La mission Darwin, un projet d'interférométrie spatiale initié par l'ESA, nécessite l'utilisation de filtres modaux fonctionnant dans la gamme spectrale [6-20 µm]. Dans le cadre de ce travail, nous proposons la réalisation de filtres modaux basés sur des guides d'onde « tout tellurures » obtenus par la méthode d'empilement et de gravure. L'originalité de ce travail réside dans le fait que les guides réalisés sont de grandes dimensions (couches épaisses et profondeurs de gravure importantes), pour satisfaire aux exigences du projet. La première étape a donc consisté à choisir une méthode de dépôt qui permette d'obtenir des couches épaisses. La co-évaporation thermique a ainsi été mise en place et les paramètres de dépôt optimisés. Des couches d'épaisseur pouvant atteindre 17 µm, de bonne qualité (adhérentes, amorphes, denses et homogènes), transparentes de 6 à 20 µm et d'indice de réfraction contrôlé ont pu être obtenues. La gravure physique réactive (RIE) de ces couches, en utilisant un mélange gazeux CHF3/O2/Ar, a constitué la deuxième partie de ce travail. L'obtention de marches de profondeur pouvant dépasser 10 µm, présentant des profils de gravure de qualité, a été démontrée. Les différents guides d'onde IR réalisés ont été caractérisés optiquement après préparation de leurs faces d'entrée et de sortie. L'observation d'un bon confinement de la lumière sur un banc de guidage à λ = 10,6 µm et l'obtention d'un taux de réjection de 10-3 sur un banc d'interférométrie annulante nous ont permis de confirmer que les guides d'onde à base de couches tellurures et réalisés par la méthode d'empilement et de gravure constituaient une solution de choix en tant que filtres modaux pour l'interférométrie spatiale. / The Darwin mission, an interferometric spatial project initiated by ESA, requires modal filters being able to work in the whole spectral range [6-20 µm]. In the framework of this work, we propose the realization of modal filters based on waveguides obtained by stacking and etching chalcogenide films. The originality of this work lies in the fact that the realized waveguides have large dimensions (thick films and deep etching), to satisfy the project requirements. The first step consisted in choosing the deposition method which allows obtaining thick films. The thermal co-evaporation was setting up and the deposition parameters were optimized. Films with thickness which can reach 17 µm, of good quality (adhesive, amorphous, dense and homogeneous), transparent from 6 to 20 µm and with controlled refractive index were obtained. The physical reactive etching of these films, by using a gas mixture CHF3/O2/Ar, constituted the second part of this work. The obtaining of deep rib which can exceed 10 µm, presenting etching profiles of good quality was demonstrated. The elaborated IR waveguides were optically characterized after preparation of their entrance and exit faces. The observation of light confinement on a guiding bench at λ = 10.6 µm and the obtaining of a rejection rate of 10-3 on a nulling interferometry bench allowed confirming that the waveguides based on the stacking and etching of telluride films was a choice solution as modal filters for the spatial interferometry.

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.

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.