<p>  </p> <p>Due to miniaturization of electronic devices new electronic packaging strategies, such as Heterogeneous Integration Packaging (HIP), are being developed. In HIP, the space in the package is strategically mapped out to maximize the placement of components including all types of materials. Thus, there is a need to develop and understand the behavior of lower-melting point metallic interconnects as they will be located next to lower melting point materials, such as polymers. </p> <p>The composition of alloying elements in Sn-rich solder plays a pivotal role in determining the microstructural properties of the solder joint. However, the complex mechanisms governing the solidification processes of Sn-In, and Sn-Bi alloys are still not fully understood. Furthermore, the experimental characterization of phase formation poses significant challenges.</p> <p>This dissertation focuses on understanding microstructural evolution in Sn-In and Sn-Bi alloys during reflow. A systematic approach to characterizing the microstructure of alloys was developed, utilizing electron microscopy, non-destructive x-ray tomography and diffraction techniques, ranging from lab-scale to synchrotron experiments. The influence of In addition on microstructure was correlated with the mechanical behavior obtained using nanoindentation. The experimental understanding was further correlated with the Density Functional Theory (DFT) calculations. To study the Sn-Bi microstructures, the effect of experimental parameters, such as the cooling rate during solidification was elucidated. A 4D study was conducted, involving the analysis of 3D microstructures along with time evolution, to gain a comprehensive understanding of the solidification dynamics using synchrotron white beam tomography. For the first time, we observed a regular pyramidal morphology of Bi forming in the solder alloy. The 4D analysis provided crucial insights into morphology formation, growth kinetics, defect formation during solidification. The crystallographic analysis unraveled unique insights into the solid-liquid interface stability for semi-metals. Furthermore, the simultaneous Energy Dispersive Diffraction (EDD) analysis yielded a deeper understanding into the phase formation and lattice strain evolution. A fundamental relationship between the diffraction intensity and phase fractions, from imaging, was obtained. The experimental methodology developed in this work has the potential to be extended to investigate a wide range of alloy solidification mechanisms, enabling a deeper understanding of these materials.</p>

No description available.

In this study, we used UV-ozone Ar sputtering, X-ray photoelectron and ultra-violet photoelectron spectroscopies and sputtering based depositions of RuO2 and Se nano-layers on indium tin oxides (ITOs). We elucidated the effect of Ar sputtering on the composition and chemistry of Sn rich ITO surface. We demonstrated that while a combination of UV-ozone radiation and Ar sputtering removes most of the hydrocarbons responsible for degrading the work function of ITO, it also removes significant amount of the segregated SN at the ITO surface that's responsible for its reasonable work function of 4.7eV. We also demonstrated for the first time that sputtering cleaning ITO surface leads to the reduction of the charge state of Sn from Sn4+ to Sn2+ that adds to the degradation of the work function. For the nano-layers coverage of ITO studies, we evaluated both RuO2 and Se. For RuO2 coated ITO, XPS showed the formation of a Ru-Sn-O ternary oxide. The RuO2 nano-layer reduced the oxidation state of Sn in the Sn-rich surface of ITO from +4 to +2. The best work function obtained for this system is 4.98eV, raising the effective work function of ITO by more than 0.5 eV. For the Se coated ITO studies, a systematic study of the dependence of the effective work function on the thickness of Se overage and its chemistry at the Se/ITO interface was undertaken. XPS showed that Se reacts with Sn at the Sn-rich surface of ITO determined the presence of both negative and positive oxidation state of Se at the Se/ITO interface. The Se also reduced the oxidation state of Sn from Sn4+ to Sn2+ in the Sn-rich ITO surface. The highest effective work function obtained for this system is 5.06eV. A combination of RuO2/Se nanoscale coating of optimally cleaned ITO would be a good alternative for device applications that would provide work function tuning in addition to their potential ability to act as interface stabilizers and a barrier to reaction and inter-diffusion at ITO/active layers interfaces responsible for long term stability of devices and especially organic solar cells and organic light emitting diodes.

Das Wachstum von monolagen dünnen Schichten von InN und GaN/InN auf ZnO wurde untersucht. Ebenso der Einfluss der Verspannung, welche durch das Substrat bedingt ist, auf den Indiumgehalt von (In, Ga)N Heterostrukturen, welche auf GaN und ZnO gewachsen wurden. Alle Proben wurden mittels Molekularstrahlepitaxy gewachsen. Es wurde eine Prozedur entwickelt zum Glühen von ZnO Substraten, um glatte Oberflächen mit Stufenfluss-Morphologie zu erhalten, welche sich für das Wachstum von monolage-dünnen Heterostrukturen eignen. Solche Zn-ZnO und O-ZnO Oberflächen konnten produziert werden, wenn die Proben bei 1050 °C in einer O2 Atmosphäre bei 1 bar für eine Stunde geglüht wurden. Reflection high energy electron diffraction wurde eingesetzt, um in situ den Wachstumsmodus und die Entwicklung des a-Gitterabstandes zu untersuchen. Die kritische Schichtdicke, ab welcher ein Übergang im Wachstumsmodus von glattem zu rauhem Wachstum statt findet, war für das Wachstum von InN auf ZnO geringer als 2 ML und setzt gemeinsam mit dem Beginn der Relaxation ein. Für das Wachstum von GaN auf monolagen-dünnem InN/ZnO konnte gezeigt werden, dass höchstens wenige ML abgeschieden werden können, bevor Relaxation eintritt und/oder eine Vermischung zu (In, Ga)N stattfindet. Untersuchungen durch Röntgenbeugung und Raman Spektroskopie geben Hinweise darauf, dass das Abscheidung der nominalen Struktur 100x(1 ML InN/2 MLs GaN) vermutlich zum Wachstum von (In, Ga)N führte. Die chemische Zusammensetzung war für alle Proben sehr ähnlich mit einem indium Gehält von etwa x: 0.36 und einem Relaxationsgrad von 65% - 73% für Proben, die auf ZnO gewachsen wurde und 95% für Wachstum auf 300 nm In0.19Ga0.81N/GaN. Ein unbeabsichtigter Unterschied im V/III-Verhältnis während des Wachstums von (In, Ga)N Heterostrukturen, auf welchen die Anwesenheit von Metalltröpchen auf manchen Proben hinwies, lies auf einen möglichen Einfluss auf das Relaxationsverhalten und die Oberflächenrauhigkeit schließen. / Several thin InN and GaN/InN films and (In, Ga)N heterostructures were grown using molecular beam epitaxy to investigate their growth mode. InN and GaN/InN films were grown on ZnO substrates and (In, Ga)N heterostructures were grown on (In, Ga)N buffers and ZnO substrates. Fabricating the heterostructures on two different types of substrates was a means of strain engineering to possibly increase the indium content in the (In, Ga)N layers. An annealing procedure was established to treat ZnO substrate to gain smooth, stepped surfaces suitable for ML thin heterostructure devices. Reflection high energy electron diffraction was used to investigate in situ the growth mechanism and evolution of the a-lattice spacing. The critical layer thickness for growth mode transition of InN from smooth to rough is below 2 MLs and fairly coincides with the onset of main relaxation. The deposition of GaN on ML thin InN/ZnO shows that at best a few MLs can be deposited before relaxation and/or intermixing into (In, GaN) takes place. Investigations by X-ray diffraction and Raman spectroscopy indicate that the deposition of a nominal structure of 100x(1 ML InN/2 MLs GaN) seems to result in the growth of (In, Ga)N instead. The average chemical composition was similar for all samples with an indium content close to x: 0.36 and a degree of relaxation between 65%-73% for samples grown on ZnO and 95% for the sample grown on 300 nm In0.19Ga0.81N/GaN pseudo-substrate. The surface was probed with atomic force microscopy and showed that starting with smooth surfaces with root mean square roughness around 0.2 nm there was a considerable roughening during growth and surfaces with grain like morphology and a roughness around 2 to 3 nm was produced. Unintentional differences in V/III ratio during growth of (In, Ga)N heterostructures, indicated by the presence of droplets on some of the sample surfaces, were possible, impacting on the sample relaxation behavior and the surface roughness.

Des monocristaux des semiconducteurs ternaires AIn2Te4 (A=Cd, Zn, Mn) ont été préparés par une methode de croissance dérivant de la méthode Bridgman et applicable aux composes a fusion non congruente. Les caractérisations physico-chimiques et cristallographiques ont montre l'homogéneite, la stoéchiometrie et la bonne qualité cristalline des cristaux obtenus. L' etude structurale, réalisee sur CdIn2Te4 a permis de conclure que ce compose appartient au groupe d'espace 14 2m. La réflectivité infrarouge et la spectroscopie Raman ont confirme ce groupe d' espace. Les caractérisations électrique et optique de ces matériaux ont été réalises. L'étude des transitoires de courant photo-induit a révélé la présence d' une distribution continue d' etats dans la bande interdite

Ziel der Arbeit war die Synthese von ZnS, welches strukturell natürlichen Sphalerit imitieren und für die Untersuchung und Optimierung von biologischen Laugungsexperimenten genutzt werden soll. Zur Herstellung von chemisch reinem sowie mit den Wertelementen Indium, Kupfer und Eisen dotierten ZnS wurden vier verschiedene Synthesemethoden getestet: Ofentempern, chemische Gasphasentransportreaktion (CVT), feldunterstütztes Sintern (SPS) und die Hochdruck-Hochtemperatur-Synthese (HP/HT). Es folgte die Charakterisierung der synthetisierten Produkte hinsichtlich der Realstruktur und chemischen Reinheit mittels XANES, REM, XRD, EPMA und nasschemischer Verfahren. Abschließend wurden die Synthesemethoden nach ihrer Effizienz evaluiert. Das Ziel, defektfreies kubisches ZnS zu erzeugen, wurde nur mittels CVT und HP/HT erreicht. In dieser Arbeit konnte weiterhin gezeigt werden, dass der Einbau von Indium ohne gleichzeitige Aufnahme von Kupfer bis zu 1 Ma-% möglich ist.:Abbildungsverzeichnis VII Tabellenverzeichnis XI Abkürzungen, Akronyme und Symbole XII Einheiten XV 1 Einleitung 1 2 Forschungsstand zur Synthese von Zinksulfid 6 2.1 Kristallographie von ZnS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.2 p-T -Phasendiagramm von ZnS . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3 Synthesematerial 15 3.1 Gefälltes ZnS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 3.2 Dotierungsmaterialien . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 3.3 Recherche zu kommerziellen Metallsulfiden . . . . . . . . . . . . . . . . . . . . 18 4 Synthesemethoden 21 4.1 Ofentempern . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 4.2 FAST-SPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 4.3 CVT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 4.4 HP/HT-Synthese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 4.4.1 Toroid-Zelle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 4.4.2 HP/HT-Experimentalaufbau und -ablauf . . . . . . . . . . . . . . . . . 27 4.4.3 HP/HT-Kalibrierung . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 5 Analysemethoden 42 5.1 ICP-MS & ICP-OES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 5.2 XRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 5.3 UV-VIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 5.4 REM-EDX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 5.5 EBSD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 5.6 EPMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 5.7 XANES Spektroskopie . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 5.8 Ramanspektroskopie . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 5.9 Dichtebestimmung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 5.10 BET-Messung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 6 Ergebnisse 63 6.1 Charakterisierung industriell verfügbarer Materialien und natürlicher Proben . 63 6.1.1 Synthetische, industriell verfügbare Materialien . . . . . . . . . . . . . . 63 6.1.2 Referenzspektren für XANES-Analysen . . . . . . . . . . . . . . . . . . 65 6.2 Charakterisierung der Synthesematerialien . . . . . . . . . . . . . . . . . . . . 74 6.2.1 ZnS der Leuchtstoffwerke Breitungen GmbH (LWB) . . . . . . . . . . . 74 6.2.2 Dotierungsmaterialien In, Cu und Fe . . . . . . . . . . . . . . . . . . . . 77 6.3 Charakterisierung der synthetisierten Produkte . . . . . . . . . . . . . . . . . . 80 6.3.1 Einkristalle (CVT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 6.3.2 Polykristalline Produkte (Ofentempern, FAST-SPS und HP/HT) . . . . 112 6.4 Bestimmung des Stapelfehleranteils mittels Ramanspektroskopie? . . . . . . . . 152 7 Diskussion 155 7.1 Synthesematerialien und industriell verfügbare Materialien . . . . . . . . . . . 155 7.2 Syntheseprodukte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160 7.2.1 Syntheseprodukte: Einkristalle (CVT) . . . . . . . . . . . . . . . . . . . 160 7.2.2 Syntheseprodukte: Polykristalline Produkte (Ofentempern, FAST-SPS und HP/HT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183 7.2.3 Vergleich der Syntheseprodukte: Einkristalle und Polykristalline Produkte 202 8 Laugungsexperimente: Zusammenfassung und Schlussfolgerung 213 9 Schlussfolgerung 220 10 Zusammenfassung 221 Literaturverzeichnis 225 Anhang A Ergebnispräsentation auf internationalen Fachtagungen 247 B Pulver vs. Kompaktprobe-Diffraktometrie 249 C ZnSdis.str-Datei 252 D Bestimmung der Bandlücke 254 E Messpunkte EPMA 256 F Einwaagen der Synthese 258 G Texturfaktoren der Röntgenbeugung X-Ray Diffraction (XRD)-Analyse 260

Group III-nitride semiconductors have received much research attention and witnessed a significant development due to their ample applications in solid-state lighting and high-power/high-frequency electronics. Numerous growth methods were explored to achieve device quality epitaxial III-nitride semiconductors. Among the growth methods for III-nitride semiconductors, molecular beam epitaxy provides advantages such as formation of abrupt interfaces and in-situ monitoring of growth. The present research work focuses on the growth and characterizations of III-nitride based epitaxial films, nanostructures and heterostructures on c-sapphire substrate using plasma-assisted molecular beam epitaxy system. The correlation between structural, optical and electrical properties of III-nitride semiconductors would be extremely useful. The interfaces of the metal/semiconductor and semiconductor heterostructures are very important in the performance of semiconductor devices. In this regard, the electrical transport studies of metal/semiconductor and semiconductor heterostructures have been carried out. Besides, studies involved with the defect induced room temperature ferromagnetism of GaN films and InN nano-structures have also been carried out. The thesis is organized in eight different chapters and a brief overview of each chapter is given below. Chapter 1 provides a brief introduction on physical properties of group III-nitride semiconductors. It also describes the importance of III-nitride heterostructures in the operation of optoelectronic devices. In addition, it also includes the current strategy of the emergence of room temperature ferromagnetism in III-nitride semiconductors. Chapter 2 deals with the basic working principles of molecular beam epitaxy system and different characterization tools employed in the present work. Chapter 3 describes the growth of GaN films on c-sapphire by plasma-assisted molecular beam epitaxy. The effects of N/Ga flux ratio on structural, morphological and optical properties have been studied. The flux ratio plays a major role in controlling crystal quality, morphology and emission properties of GaN films. The dislocation density is found to increase with increase in N/Ga flux ratio. The surface morphologies of the films as seen by scanning electron microscopy show pits on the surface and found that the pit density on the surface increases with flux ratio. The room temperature photoluminescence study reveals the shift in band-edge emission towards the lower energy with increase in N/Ga flux ratio. This is believed to arise from the reduction in compressive stress in the GaN films as it is evidenced by room temperature Raman study. The transport studies on the Pt/GaN Schottky diodes showed a significant increase in leakage current with an increase in N/Ga ratio and is found to be caused by the increase in dislocation density in the GaN films. Chapter 4 deals with the fabrication and characterization of Au/GaN Schottky diodes. The temperature dependent current–voltage measurements have been used to determine the current transport mechanism in Schottky diodes. The barrier height (φb) and the ideality factor (η) are estimated from the thermionic emission model and are found to be temperature dependent in nature, indicating the existence of barrier height inhomogeneities at the Au/GaN interface. The conventional Richardson plot of ln(Is/T2) versus 1/kT gives Richardson constant value of 3.23×10-5 Acm-2 K-2, which is much lower than the known value of 26.4 Acm-2 K-2 for GaN. Such discrepancy of Richardson constant value was attributed to the existence of barrier height inhomogeneities at the Au/GaN interface. The modified Richardson plot of ln(Is/T2)-q2σs2/2k2T2 versus q/kT, by assuming a Gaussian distribution of barrier heights at the Au/GaN interface, provides the Schottky barrier height of 1.47 eV and Richardson constant value of 38.8 Acm-2 K-2 which is very close to the theatrical value of Richardson constant. The temperature dependence of barrier height is interpreted on the basis of existence of the Gaussian distribution of the barrier heights due to the barrier height inhomogeneities at the Au/GaN interface. Chapter 5 addresses on the influence of GaN underlayer thickness on structural, electrical and optical properties of InN thin films grown using plasma-assisted molecular beam epitaxy. The high resolution X-ray diffraction study reveals superior crystalline quality for the InN film grown on thicker GaN film. The electronic and optical properties seem to be greatly influenced by the structural quality of the films, as can be evidenced from Hall measurement and optical absorption spectroscopy. Also, we present the studies involving the dependence of structural, electrical and optical properties of InN films, grown on thicker GaN films, on growth temperature. The optical absorption edge of InN film is found to be strongly dependent on carrier concentration. Kane’s k.p model is used to describe the dependence of optical absorption edge on carrier concentration by considering the non-parabolic dispersion relation for carrier in the conduction band. Chapter 6 deals with the analysis of the temperature dependent current transport mechanisms in InN/GaN heterostructure based Schottky junctions. The barrier height (φb) and the ideality factor (η) of the InN/GaN Schottky junctions are found to be temperature dependent. The temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. The higher value of the ideality factor and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission (TFE) other than thermionic emission (TE). The room temperature barrier height and the ideality factor obtained by TFE model are 1.43 eV and 1.21, respectively. Chapter 7 focuses on the defect induced room temperature ferromagnetism in Ga deficient GaN epitaxial films and InN nano-structures grown on c-sapphire substrate by using plasma-assisted molecular beam epitaxy. The observed yellow emission peak in room temperature photoluminescence spectra and the peak positioning at 300 cm-1 in Raman spectra confirms the existence of Ga vacancies in GaN films. The ferromagnetism in Ga deficient GaN films is believed to originate from the polarization of the unpaired 2p electrons of nitrogen surrounding the Ga vacancy. The InN nano-structures of different size are grown on sapphire substrate, the structural and magnetic properties are studied. The room temperature magnetization measurement of InN nano-structures exhibits the ferromagnetic behavior. The saturation magnetization is found to be strongly dependent on the size of the nano-structures. Finally, Chapter 8 gives the summary of the present work and the scope for future work in this area of research.

The focus of this thesis is the investigation of thin-film transistors (TFTs) based on amorphous oxide semiconductors (AOSs) in two circuit applications. To date, circuits implemented with AOS-based TFTs have been primarily enhancement-enhancement inverters, ring oscillators based on these inverters operating at peak frequencies up to ~400 kHz, and two-transistor one-capacitor pixel driving circuits for use with organic light-emitting diodes (OLEDS). The first application investigated herein is AC/DC rectification using two circuit configurations based on staggered bottom-gate TFTs employing indium gallium oxide (IGO) as the active channel layer; a traditional full bridge rectifier with diode-tied transistors and a cross-tied full-wave rectifier are demonstrated, which is analogous to what has been reported previously using p-type organic TFTs. Both circuit configurations are found to operate successfully up to at least 20 MHz; this is believed to be the highest reported operating frequency to date for circuits based on amorphous oxide semiconductors. Output voltages at one megahertz are 9 V and ~10.5 V, respectively, when driven with a differential 7.07 Vrms sine wave. This performance is superior to that of previously reported organic-based rectifiers. The second AOS-based TFT circuit application investigated is an enhancement-depletion (E-D) inverter based on heterogeneous channel materials. Simulation results using models based on a depletion-mode indium zinc oxide (IZO) TFT and an enhancement-mode IGO TFT result in a gain of ~15. Gains of other oxide-based inverters have been limited to less than 2; the large gain of the E-D inverter makes it well suited for digital logic applications. Deposition parameters for the IGO and IZO active layers are optimized to match the models used in simulation by fabricating TFTs on thermally oxidized silicon and patterned via shadow masks. Integrated IGO-based TFTs exhibit a similar turn-on voltage and decreased mobility compared to the shadow masked TFTs. However, the integrated IZO-based TFTs fabricated to date are found to be conductive and exhibit no gate modulation. Due to the conductive nature of the load, the fabricated E-D inverter shows no significant output voltage variation. This discrepancy in performance between the integrated and shadow-masked IZO devices is attributed to processing complications. / Graduation date: 2009

No description available.

No description available.