen content of the La-Ni-A1 film was found to be 1.45 wt% at 333 K which was very close to the theoretical capacity of 1.47 wt%; and higher than that of the La-Ni-AI powder materials (1.2 wt%). Electrochemical properties of the films were measured by simulated battery tests. When discharged at low current, the discharge capacity of the film was similar to that of powder materials - about 220 mAh/g for the first 30 cycles. When the thin film electrode was discharged at a high rate, 4C (current density of 100 mA/g), it could reach the maximum specific capacity of 200 mAh/g and maintained this capacity for 200 cycles; the value was not attainable for La-Ni-AI powder electrode. The presence of crack propagation in film during charge/discharge cycles would improve the electrochemical performance which was different to that of powder materials. Cyclic voltammetry reported that the efficiency of the film could maintain at 80% for the first 200 cycles and gradually decreased due to the formation of corrosion products on surface, which is consistent with the galvanostatic results. XPS (X-ray Photoelectron Spectroscopy) revealed that the corrosion products ??? A1203, La203 and La(OH)3 formed on the film surface after cyclic voltammetry. The second part reported the hydrogen absorption/desorption behaviour of porous silicon thin films. The hydrogen content was determined quantitatively by both volumetric method and thermogravimetric analysis (TGA) and found to be 15 wt% at 423 K under 15 atm of hydrogen pressure. This is an extraordinary amount of hydrogen absorption which supersedes the US Department of Energy's 2007 target of 6.5 wt%. Hydrogen depth profiles of the film after hydrogenation performed by Secondary Ion Mass Spectroscopy confirmed there was hydrogen within the film structure, this was an indication that hydrogen was not just physisorbed on the film surface, but chemisorbed into the porous Si lattice. X-ray diffraction found that there was a lattice contraction upon hydrogen insertion, again suggesting the hydrogen entered into the film structure by chemisorption.

Thesis (M. S.)--Mechanical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Pierron, Olivier N.; Committee Member: McDowell, David L.; Committee Member: Neu, Richard W.. Part of the SMARTech Electronic Thesis and Dissertation Collection.

The photoluminescence (PL) emitted by porous silicon has been investigated under different conditions of excitation using a pulsed nitrogen laser source, and the continuous tunable DV synchrotron source at Daresbury Laboratory. The project involved sample preparation, and PL measurements using a custom-built optical laser-based system for lifetime measurements. This in itself necessitated software and hardware development to enable interfacing and data-logging using an IBM-compatible PC. The equipment development formed a major part of the project.

Thesis (Ph. D. in Electrical Engineering)--Vanderbilt University, Aug. 2003. / Title from title screen. Includes bibliographical references.

Amorphous Silicon(a-Si) films have attracted the attention of several investigators as it is an economical material for devices. One of the problems that is addressed is the doping of these films after they are prepared. In this thesis, we investigated the effects of doping amorphous Sil­icon films(prepared by r.f. sputtering) with Aluminium(Al) by ther­mal diffusion. Amorphous Silicon films have been prepared on glass substrates at optimal process parameters. Then, the a-Si films are coated with Al by vacuum evaporation and subjected to heating in N2 atmosphere in the temperature range 300°C to 600°C for different durations. After etching Al layer, it has been found that some of the films which are heated around 550°C contain filament like polycrystalline regions surrounding islands of a-Si. This structure has been confirmed through Scanning Electron Mi-croscope(SEM) photographs and electrical conductivity measurements. SEM photographs indicate that, bright regions of amorphous mate­rial are surrounded by dark regions of relatively higher conducting boundaries. The electrical conductivity study shows that there is sharp increase in conductivity of Al doped films, which is attributed to the conduct­ing polycrystalUne filament. A simple model has been proposed to explain the variation of con­ductivity of these transformed films, with process parameters and with temperature. Schottky barrier diodes have been fabricated using these trans­formed materials and their characteristics explained.

The present thesis deals with Nb-Si alloy composites in both bulk and multilayer forms. The work has been divided into two parts. First part (chapter 4-6) deals with Nb based silicides binary and ternary alloys with alloying additions like Ga and Al. These alloys are synthesized by vacuum arc melting and suction casting (non-equilibrium processing techniques). The studies on intermetallic coatings of Nb-Si alloys and Nb/Si multilayer synthesized by pulsed laser deposition technique have been presented in the second part (chapter7-8). Nb-Si alloys are one of the candidate materials for the advanced structural and microelectronic applications. There are few issues with these materials like poor oxidation resistance, low fracture toughness and brittleness which need to be solved. Microstructure plays a crucial role to control these properties. The main focus of this work is to understand the process of phase transformation and thereby control the microstructure in both bulk alloys and thin films. We have also investigated in a limited manner mechanical and environmental properties of bulk alloys. This thesis is subdivided into nine chapters. After a brief introduction in the first chapter, a brief overview on Nb-Si phase diagram and literature reviews on Nb-Si based alloys are presented with emphasis on the current work in the second chapter. Literature reviews on the phase formations sequence and stability in Nb-Si alloys thin films and Nb/Si multilayers are also discussed in the same chapter. In the third chapter different experimental techniques, processing parameters and characterization tools like XRD, SEM, TEM etc. are briefly discussed. Special emphasis is given on two non-equilibrium techniques: laser deposition technique to deposit the thin film/multilayer and vacuum suction casting to produce the 3 mm diameter rods of different Nb-Si alloys. The fourth chapter discusses the microstructural aspects of Nb-Si alloys prepared by suction casting and its mechanical behavior. The samples have the compositions hypoeutectic (Nb-10at.%Si and Nb-14at.%Si), eutectic (Nb-18.7at.%Si) and hypereutectic (Nb-22at.% Si and Nb-25at.% Si). SEM microstructural analyses of all the samples clearly show the enhancement in the volume fraction of eutectic and decease in the eutectic spacings in microstructure due to large undercooling. Rod eutectic is observed in most of places with irregular eutectic a few places in all samples. First check of phases has been done by XRD in all samples. Phase confirmation using TEM showed the eutectic between Nbss and Nb3Si phases in all samples. The primary phase for hypoeutectic alloys is Nbss (dendritic structure), Nb3Si phase for eutectic composition and β-Nb5Si3 phase for hypereutectic alloys. Compositional analysis using EDS and EPMA also supported the above results. No signature of eutectoid reaction (Nb3Si→Nb+α-Nb5Si3) is observed. Mechanical properties like hardness, strength, ductility and indentation fracture toughness have been determined for above mention alloy compositions. SEM micrographs showed that silicides fractured by cleavage and Nb phase in a ductile manner during the compression tests carried out at room temperature. We attempt to explain how the above mention mechanical properties change with alloy compositions and processing. Chapter five deals with the effect of Ga addition on the microstructure and mechanical properties of the Nb-Si alloy. The composition selected for this study is Nb-20.2at.%Si-2.7at.%Ga. The results of ternary alloy have been compared with the binary alloy composition Nb-18.7at.%Si. Phase analysis has been carried out using TEM and XRD. Ga addition has suppressed the formation of Nb3Si phase and promoted the formation of β-Nb5Si3 phase. Ga addition also established the eutectic between Nbss and β-Nb5Si3, which is a metastable eutectic. Ga added ternary alloy, on suction casting, yields ultrafine eutectic with nanometer length scale (50-100nm). From the compression tests, it is concluded that the combination of ultrafine eutectic (Nbss-β-Nb5Si3) and primary β-Nb5Si3 in ternary alloy results in a high compressive strength ~2.8±0.1 GPa with 4.3% plasticity. In contrast binary alloy under identical conditions shows the compressive strength ~1.35±0.1 GPa and 0.2% plasticity. Ga addition also enhances the indentation fracture toughness from 9.2±0.05 MPa√m (binary) to 24.11±0.5 MPa√m (ternary). Composite hardness values of the ternary and binary alloys are 1064±20 Hv and 1031±20 Hv respectively. Chapter six deals with Al added Nb-Si ternary alloy. Here we have discussed microstructural and mechanical properties like in chapter 5 along with oxidation behavior for the alloy composition Nb-12.7at.%Si-9at.%Al. SEM micrograph shows the presence of primary dendrites structure with ultra fine lamellar eutectic (50-100nm). Detailed TEM studies confirm the Nbss as primary phase present in form of dendrites. These dendrites contain the plate shape precipitates of δ-Nb11Si4 (body centered orthorhombic structure) phase in Nb matrix (primary dendrites). Eutectic phases are Nbss and β-Nb5Si3. The analysis of the results indicates that Al addition promote the formation of β-Nb5Si3 phase in the eutectic. The results of this ternary composition were also compared with the binary alloy composition Nb-18.7at.%Si. Compression tests have been carried out at room and elevated temperatures to measure the strength of the material. Al added ternary alloy yields the compressive strength value 1.6±0.01 GPa whereas binary alloy yields the compressive strength value 1.1±0.01 GPa. Enhancement in indentation fractured toughness is observed in Al added ternary alloy (20.4±0.5MPa√m) compare to binary alloy (9.2±0.05 MPa√m). Thermal analysis by TGA and DTA were used to see the oxidation behavior of Al added ternary alloy. Chapter seven deals with the deposition characteristics and the TEM studies on the laser deposited Nb-Si thin films. Films were deposited on the NaCl crystals and Si single crystal substrates. The compositions chosen in this case are Nb-25at.%Si, Nb-37.5at.%Si and Nb-66.7at.%Si. These compositions correspond to the equilibrium intermetallic compounds Nb3Si, Nb5Si3 and NbSi2 respectively. In this chapter we have briefly discussed the microstructural and phase evolutions in the intermetallic coatings. The smooth films quenched from the vapor and/or plasma state show amorphous structure. The sequence of crystallization was studied by hot stage TEM experiments as well as by cross sectional TEM in the films deposited at the elevated temperatures (600oC and 700oC) on Si substrates. During the hot stage experiment, crystallization is observed in Nb-25at.%Si film around 850oC with nucleation of metastable cubic Nb3Si phase. Occasionally metastable hexagonal Nb3Si3 phase has also been observed (close to Si substrate) along with cubic Nb3Si phase in the films at elevated temperatures. For Nb-37.5at.%Si film, crystallization is observed at 800oC with the nucleation of grains of metastable hexagonal Nb5Si3 phase. Cross-sectional TEM shows the presence of hexagonal Nb5Si3 phase along with few grains of NbSi3 (equilibrium) phase in the films deposited at elevated temperatures. Hot stage experiment of Nb-66.3at.%Si film showed the onset of crystallization much earlier at 400oC and complete crystallization at 600oC. This crystallization leads to the nucleation of grains of NbSi2 phase. Films of this composition deposited at elevated temperatures showed the presence of NbSi2 and metastable hexagonal Nb5Si3 phases (occasionally). The laser ablated films, besides the film matrix also contain the micron and submicron sized spherical droplets of different sizes. These droplets travel at very high velocities and impinge on the substrate resulting in a very high rate of heat transfer during solidification from liquid state. Therefore in this work we have also studied the microstructural evolution in the droplets for each composition. The phases observed in the droplets embedded in the matrix of Nb-25 at% Si alloy film are the bcc Nb and the cubic Nb3Si (metastable phase). The droplets in the matrix of Nb-37.5 at% Si alloy showed the bcc Nb and tetragonal β-Nb5Si3 phases. The phases observed in the droplets of in the Nb-66.3at.%Si alloy are the bcc Nb, tetragonal β-Nb5Si3 and the hexagonal NbSi2 (metastable phase). Chapter eight describes the synthesis and microstructural characterization using TEM of Nb/Si multilayers. The aim of this work is to check the stability and phase formation sequence in Nb/Si multilayer. Nb/Si multilayers were first annealed at different time intervals at 600oC and at different temperatures (for 2 hours) and then characterized by the cross-sectional transmission electron microscopy. As-deposited Nb layer is crystalline while Si layer is amorphous. Microstructural and compositional evidences suggest the intermixing between the Nb and Si layers at the interfaces. Nb/Si multilayer annealed at 600oC for 1 hour, NbSi2 was identified as the first crystalline nucleating phase. However amorphous silicide layers were also observed between Nb and NbSi2 layers. Metastable hexagonal Nb5Si3 was identified as the next crystalline phase that nucleated from the amorphous silicide layers at the interfaces of Nb and NbSi2 layers. Occasionally few grains of cubic Nb3Si phase were also observed after 8 hours of annealing at 600oC. In the chapter we have compared the results to the other reported works in Nb-Si bulk diffusion couples and also thin film couples. The final chapter summarizes the major conclusions of the present work and scope of future work.

Modulation doped heterostructures have revolutionized the operation of field effect devices by increasing the speed of operation. One of the factors that affects the speed of operation of these devices is the mobility of the carriers, which is intrinsic to the material used. Mobility of electrons in silicon based devices has improved drastically over the years, reaching as high as 50.000cm2/Vs at 4.2K and 2600cm2/Vs at room temperature. However, the mobility of holes in p-type silicon devices still remains comparatively lesser than the electron mobility because of large effective masses and complicated valence band structure involved. Germanium is known to have the largest hole mobility of all the known semiconductors and is considered most suitable to fabricate high speed p-type devices. Moreover, it is also possible to integrate germanium and its alloy (Si1_zGex ) into the existing silicon technology. With the use of sophisticated growth techniques it has been possible to grow epitaxial layers of silicon and germanium on Si1_zGex alloy layers grown on silicon substrates. In tills thesis we investigate in detail the electrical properties of p-type germanium and n-type silicon thin films grown by these techniques. It is important to do a comparative study of transport in these two systems not only to understand the physics involved but also to study their compatibility in complementary field effect devices (cMODFET). The studies reported in this thesis lay emphasis both on the low and high field transport properties of these systems. We report experimental data for the maximum room temperature mobility of holes achieved m germanium thin films grown on Si1_zGex layers that is comparable to the mobility of electrons in silicon films. We also report experiments performed to study the high field degradation of carrier mobility due to "carrier heating" in these systems. We also report studies on the effect of lattice heating on mobility of carriers as a function of applied electric field. To understand the physics behind the observed phenomenon, we model our data based on the existing theories for low and high field transport. We report complete numerical calculations based on these theories to explain the observed qualitative difference in the transport properties of p-type germanium and ii-type silicon systems. The consistency between the experimental data and theoretical modeling reported in this work is very satisfactory.