No description available.

The semiconducting compounds CdTe and CdZnTe have important applications in high-energy radiation detectors and as substrates for infrared devices. The materials offer large band gaps, high resistivity, and excellent charge transport properties; however all of these properties rely on very precise control of the material composition. Growing bulk crystals by the travelling heater method (THM) offers excellent compositional control and fewer defects compared to gradient freezing, but it is also much slower and more expensive. A particular challenge is the current need to grow new crystals onto existing seeds of similar size and quality. Simulations and experiments are used in this work to investigate the feasibility of growing these materials by THM without the use of large seed crystals. A new fixed-grid, multiphase finite element model was developed based on the level set method and used to calculate the mass transport regime and interface shapes inside the growth ampoule. The diffusivity of CdTe in liquid tellurium was measured through dissolution experiments, which also served to validate the model. Simulations of tapered THM growth find conditions similar to untapered growth with interface shapes that are sensitive to strong thermosolutal convection. Favourable growth conditions are achievable only if convection can be controlled. In preliminary experiments, tapered GaSb crystals were successfully grown by THM and large CdTe grains were produced by gradient freezing. Beginning with this seed material, 25 mm diameter CdTe and CdZnTe crystals were grown on 10 mm diameter seeds, and 65 mm diameter CdTe on 25 mm seeds. Unseeded THM growth was also investigated, as well as ampoule rotation and a range of thermal conditions and ampoule surface coatings. Outward growth beyond one or two centimeters was achieved only at small diameters and included secondary grains and twin defects; however, limited outward growth of larger seeds and agreement between experimental and numerical results suggest that tapered growth may be achievable in the future. This would require active temperature control at the base of the crystal and reduction of convection through thermal design or by rotation of the ampoule or applied magnetic fields. / Graduate / 0346 / 0794 / 0548 / jordan.roszmann@gmail.com

Waste heat recovery is a multi-billion-dollar industry with a compound annual growth rate of 8.8% assessed between 2016 to 2024 and low-grade waste heat (< 230^oC ± 20^oC) makes up 66% of this ubiquitous resource. Thermoelectric generators are preferred for the recovery process because they are cheap and are well suited for this temperature range. They generate power by converting thermal potential to electric potential, known as the Seebeck effect. Since they have no moving parts, they are inherently immune to mechanical failure or an intermittent need for maintenance. However, the challenge has been to effectively harvest waste heat with these modules to generate power, using passive processes. This work is focused on designing a device for optimized harvesting of waste energy from the ambient with a custom, evaporatively-cooled heat sink. This heat sink is designed to passively handle the cooling of the other side of the thermoelectric module so as to enable the attainment of a minimum of 5V, which is the minimum voltage required to power small mobile devices. The heat sink model is similar to a loop heat pipe but engineered for compactness. To ensure this level of efficacy is attained, several studies are made to optimize the wick. Non-metal wicks were considered as they do not contribute to an increase in temperature of the compensation chamber in loop heat pipes. A non-metal wick integrated with nanoparticles is tested and results show a clear thermal management enhancement over similar but virgin non-metal wicks, at over 16%. The heat source section of the device is optimized for energy-harvesting in low grade temperature regimes by incorporating a near-black body coating on the metal heat source section. Experimental results show that both the heat source and sink sections were able to induce sufficient thermal potential for the thermoelectric modules to passively generate up to 5V using eight 40mm by 40mm Bismuth Telluride modules in 3.5 minutes. The prototype is relatively cheap, inherently reliable and presents the possibility of passively harvesting low-grade waste heat for later use, including powering small electronic devices.

The Phase Change Memories (PCM) based on chalcogenide glasses are being considered recently as a possible replacement for conventional Non Volatile Random Access Memories (NVRAM). The main advantages of chalcogenide phase change memories are their direct write/overwrite capability, lower voltages of operation, large write/erase cycles, easiness to integrate with logic, etc. The phase change random access memories work on the principle of memory switching exhibited by chalcogenide glasses during which a local structural change (between amorphous and crystalline states) occurs due to an applied electric field. The development of newer phase change materials for NVRAM applications is based on synthesizing newer glass compositions and investigating their electrical switching characteristics by applying current/voltage pulses of different waveforms. The thermal studies on chalcogenide glasses which provide information about thermal stability, glass forming ability, etc., are also important while selecting a chalcogenide glass for PCM applications. The present thesis work deals with electrical switching and thermal studies on certain silicon based ternary telluride glasses (As-Te-Si, Ge-Te-Si and Al-Te-Si). The effect of network topological thresholds on the composition dependence of switching voltages and thermal parameters such as glass transition temperature, specific heat capacity, non-reversing enthalpy, etc., of these glasses has been investigated. The first chapter of the thesis provides an introduction to various properties of chalcogenide glasses, including their applications in phase change memories. The fundamental aspects of amorphous solids such as glass formation, glass transition, etc., are presented. Further, the concepts of rigidity percolation and self organization in glassy networks and the influence of local structural effects on the properties of glassy chalcogenides are discussed. Also, a brief history of evolution of phase change memories is presented. The second chapter deals with the experimental techniques employed in this thesis work; for sample preparation and for electrical switching studies, Alternating Differential Scanning Calorimetry (ADSC), Raman spectroscopy, NMR spectroscopy, etc. The third chapter discusses the electrical switching and thermal studies on As30Te70-xSix (2 ≤ x ≤ 22) and As40Te60-xSix (2 ≤ x ≤ 17) glasses. The composition dependence of electrical switching voltage (VT) and thermal parameters such as glass transition temperature (Tg), crystallization temperature (Tc), thermal stability (Tc-Tg), etc., reveals the occurrence of extended rigidity percolation and chemical thresholds in As30Te70-xSix and As40Te60-xSix glasses. Chapter 4 presents the electrical switching and thermal studies on Ge15Te85-xSix glasses (2 ≤ x ≤ 12). These glasses have been found to exhibit memory type electrical switching. While Ge15Te85-xSix glasses with x ≤ 5 exhibit a normal electrical switching, an unstable behavior is seen in the I-V characteristics of Ge15Te85-xSix glasses with x > 5 during the transition to ON state. Further, the switching voltage (VT) and initial resistance (R) are found to increase with addition of Si, exhibiting a change in slope at the rigidity percolation threshold of the Ge15Te85-xSix system. The ADSC studies on these glasses indicate the presence of an extended stiffness transition and a thermally reversing window in Ge15Te85-xSix in the composition range of 2 ≤ x ≤ 6. The fifth chapter deals with electrical switching investigations, thermal and structural studies on Al15Te85-xSix glasses (2 ≤ x ≤ 12). These glasses have been found to exhibit two crystallization reactions (Tc1 and Tc2) for compositions with x < 8 and a single stage crystallization is seen for compositions above x = 8. Also, a trough is seen in the composition dependence of non-reversing enthalpy (ΔHNR), based on which it is proposed that there is a thermally reversing window in Al15Te85-xSix glasses in the composition range 4 ≤ x ≤ 8. Further, Al15Te85-xSix glasses are found to exhibit a threshold type electrical switching at ON state currents less than 2 mA. The start and the end of the thermally reversing window seen in the thermal studies are exemplified by a kink and saturation in the composition dependence of switching voltages respectively. 27Al Solid State NMR measurements reveal that in Al15Te85-xSix glasses, Al atoms reside in 4-fold as well as 6-fold coordinated environments. Unlike in Al-As-Te glasses, there is no correlation seen between the composition dependence of the fraction of 4-fold and 6-fold coordinated aluminum atoms and the switching behavior of Al-Te-Si samples. Chapter 6 provides a comparison of the properties of the three glassy systems studied (As-Te-Si, Ge-Te-Si and Al-Te-Si), made to identify the system better suited for phase change memory applications. It is found that the Ge-Te-Si glassy system has better electrical/thermal properties for phase change memory applications. The seventh chapter describes easily reversible SET-RESET processes in Ge15Te83Si2 glass which is a promising candidate for phase change memory applications. This sample exhibits memory switching at a comparatively low threshold electric field (Eth) of 7.3 kV/cm. The SET and RESET processes have been achieved with 1 mA triangular current pulse for the SET process and 1 mA rectangle pulse (of 10 msec width) for RESET operation respectively. Further, a self-resetting effect is seen in this material upon excitation with a saw-tooth/square pulse. About 6.5x104 SET-RESET cycles have been achieved without any damage to the device. In chapter 8, results of in-situ Raman scattering studies on the structural changes occurring during the SET and RESET processes in Ge15Te83Si2 sample, are presented. It is found that the degree of disorder in the glass is reduced from OFF to SET state. The local structure of the sample under RESET condition is similar to that in the OFF state. The Raman results are found to be consistent with the switching results which indicate that the Ge15Te83Si2 glass can be SET and RESET easily. Further, Electron Microscopic studies on switched samples indicate the formation of nanometer sized particles of cSiTe2. A summary of the results obtained and the scope for future work are included in the chapter 9 of the thesis.

Chalcogenide glasses are a class of covalent amorphous semiconductors with interesting properties. The presence of short-range order and the pinned Fermi level are the two important properties that make them suitable for many applications. With flash memory technology reaching the scaling limit as per Moore’s law, alternate materials and techniques are being researched at for realizing next generation non-volatile memories. Two such possibilities that are being looked at are Phase Change Memory (PCM) and Programmable Metallization Cell (PMC) both of which make use of chalcogenide materials. This thesis starts with a survey of the work done so far in realizing PCMs in reality. For chalcogenides to be used as a main memory or as a replacement to FLASH technology, the electrical switching parameters like switching voltage, programming current, ON state and OFF state resistances, switching time and optical parameters like band gap are to be considered. A survey on the work done in this regard has revealed that various parameters such as chemical composition of the PC material, nature of additives used to enhance the performance of PCM, topological thresholds (Rigidity Percolation Threshold and Chemical Threshold), device geometry, thickness of the active volume, etc., influence the electrical switching parameters. This has motivated to further investigate the material and experimental parameters that affect switching and also to explore the possibility of multi level switching. In this thesis work, the feasibility of using two chalcogenide systems namely Si15Te85-xGex and Ge15Te85-xAgx in the form of amorphous thin films for PCM application is explored. In the process, electrical switching experiments have been carried out on thin films belonging to these systems and the results obtained are found to exhibit some interesting anomalies. Further experiments and analysis have been carried out to understand these anomalies. Finally, the dynamics of electrical switching has been investigated and presented for amorphous Si15Te85-xGex thin films. From these studies, it is also seen that multi state switching/multiple resistance levels of the material can be achieved by current controlled switching, the mechanisms of which have been further probed using XRD analysis and AFM studies. In addition, investigations have been carried out on the electrical switching behavior of amorphous Ge15Te85-xAgx thin film devices and optical band gap studies on amorphous Ge15Te85-xAgx thin films. Chapter one of the thesis, gives a brief introduction to the limitations in existing memory technology and the alternative memory technologies that are being researched, based on which it can be inferred that PCM is a promising candidate for the next generation non volatile memory. This chapter also discusses the principle of using PCM to store data, realization of PCM using chalcogenides, the material properties to be considered in designing PCM, the trade offs in the process of design and the current trends in PCM technology. Chapter two provides a brief review of the electrical switching phenomenon observed in various bulk chalcogenide glasses, as electrical switching is the underlying principle behind the working of a PCM. In the process of designing a memory, many parameters like read/write operation speed, data retentivity and life, etc., have to be optimized for which a thorough understanding on the dependence of electrical switching mechanism on various material parameters is essential. In this chapter, the dependence of electrical switching on parameters like network topological thresholds and electrical and thermal properties of the material is discussed. Doping is an efficient way of controlling the electrical parameters of chalcogenides. The nature of dopant also influences switching parameters and this also is briefly discussed. Chapter three provides a brief introduction to the different experimental techniques used for the thesis work such as bulk chalcogenide glass preparation, preparation of thin amorphous films, measurement of film thickness, confirmation of amorphous nature of the films using X-Ray Diffraction (XRD), electrical switching experiments using a custom made setup, crystallization study using XRD and Atomic Force Microscopy (AFM) and optical band gap studies using UV-Vis spectrometer. Vt is an important parameter in the design of a PCM. Chapter four discusses the dependence of Switching voltage, Vt, on input energy. It is already established that the Vt is influenced by the composition of the base glass, nature of dopants, thickness of films and by the ambient temperature. Based on the results of electrical switching experiments in Si15Te74Ge11 amorphous thin films a comprehensive analysis has been done to understand the kinetics of electrical switching. Chapter five discusses a current controlled crystallization technique that can be used to realize multi-bit storage with a single layer of chalcogenide material. In case of PCM, data is stored as structural information; the memory cell in the amorphous state is read as data ‘0’ and the memory cell in crystalline state is read as data ‘1’. This is accomplished through the process of electrical switching. In order to increase the memory density or storage density, multi-bit storage is being probed at by having multiple layers of chalcogenide material. However, with this technique, the problems of inter-diffusion between different layers cannot be ruled out. In this thesis work, a current controlled crystallization technique has been used to achieve multiple stable resistance states in Si15Te75Ge10 thin films. Chapter six discusses the mechanism behind multi state switching exhibited by certain compositions of Si15Te85-xGex thin films. Crystallization studies on certain Si15Te85-xGex films have been carried out using XRD and AFM to understand the phenomenon of multiple states. The results of these experiments and analysis are presented in this chapter. Chapter seven discusses the results of electrical switching experiments and optical band gap studies on amorphous Ge15Te85-xAgx thin films. Chapter eight gives the conclusion and scope for future work.

Transparente Elektroden finden breite Verwendung in unterschiedlichen kommerziellen Produkten. Dünnschichtsolarzellen basieren ebenso auf diesen Funktionsschichten wie Displays oder organische Leuchtdioden. Im Falle von Dünnschichtsolarzellen kann durch gezielte Einstellung der Oberflächentextur der transparenten Elektrode ein entscheidender Einfluss auf die erreichbare Effizienz genommen werden. Dabei wird eine Verlängerung der Weglänge des Lichtes im Absorbermaterial durch Mehrfachreflexionen angestrebt. Häufig werden dafür Schichten transparenter leitfähiger Oxide (TCO) gezielt texturiert. Eine weitere Möglichkeit zur Erzeugung transparenter Elektroden stellt die Verwendung feiner Metallgitter dar. Diese ermöglichen hohe Leitfähigkeiten im Bereich der Gitterstege und hohe Transparenz im Bereich zwischen den Stegen. In dieser Arbeit sollte ein auf nasschemischen Prozessen basierendes Verfahren entwickelt werden, mit dem es möglich ist, sowohl strukturierte TCO-Elektroden als auch Metallgitter unterschiedlicher Geometrien gezielt herzustellen. Die Leistungsfähigkeit der Elektroden sollte anhand der Integration in entsprechende Bauteile bewertet werden. Namentlich sollte dieser Prozess für Cd2SnO4 (engl. Cadmium Tin Oxide, CTO) als ein TCO-Material hoher Transparenz und Leitfähigkeit sowie für Silber und Kupfer als metallische Systeme anwendbar sein. Als zielführende Methode kam die Nanoprägelithographie (von engl. Nanoimprint Lithography, NIL) zum Einsatz. Dieses Verfahren erlaubt die schnelle, einfache und kostengünstige Herstellung strukturierter Oberflächen. Grundsätzlich wird dazu ein strukturierter Elastomerstempel in eine Schicht eines zu vernetzenden Materials gepresst. Während des Pressens findet die Vernetzung statt. Nach anschließender Separation von Stempel und Schicht resultiert eine strukturierte Oberfläche. Gängige Präkursorensysteme für anorganische Verbindungen, bei denen Vernetzungsprozesse ablaufen, stellen Sol-Gel-Methoden und sogenannte polymere Präkursoren dar. Für letztere werden Metallzitrate mit Ethylenglykol verestert, um ein vernetztes Polymer zu generieren. Nach thermischem Entfernen der Organik bleibt das Metalloxid zurück. Im Rahmen dieser Arbeit ist ein Präkursorensystem entwickelt worden, das Metallionen komplexiert, auf Glassubstrate beschichtet werden kann und eine thermische Polymerisation erlaubt. Aus dem erhaltenen polymeren Präkursor konnten die Zielverbindungen durch thermisches Zersetzen einerseits in Pulverform und andererseits über vorhergehende Schleuderbeschichtung in Form dünner Schichten erhalten werden. Im Falle des kubischen Cd2SnO4 wurde im Rahmen dieser Arbeit erstmals eine Nanopulver-Synthese mit phasenreinem Produkt aus flüssigem Präkursor beschrieben. Dafür stellten sich der Anteil der verwendeten organischen Bestandteile sowie die Zersetzungsgeschwindigkeit als entscheidende Einflussparameter heraus. Zudem wurden CTO Dünnschichten mit dem beschriebene Präkursor hergestellt. Eine optimale Brenntemperatur zur Erzeugung phasenreiner CTO-Schichten von 700 ‰ wurde ermittelt. Die Zersetzungsgeschwindigkeit (bzw. Aufheizrate) beeinflusste die Oberflächenmorphologie der erhaltenen Schichten maßgeblich. Eine schrittweise Zersetzung (100 ‰°C, 200 °C‰, Zieltemperatur) führte dabei in effizienter Weise zu kompakten Schichten. Diese zeigten sehr gute optische und elektronische Eigenschaften. So konnten etwa 300 nm dicke CTO-Schichten mit spezifischen Widerständen von ca. 1 • 10^(−5) Ohm m bei einer Transmission von etwa 80 % (inklusive Glassubstrat) erhalten werden. Derartige CTO-Schichten konnten erfolgreich als transparente Frontelektroden für a-Si Dünnschichtsolarzellen verwendet werden. Ein positiver Einfluss periodischer Linienstrukturen auf die Lichteinfangeigenschaften und den resultierenden Photostrom im Vergleich zu flachen CTO-Schichten wurde bestätigt. Auch für die Herstellung von CdTe-Dünnschichtsolarzellen konnten die CTO-Schichten erfolgreich eingesetzt werden. Die erreichten Effizienzen lagen jedoch lediglich im Bereich von 3 bis 3,6 %. Ein signifikanter Unterschied zwischen flachen und strukturierten Proben konnte nicht ausgemacht werden. Durch die reduzierenden Eigenschaften von Zitronensäure und Ethylenglykol gegenüber Ag+ und Cu2+ Ionen war es möglich, die Metalle in elementarer Form durch einfache thermische Behandlung des Präkursors zu erhalten. Während dieser Prozess für silberhaltige Systeme relativ einfach zu realisieren war, musste bei kupferhaltigen Proben die Bildung oxidischer Nebenphasen festgestellt werden. So war für Letzteres eine reduktive Nachbehandlung vollständig oxidierter Proben im Wasserstoffplasma zielführend und lieferte leitfähige Dünnschichten mit hohem Cu(0)-Anteil. Im Falle von Silber führte eine geeignete thermische Behandlung der Präkursorschicht zu dünnen, leitfähigen Silberschichten mit spezifischen Widerständen von ca. 6 • 10^(−8) Ohm m (Festkörper: ca.1 • 10^(−8) Ohm m). Die Übertragung des NIL-Prozesses gelang sowohl für silber- als auch kupferhaltige Systeme. Mit NIL-strukturierten Silberdünnschichten gelang so die Herstellung semitransparenter Elektroden mit spezifischen Widerständen von 2,2 • 10^(−7) Ohm m, welche in Elektrolumineszenzbauteilen verwendet wurden. Aufgrund der relativ niedrigen Temperaturen, die für die Zersetzung des Silberpräkursors nötig waren (ca. 250 ‰ ), war die Fertigung entsprechender Elektroden und Bauteile auch auf Polyimidfolien möglich. Insgesamt bleibt die Erkenntnis, dass NIL-strukturierte dünne Schichten erfolgreich in optoelektronische Bauteile integriert werden konnten. Variable Präkursorsysteme erlauben die Herstellung verschiedener Schichten und somit Anwendungen in unterschiedlichen Bauteilen. Polymere Präkursoren haben sich als geeignet für dieses Vorgehen erwiesen und können relativ einfach auf diverse oxidische Stoffsysteme übertragen werden. Gleichzeitig eignen sie sich zur Herstellung metallischer transparenter Elektroden durch NIL-Strukturierung, was insbesondere im Hinblick auf flexible Bauteile von Vorteil ist.

The ability to tune the properties over a wide range of values by changing the additives, composition, etc., has made chalcogenide glassy semiconductors, most interesting from both fundamental physics as well as technology point of view. In particular, the occurrence of the two network topological thresholds namely the Rigidity Percolation Threshold (RPT) and the Chemical Threshold (CT) and their influence on various properties of chalcogenide glasses have been of immense interest during the last three decades. The Rigidity Percolation Threshold (also known as the Stiffness Threshold or Mechanical Threshold) corresponds to the composition at which the material transforms from a floppy polymeric glass to a rigid amorphous solid, whereas at Chemical Threshold the sample tends towards an ordered state. Though the rigidity percolation has been considered for long to occur at a critical threshold defined by the constraint’s theory, the recent theoretical and experimental investigations have found the RPT to occur over a range of compositions. In systems exhibiting an extended rigidity percolation, two distinct transitions namely from a floppy to an isostatically rigid phase and from an isostatically rigid to a stressed rigid phase are seen. In the category of chalcogenide glasses, tellurides have been found to exhibit interesting properties including the phenomenon of electrical switching which finds applications in Phase Change Memories (PCM). Studies on various thermal, electrical and photoelectrical properties of glassy tellurides help us in identifying suitable materials for different technological applications. This thesis deals with Differential Scanning Calorimetric (DSC) & Temperature Modulated Alternating Differential Scanning Calorimetric (ADSC) studies, electrical switching investigations, photoconductivity & photothermal measurements on certain metal doped telluride glasses. The composition dependence of properties such as glass transition & crystallization temperatures, switching voltage, thermal diffusivity, photosensitivity, etc., have been analyzed to obtain information about topological thresholds, thermally reversing window, etc. The first chapter of thesis provides an overview of properties of amorphous semiconductors, in particular chalcogenide glasses. The local & defect structure, the electronic band structure & electrical properties, electrical switching behavior, etc., are discussed in detail. The theoretical aspects related to the experiments undertaken in this thesis work have also been described. The instrumentation used for various experiments conducted to measure thermal, electrical, photoelectrical and photothermal properties have been discussed in chapter two. The chapter three deals with the photocurrent measurements on As40Te60-xInx (7.5 ≤ x ≤ 16.5) glasses. In these samples, it has been found that the photocurrent increases with illumination, which is understood on the basis of the large dielectric constant and also due to the presence of a large number of positively charged defect states. Further, the composition dependence of the conductivity activation energy and the photosensitivity exhibit a maximum at x = 12.5 (<r> = 2.65) and a minimum at x = 15.0 (<r> = 2.70) which has been identified to be the Rigidity Percolation Threshold (RPT) and the Chemical Threshold (CT) respectively. The results of electrical switching, DSC and Photothermal Deflection (PTD) studies on As20Te80-xGax (7.5 ≤ x ≤ 18.5) glasses, undertaken to elucidate the network topological thresholds, are described in chapter four. It has been found that all the As20Te80-xGax glasses studied exhibit memory type electrical switching. The switching voltage (VT) of these glasses increases monotonically with x, in the composition range 7.5 ≤ x ≤ 15.0. The increase in VT with gallium addition leads to a local maximum at x = 15.0 and VT decreases with x thereafter, reaching a distinct minimum at x = 17.5. Based on the variation with composition of the electrical switching voltages, the composition x = 15.0 and x = 17.5 have been identified to be the rigidity percolation and chemical thresholds of the As20Te80-xGax glassy system respectively. Further, the DSC studies indicate that As20Te80-xGax glasses exhibit a single glass transition (Tg) and two crystallization reactions (Tc1 & Tc2) upon heating. There is no appreciable change in Tg of As20Te80-xGax glasses with the addition of upto about10 atom% of Ga, whereas a continuous increase is seen in the crystallization temperature (Tc1). It is interesting to note that both Tg and Tc1 exhibit a maximum at x = 15.0 and a minimum at x = 17.5, the compositions identified to be the RPT and CT respectively by the switching experiments. The composition dependence of thermal diffusivity estimated from the PTD signal, indicate the occurrence of an extended stiffness transition in As20Te80-xGax glasses, with the compositions x = 9.0 and x = 15.0 being the onset and the completion of an extended rigidity percolation. A maximum and a minimum are seen in the thermal diffusivity respectively at these compositions. Further, a second maximum is seen in the thermal diffusivity of As20Te80-xGax glasses, the Chemical Threshold (CT) of the glassy system. The fifth chapter of the thesis describes the ADSC, electrical switching and photocurrent measurements on Ge15Te85-xInx (1 ≤ x ≤ 11) glasses. It is found there is not much change in the Tg of Ge15Te85-xInx glasses in the composition range 1 ≤ x ≤ 3. An increase is seen in Tg beyond x = 3, which continues until x = 11. Further, the composition dependence of non-reversing enthalpy shows the presence of a thermally reversing window in the compositions range x = 3 and x = 7. Electrical switching studies indicate that Ge15Te85-xInx glasses exhibit threshold type of switching at input currents below 2 mA. It is observed that switching voltages decrease initially with indium addition, exhibiting a minimum at x = 3, the onset of the extended rigidity percolation as revealed by ADSC. An increase is seen in VT above x = 3, which proceeds till x = 8, with a change in slope (lower to higher) seen around 7 atom% of indium which corresponds to the completion of the stiffness transition. The reversal in trend exhibited in the variation of VT at x = 8, leads to a well defined minimum around x = 9, the chemical threshold of the Ge15Te85-xInx glassy system. Photocurrent measurements indicate that there is no photodegradation in Ge15Te85-xInx glasses with x < 3, whereas samples with x ≥ 3 show photodegradation behavior. The composition dependent variation in the glass transition temperature has been attributed for this behavior. Further, the composition dependence of photo sensitivity has been found to show the signatures of the extended rigidity percolation and the chemical threshold in Ge15Te85-xInx glasses. The last chapter of thesis (chapter six) summarizes the results obtained and also the scope of future work to be undertaken.

Philosophiae Doctor - PhD / Breast cancer is regarded as the most common cancer in South Africa and its rate of occurrence is increasing. About one in every 31 South African women are at the risk of developing breast cancer and early diagnosis and treatment guarantee 90% survival rate. Tamoxifen is the drugs of choice for the treatment of all stages of breast cancer. The drug binds with estrogen receptor (ER) to minimize the transcription of estrogen dependent genes. However, nearly 50% of ER-positive breast cancer patients either become resistant or fail to respond to tamoxifen resulting in a serious clinical challenge in breast cancer management. The Grand Health Challenges of South Africa includes the development of cost effective diagnostic systems suitable for early detection of diseases and drug resistivity for timely invention and better patient management. / 2020-08-31

The objective of this study is analysing the characteristics of five different solar cell technologies regarding their efficiency, fill factor, cost and environmental impacts and comparing their improvement records over years considering their efficiency. The five solar cell technologies of interest are amorphous silicon, monocrystalline silicon, polycrystalline silicon, cupper indium gallium selenide thin film and cadmium telluride thin film. The structure and manufacturing process of each of cell technologies were discussed. The study was conducted by the aid of available scientific reports regarding the electrical characteristics of different solar cell technologies. The extracted information regarding efficiency rate and fill factor was analysed using graphs and significant findings are discussed. The five technologies are also compared regarding their cost and ease of fabrication and their impacts on environment and recycling challenges. The result of this study is suggesting the most promising technology that may be the optimal option for further investment and research.

In this work, we have designed, simulated, fabricated and characterized homojunction Hg1-xCdxTe detector for high operating temperature in the MWIR region. The IR photon detectors need cryogenic cooling to suppress thermal generation. The temperature of operation in narrow gap semiconductor devices is limited by the noise due to statistical nature of thermal generation-recombination in narrow gap semiconductors. To make IR systems affordable they have to be operated without cooling or with minimal cooling compatible with low cost, low power and long life. Several fundamental and technological limitations to uncooled operation of photon detectors have been discussed in Chapter-1 of this thesis. Way and means adopted to increase the operating temperature, such as non-equilibrium operation, use of multilayer stacked hetero¬structures, optical immersion etc. have also been discussed. Key to improving the detector performance at any temperature is reduction of dark currents to level below the photocurrent and ultimately to the level where detector noise is determined by the fluctuations in photon flux from the scene (BLIP limit). In addition, design of present generation uncooled Hg1-xCdxTe infrared photon detectors relies on complex hetero-structures with a basic unit cell of type n+/π/p+. Theoretical modeling and numerical simulations on TLHJ device consisting of backside illuminated n+/π/p+ photodiodes have been performed. A numerical model for solving carrier transport equations for Hg1-xCdxTe infrared photodiodes was developed in MATLAB. Finite difference discretization of carrier transport equations and successive over relaxation method have been adopted. Numerical models are more appropriate than analytical models when analyzing multi-layer hetero-structures because we can account for realistic doping profiles, compositional grading and hetero-structures using this model. The model can be suitably modified to accommodate different device architectures, designs, material properties and operating temperature. Such a generalized model is useful to a device designer to customize the detector performance as per the availability of the material to suit the application specific requirements. The present work therefore proposes a more flexible, accurate and generalized methodology to accommodate the user needs by simulating the position dependence of carrier concentration, electrostatic potential and g-r rates and their effect on detector performance vis-à¬vis contact doping, absorber doping and absorber width on device performance. We detail aspects of our simulation model by developing a library of Hg1-xCdxTe properties using analytical and empirical expressions for material parameters (energy band gap, electron affinity, intrinsic carrier concentration, carrier effective mass, carrier mobility, dielectric constant and absorption coefficient). The PDEs were solved using the FDM coupled with SOR method. Behavior of Hg1-xCdxTe diodes (homo/hetero-junction) under different biasing, illumination and non equilibrium situations were modeled. Model has been validated for experimental measured data on n on p Hg1-xCdxTe photodiodes. The numerical computations are next applied to simulation/modeling of MWIR (λc=4.5 μm) n+/π/p+ TLHJ device for operation at T=250K. Several recombination processes occur in Hg1¬-xCdxTe depending on material quality, operating temperature, device design and processing conditions. Detailed mathematical models of radiative, Auger, Shockley Read Hall (SRH), surface recombination and optical g-r are analyzed and their effect on carrier lifetime have been evaluated. Analytical models for dark currents affecting the performance of Hg1-xCdxTe diodes at different temperatures are discussed. The mechanisms contributing to dark current are: (i) the thermal diffusion of minority carriers from the neutral regions (IDiff); (ii) generation-recombination from the space charge region of diode (IG-R) (iii) trap assisted tunneling currents, wherein the traps in the depletion region or the traps in the quasi neutral p region close to the depletion edge participate in the tunneling process(ITAT); (iii) band-to-band tunneling currents (IBTB) and (iv) surface leakage currents due to shunt resistance. Total current of a photodiode is ITOT=IDiff+IG-R+ITAT+IBTB+ISH-IP, where IP is the photocurrent. We evaluate the variation of electrostatic potential, carrier concentration, and electric field and g-r profiles as a function of position. The effect of variation in absorber width, doping and contact doping on D* is also analyzed. The mathematical models of different g-r processes (Auger, SRH, radiative, surface recombination and optical generation) affecting the device performance analyzed and their affect on carrier lifetimes are investigated. Responsivity ~3.25Amp-Watt-1, noise current~2pA/Hz1/2 and D* ~8x109 cmHz1/2watt-1 at 0.1V reverse bias have been calculated using optimized values of doping concentration, absorber width and carrier lifetime. The suitability of the method has been illustrated by demonstrating the feasibility of achieving the optimum device performance by carefully selecting the device design and other parameters. The numerical models provided insight about the operation and performance of Hg1-xCdxTe Auger-suppressed infrared photodiodes. Hetero-junction configuration increases the dynamic resistance, while the heavily doped contacts reduce the contact resistance. Wide gap/heavily doped contacts present a barrier to injection of minority carries into the absorber layer. At the same time they allow collection of minority carriers generated in the absorber region at the contacts. Hg1-xCdxTe hetero-diodes are grown by MOCVD and MBE with precise doping and compositional gradient control to reduce g-r contributions from defects and dislocations to the dark current in order to reap advantages of Auger suppression. Measured dark currents in hetero-junction photodiodes continue to be larger than expected in spite of the advancements in MBE technique. Delineation of an array on hetero-structures involves mesa separation of the diodes thus creating additional surface requiring passivation. Overall, the whole effort of fabricating a hetero Hg1-xCdxTe detector array is disproportionate to the overall gain in the performance. Therefore, we employ a much simpler fabrication process of homo-junction Hg1-xCdxTe detectors. It involves a planar device fabrication approach thus minimizing the surface passivation problem. We have deliberated upon the specific growth, characterization techniques and processing steps employed in our study. We discuss some of the experimental issues. We also presented results on the novel processing techniques developed that are potentially applicable to HOT technology and Hg1-xCdxTe technology in general. Hg1-xCdxTe (x=0.27-0.31) layer of ~ 15×15mm2 area and 15-20µm thickness is grown on CdZnTe substrate by Liquid Phase Epitaxy (LPE) in-house. As grown wafer is vacancy doped p-type with a carrier concentration of ~5×1015-1x1016 cm-3 and hole mobility of ~400cm2V-1s-1@80K. Planar n+/ν/p junction ~2-3µm deep is formed by B+ ion implantation and subsequent annealing; details are outlined in Chapter-4. Hall measurements and differential Hall measurements were used to find the carrier concentration, carrier mobility, resistivity of the wafer. The diodes are formed in the form of a 2D array along with various PEV’s for process characterization. Composition of Hg1-xCdxTe wafers used for the work is in the range of 0.27¬ 0.31 as determined by FTIR, corresponding to cutoff wavelength of 4.5-6.5µm. Junction depth and doping profile of the diodes after ion implantation was characterized by differential Hall technique. Transient minority carrier lifetime in fabricated MWIR n+/ν/p Hg1-xCdxTe (x=0.27) diodes were characterized using diode reverse-recovery technique. We prefer this method because it is a direct indicator of device as well as material quality post processing. By this time the device has undergone all the chemical/mechanical treatments and the measured lifetime is the cumulative of g-r mechanisms operative in bulk, space charge region and surface of diode. The value of lifetime extracted from the measured data lies in the range of 80-160ns. Variable temperature lifetime data was also extracted to determine the prevalent g-r process operative in the device. Diode dark I-V and junction C-V measurements were also made to correlate the observed behavior of the measured lifetime with g-r processes. Evidence of Auger suppression at room temperature is seen in the dark I-V characteristics via observation of negative differential resistance in the homo-junction Hg1-xCdxTe diodes. The experimental data is fitted using the numerical and analytical models developed. Based on this fitting, the current mechanisms limiting the dark current in these photodiodes are extracted. An improved analytical I-V model is reported by incorporating TAT and electric field enhanced Shockley-Read-Hall generation recombination process due to dislocations. Tunneling currents are fitted before and after the Auger suppression of carriers with energy level of trap (Et), trap density (Nt) and the doping concentrations of n+ and νregions as fitting parameters. Values of Et and Nt were determined as 0.78-0.80Eg and ~7-9×1014 cm-3 respectively in all cases. Doping concentration of νregion was found to exhibit non-equilibrium depletion from a value of 2×1016 to 4×1015 cm-3. Quantum efficiency of the diodes was found to ~25-30%. Note, that these are wafer level measurements on unpackaged device without backside AR coating. In addition to junction diodes, we present results on several PEV's such as VADA, MIS/MIM capacitors and TLM structures both at room and low temperature. Variable temperature measurements for a VADA tile and subsequent analysis provide evidence of g-r processes originating from defects, dislocations and dislocation loops, which are non-uniformly distributed across the Hg1-xCdxTe wafer and contributes to TAT current at high temperatures. MIS analysis yielded surface charge density lying between 3×1010-1×1011 cm-2 for ZnS/CdTe surface corresponding to a near flat band condition. Results of low and variable temperature measurements on the devices have also been shown to correlate it with the possibility of operating the device at mid temperatures such as 180-250K.