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M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology / The understanding of the fundamental properties and potential use of semiconductor materials in nanotechnology has stimulated the interest of many researchers. Coordination compounds containing ligands with chalcogenide atoms as donors have received considerable attention. Among these chalcogenide ligands, thiourea and urea have been extensively used previously to form single source precursors for the synthesis of group II–VI semiconductor nanoparticles. The synthesis and study of semiconductor nanocrystals has become a subject area of considerable research interest because they have potentially useful applications such as biomedical imaging, sensing, light-emitting diodes (LEDs), photovoltaics and displays. In this work, special attention has been given to the synthesis and characterization of cadmium and nickel chalcogenides nanoparticles because of their interesting and unique optical properties, using a single source precursor method. The mixed chalcogenide sources are also explored for their complexes or simple reactions to produce semiconductor nanoparticles. The advantages of single molecular precursors over other existing methods for the synthesis of metal chalcogenide nanoparticles has proven to be a more efficient route for the synthesis of high-quality nanocrystals. Cadmium and nickel complexes of urea and thiourea were successfully synthesized by refluxing metal salts of cadmium and nickel with thiourea and urea at 30-40 °C for an hour and the complex mixture was cooled at room temperature. The synthesized complexes were washed with methanol and acetone to remove impurities and dried in air. All other complexes were synthesized using the same refluxing synthesis method mentioned above. The characterization of all complexes was done using Fourier-Transform infrared spectroscopy, thermogravimetric analysis and CARLO ERBA elemental analysis. Nickel thiourea and cadmium thiourea complexes were found to be coordinating with the center metal through a sulfur atom, and the urea complexes through an oxygen atom. This observation of the coordination of metals with ligands makes these complexes suitable for use as the single source precursor for the synthesis of metal chalcogenides nanoparticles. The six resulted complexes from above synthesis are of cadmium sulphide, cadmium oxide, and nickel sulphide, nickel oxide. The TGA showed that all the complexes were stable at room temperature, as they decomposed around 200 °C, which makes these complexes suitable to be used for the synthesis of nanoparticles. The synthesized complexes reported in this study were used as a single source molecular precursor in the preparation of cadmium oxide, cadmium sulfide, nickel oxide, and nickel sulfide nanoparticles. The precursors were thermalized under nitrogen gas while refluxing at 160 °C for 1 hour, using HDA as the capping agent and TOP was used as the solvent. Crystalline semiconducting nanoparticles were obtained as the end product for all complexes, the resulting nanoparticles were washed with acetone to remove any impurities. The UV-Vis spectra of all the nanoparticles were blue-shifted, with their PL spectra red-shifted from the maximum absorption peak due to change in size of particles from bulk to nano-size. XRD pattern of CdS nanoparticles from Cd-thiourea suggested that a hexagonal phase of CdS was formed, and TEM analysis showed large particle sizes that were polydispersed with the dominance of cubic and rod shaped particles. The XRD patterns of CdS nanoparticles from cadmium thiourea and urea mixture showed the mixture of hexagonal and cubic phase nanoparticles with the predominance of cubic phase and its TEM images shows small particles size ranging from less than 50 nm, and the particles were polydispersed with the predominance of spherical nanoparticles. The XRD pattern of CdO nanoparticles showed the cubic phase nanoparticles with the existence of broad peaks indicating small particle size distribution. The TEM images of CdO nanoparticles confirmed the XRD data showing small particle size distribution with a size average of 6.8 nm. The NiS nanoparticles synthesized from Ni-thiourea complex showed narrow peaks with hkl indices indicating hexagonal phase. Particles has no clear morphology due to the agglomeration of the nanoparticles that can be caused by the instability of the nanoparticles because of their high surface area. A cluster of particles can be observed from the TEM images, making it difficult to determine the particle size and shape of NiS particles from Ni-thiourea complex. NiS particles from nickel thiourea and urea mixture also showed XRD patterns of the hexagonal plane and TEM showed small size conjugated nanocrystals. The TEM of NiO indicated a spherical morphology, existence of other morphology rather than spherical can also be observed from the image. The average particle size was 8 nm, and XRD pattern showed the cubic phase of NiO nanocrystals.

This study aimed to investigate methods for determining the temperature dependence of the refractive index and absorption of IR-transparent materials through literary studies and experimental tests. Results from the experimental trials were hard to obtain due to the inherent difficulty of measuring optical properties and yielded only temperature trends of transmittance and reflectance. Despite this, the results could be used for speculation regarding the temperature dependency of the refractive index and the absorption which provides insights into the optical properties of a material. There are several suggestions to improve measurements using this method for future work to be able to determine precise values of the properties. Two additional methods have been reviewed with a literary study, the minimum deviation prism method and the improved Swanepoel thin film method. Both methods are regarded as promising candidates for determining refractive index and its temperature dependence with good accuracy. However, the improved Swanepoel method stands out as the more promising candidate. The determination of absorption and its temperature dependence is established to be inherently hard to determine with the experimental method and the two researched methods, thus suggestions for measuring the absorption in future work are given.

Silver containing chalcogenide glasses have been extensively studied during the last few decades; the main interest in these materials being their electrical conductivity which changes by several orders of magnitude upon silver doping. Glassy chalcogenides doped with silver have applications in optical elements, gratings, micro-lenses, waveguides, bio & chemical sensors, solid electrolytes, batteries, etc. Chalcohalide glasses have become important in the recent times, from both scientific & technological points of view, due to the interesting properties exhibited by these glasses such as the transparency in the infrared region, the stability against devitrification, solubility of rare earth elements, etc. In this thesis work, the thermal properties and electrical switching behavior of certain silver and iodine doped chalcogenide glasses have been investigated The thesis contains five chapters: Chapter 1: This chapter is an introduction to the fundamental aspects of amorphous semiconductors with a particular reference to chalcogenide glasses. The advantages and applications of chalcogenide glasses are also described. Chapter 2: The methods of preparation and characterization of the glasses investigated are described in this chapter. Also, the details of the experiments undertaken, namely temperature modulated Alternating Differential Scanning Calorimetry (ADSC), electrical switching analysis, Photo-thermal Deflection Spectroscopy (PDS), etc, are outlined. Chapter 3: In this chapter, the thermal behavior and electrical switching of silver doped Ge-Se and As-Se chalcogenide glasses are described. Bulk, melt-quenched Se-rich Ge0.15Se0.85-xAgx glasses have been found to be microscopically phase separated and composed of Ag2Se clusters and GeSe2-Se network. When the silver concentration exceeds 10 atom %, the Ag2Se clusters embedded in the GeSe2-Se network percolate. The signature of this percolation threshold is clearly observed as the sudden appearance of two exothermic crystallization peaks in ADSC runs. Density, molar volume and micro hardness studies also strongly support the view of a percolation transition. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be connected with the silver phase percolation. It has been found that Ge0.15Se0.85-xAgx glasses of lower silver concentration (x = 0.07 and 0.08) do not exhibit electrical switching at voltages up to 1100 V. A negative resistance behavior and threshold type electrical switching is seen in Ge0.15Se0.85-xAgx samples with x 0.09. Also, fluctuations are observed in the I-V characteristics of these samples, which have been attributed to the difference in thermal conductivities between the Ag2Se inclusions and the Ge-Se base glass. A sharp drop has been observed in the switching voltage with Ag concentration which is due to the more metallic nature of silver and the presence of Ag+ ions. Further, the saturation in the decrease of VT around x = 0.10, is related to silver phase percolation in these glasses. Bulk As20Se80-xAgx glasses (0 x 15) have been found to exhibit two endothermic glass transitions and two exothermic crystallization reactions on heating. Based on which it is suggested that As20Se80-xAgx glasses are also microscopically phase separated, containing Ag2Se phases embedded in an As-Se backbone. The occurrence of microscopic phase separation in As20Se80-xAgx glasses is also confirmed by SEM studies. With increasing silver concentration, the Ag2Se phase percolates in the As-Se matrix, with a well-defined percolation threshold at x = 8. This silver phase percolation is exemplified by sudden jumps in the composition dependence of the second crystallization peak and non-reversible heat-flow, Hnr obtained at the second glass transition reaction of As20Se80-xAgx glasses. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be associated with the observed silver phase percolation. Like Ge0.15Se0.85-xAgx glasses, As20Se80-xAgx glasses also exhibit threshold type electrical switching with fluctuations in the I-V characteristics; these fluctuations have been attributed to the difference in thermal conductivities between the Ag2Se inclusions and the As-Se base glass. A sharp drop has been observed in the switching voltage with Ag concentration which is due to the more metallic nature of silver and the presence of Ag+ ions. Further, the saturation in the decrease of VT around x = 8, is found to be related to silver phase percolation in these glasses, which has been proposed on the basis of ADSC experiments. Chapter 4: The chapter 4 deals with thermal studies, electrical switching investigations and Photo-thermal Deflection Spectroscopic (PDS) measurements on certain Ge-Te-I and As-Te-I chalcohalide glasses. It has been found that the compositional variation of the glass transition temperature of Ge22Te78-xIx glasses, obtained by Alternating Differential Scanning Calorimetry (ADSC), exhibits a broad hump around 5 atom % of iodine. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Hnr) of Ge22Te78-xIx glasses at x = 5, which is suggestive of a thermally reversing window at this composition. Electrical switching studies on Ge22Te78-xIx glasses indicate that these glasses exhibit memory type electrical switching. At lower iodine concentrations, a decrease is seen in switching voltages with an increase in iodine content (in comparison with the base Ge22Te78 glass), which is due to the decrease in network connectivity. The increase seen in switching voltages of Ge22Te78-xIx glasses at higher iodine contents, suggests that the influence of the metallicity is stronger at higher iodine proportions. It is also interesting to note that the composition dependence of the threshold voltages shows a slope change at x = 5, the inverse rigidity percolation threshold of the Ge22Te78-xIx system. . Further, it is found that the thermal diffusivities ( D) of Ge22Te78-xIx glasses decrease with the increase in iodine content, which has been understood on the basis of fragmentation of the Ge-Te network with the addition of iodine. Also, a cusp is seen in the composition dependence of thermal diffusivity at the composition x = 5 (average coordination number, r = 2.39), which has been identified to be the inverse rigidity percolation threshold of the system at which the network connectivity is lost. ADSC studies on As45Te55-xIx chalcohalide glasses (3 x 10) reveal that there is not much variation in the glass transition temperature of As45Te55-xIx glasses, even though there is a wide variation in r . Based on this observation we suggest that the variation in glass transition temperature of network glasses is dictated by the variation in average bond energy rather than the average coordination number. Further, the non-reversing enthalpy Hnr of As45Te55-xIx glasses is found to exhibit a sharp minimum at the composition x = 6. A broad hump is also seen in glass transition and crystallization temperatures in the composition range 5 x 7. These results indicate a narrow thermally reversing window in As45Te55-xIx glasses around the composition x = 6. As45Te55-xIx glasses have been found to exhibit a memory to threshold type change in switching behavior with iodine content (x 6), which has been understood on the basis of the sharp increase in thermal diffusivity above x = 6. It is also observed that the switching voltages do not change appreciably with composition/average coordination number. Though no pronounced signature of a stiffness transition is seen in the variation with composition of VT, fluctuations are seen in the switching voltages around x = 6, the composition corresponding to the sharp thermally revering window. PDS studies indicate that the thermal diffusivities () of As45Te55-xIx chalcohalide exhibit a sharp minimum at the composition x = 6. This result reasserts the presence of a sharp thermally reversing window in As45Te55-xIx glasses around the composition x = 6. Chapter 5: The significant results obtained in the present thesis work have been summarized in this chapter. Further, the scope for future work is also presented.

GeₓSe₍₁₋ₓ₎ and AsₓSe₍₁₋ₓ₎ glasses have found use in many technological applications due to their excellent rheological properties and their wide IR transparency window. However, the low glass transition temperatures of these glasses leads to large changes in their properties, due to structural relaxation, over the weeks and months subsequent to their fabrication. Thus, obtaining a more thorough understanding of structural relaxation and its relation to the structure, composition, and processing of these glasses is important in furthering their use. Structural investigations, using NMR and Raman spectroscopies, performed on the GeₓSe₍₁₋ₓ₎ family of glasses show that the structure of these glasses is composed of two distinct microdomains. One corresponds to a rigid GeSe₂-like domain and the other corresponds to a floppy Se domain. These results are compared to other existing structural models for GeₓSe₍₁₋ₓ₎ glasses. Enthalpy measurements on both GeSe₉ and GeSe₄ optical fibers which were aged up to five years demonstrate that both compositions undergo a large amount of enthalpy relaxation in this time period. Raman spectroscopy performed concurrently with enthalpy measurements on the same GeSe₉ and GeSe₄ fibers shows that one of the structural changes taking place within the glass network is the conversion of edgesharing to corner-sharing tetrahedra in the GeSe₂-like phase. Moreover, the rate at which this conversion takes place is shown to be similar to the rate of enthalpy relaxation, suggesting that this structural change is one of the main mechanisms for structural relaxation in GeₓSe₍₁₋ₓ₎ glasses. Implementation of the Tool-Narayanaswamy-Moynihan (TNM) model as a hybrid computer model allowing the prediction of the four relaxation parameters Δh*, log(A), x, and β via optimization of simulated and experimental data was accomplished. It was found that a multi-rate version of the TNM model, which obtains an average set of model parameters via optimization of multiple experimental thermal histories simultaneously, was able to predict relaxation parameters for AsₓSe₍₁₋ₓ₎ glasses within the 2.10 ≤ <r> ≤ 2.50 compositional domain, where <r> is the average bond coordination of the glass network as defined by the Phillips and Thorpe constraints model. Above <r> = 2.50, however, the model fails, due to a bimodal distribution of relaxation times within the glass structure contrary to the TNM model assumption of a unimodal distribution of relaxation times, thus rendering the model inapplicable. Muti-rate modeling of the GeₓSe₍₁₋ₓ₎ family of glasses was also attempted, however the TNM model also fails for this family of glasses due to the inherently bimodal distribution of relaxation times which arises from their bimodal structure.

Les composés multimatériaux à base de verre connaissent aujourd’hui un intérêt croissant, en particulier sous la forme de fibres optique pour des applications dans l’infrarouge. Parmi les matériaux vitreux qui existent, les verres chalcogénures présentent de nombreux avantages, tel qu’un large domaine de transparence allant du visible à l’infrarougeou encore de bonne aptitude à pouvoir être étirer. Pour réaliser de nouvelles fibres multimatériaux, il est important d’avoir accès à un choix étendu de compositions vitreuses étirables pouvant servir de matrice hôte. Il peut être montré que les verres actuellement utilisés pour la réalisation de fibres multimatériaux couvrent deux plages de température de transition vitreuse différentes ; soit à basse température (100-250 °C), ou à haute température (1000 °C et plus). Le manque d’information sur des verres étirables couvrant un domaine intermédiaire de température entre 250 et 1000 °C, nous ont conduit à explorer les propriétés et les capacités d’étirement des verres des deux systèmes ternaires Ge-S-I et Ga-As-S. Il sera montré que ces systèmes vitreux ont en effet des Tg permettant de couvrir cette gamme intermédiaire de température et ont de larges domaines de formation vitreux. Un ensemble de caractérisations physiques et thermiques sur les verres au sein des systèmes ternaires Ge-S-I et Ge-As-S seront présentés et analysés. Il sera possible d’observer, comment notamment les résultats des mesures thermomécaniques et de viscosité des échantillons synthétisés ont permis d’aborder dans les meilleures conditions les tests d’étirement des verres. Ou encore comment l’analyse minutieuse des propriétés a pu permettre de définir un domaine de composition combinant à la fois des propriétés optimales en termes de Tg et de transparence dans le visible, avec une bonne capacité à pouvoir être étirées sous forme de fibres optiques. Pour la première fois les domaines de fibrage des deux ternaires à partir de l’étirement d’une préforme seront présentés dans ce manuscrit. Ce travail présente également une caractérisation structurale des verres Ge-S-I. Cette étude a été réalisé en combinant la spectroscopie Raman, la spectroscopie IR et des calculs de chimie théorique afin de proposer un nouveau modèle structural basé sur les avancés les plus récentes d'une part sur la structure du système binaire Ge-S, puis ternaire Ge-S-I.Enfin, les résultats préliminaires sur la réalisation de fibres multimatériaux à partir de verres Ge-S-I et Ge-As-S pour la réalisation de sources laser entre 3 et 5 µm, seront présentés. Le projet, la méthodologie et les résultats quant à la réalisation d’une fibre multimatériaux à base de verre chalcogénure avec un cœur cristallisé de ZnS à partir de deux techniques innovantes différentes, seront présentés. / Nowadays, the interest on multimaterials based on glass matrix growth constantly, in particular in the field of multimaterial optical fibers for IR applications. Among the glass materials that exist, chalcogenide glasses presents a lot of advantages as for instance large transparency windows, spanning from the visible to the infrared or also good capability to be drawn. In the aim to realize new multimaterials fibers, it is important to get a large choice of draw able glass compositions that can be used as host matrix. It can be shown that the glass used currently to make multimaterial fibers covers two glass transition temperature range ; low temperature (100-250 °C) and high temperature (1000 °C and more). The lack of information regarding the existence of glass compositions that can be drawn into fibers at intermediate temperature (between 250 and 1000 °C), has lead us to explore the properties and the draw ability of glasses into two ternary systems: Ge-As-S and Ge-S-I. It will be presented that these glass systems possess Tg that covers this intermediate range of temperature and have large glass forming regions. Some physical and thermal characterizations of Ge-As-S and Ge-S-I glasses will be presented and analyzed. It will be possible to observe how the thermomechanical and viscosity measurements made on the different samples enabled us to perform the drawing tests in the best conditions. It will be also possible to see how a careful analysis of the Ge-S-I glass properties gave us the possibility to define a glass region combining optimal properties as Tg and transparency in the visible, and good capability to be drawn. For the first time, the fiber drawing region of both systems will be presented in this thesis. This work present also a structural characterization of Ge-S-I glasses using IR and Raman spectroscopy as well as DFT calculations, in the aim to propose a new structural model based on recent development in the Ge-S network structure. Finally, preliminary results on the realization of Ge-S-I and Ge-As-S based multimaterial fibers for the production of IR laser sources between 3 and 5 µm, will be presented. The last chapter will present the project, the methodology and the results obtained to realize multimaterial fibers with ZnS core, using two different technics.

Optical amplifiers are highly sought-after in optical communications to power boost light signals carrying information. Rare Earth doped glasses have been the medium of choice for optical amplification. It is, therefore, essential to understand the interaction of light with potential host glasses for rare-earths before they could be proposed as suitable candidates. In this research, we have optically characterized three different rare earth doped bulk glasses. The glass samples investigated were Neodymium doped Gallium Lanthanum Sulfide (GLS:Nd), Erbium doped Germanium Gallium Sulfide (GeGaS:Er) and Erbium doped Fluorochlorozirconate (FCZ:Er). The transmission spectra, T(λ), was used in identifying the absorption transitions of rare earth ions from the ground level to the various excited levels and in obtaining the optical absorption coefficient, α(λ). This in turn was used in determining the Judd-Ofelt parameters, which were then used in obtaining radiative lifetimes of the energy levels of interest. Photoluminescence emission bands were also identified and their shapes were investigated. Finally, a comparison of the Judd-Ofelt lifetime with the experimental decay time was also done. From which, the major decay mechanism of the rare earth ions from the energy level under investigation was concluded.

Diamond-like semiconductors (DLSs) are a class of semiconductor materials having structures similar to that of either cubic or hexagonal diamond. These normal valence compounds are of interest for their wide variety of technologically useful properties that can be tuned for specific applications. Until recently, DLS research has been focused on binary and ternary compositions due to their relative ease of synthesis. However, quaternary DLSs have gained considerable popularity due to their increased compositional flexibility and their potential as multifunctional materials. Despite their growing reputation, the vast number of possible combinations and conceivable solid solutions, DLSs remain fairly unexplored.&lt;br&gt;This work focuses on quaternary DLSs of the formula Ag2-II-IV-S4 in order to advance the knowledge of structure-property relationships for this entire class of materials. Toward this goal, a more complete understanding of the crystal structures of these materials is necessary. This task is often problematic due to the presence of isoelectronic, or nearly isoelectonic elements, that can complicate X-ray structure refinements. In this work, Ag2CdGeS4 is used as a case study to demonstrate that this problem can be resolved with careful consideration of bonding environments as well as the use of high-resolution X-ray sources. For the novel DLS Ag2ZnSiS4, the relationship between the structure and optical properties is probed with the combination of single crystal X-ray diffraction, optical diffuse reflectance spectroscopy and electronic structure calculations using the software package Wien2k. Finally, the current set of predictive tools employed to forcast diamond-like structures are reviewed, including the adherence of these guidelines to the novel compound Ag2FeSiS4 as well all over 60 ternary and quaternary diamond-like materials currently reported in the literature. Furthermore, the most common radii sets used for the prediction of bond distance and cell parameters in these materials are compared to the observed bond distances in quaternary diamond-like nonoxide materials. / Bayer School of Natural and Environmental Sciences / Chemistry and Biochemistry / PhD; / Dissertation;

Optical amplifiers are highly sought-after in optical communications to power boost light signals carrying information. Rare Earth doped glasses have been the medium of choice for optical amplification. It is, therefore, essential to understand the interaction of light with potential host glasses for rare-earths before they could be proposed as suitable candidates. In this research, we have optically characterized three different rare earth doped bulk glasses. The glass samples investigated were Neodymium doped Gallium Lanthanum Sulfide (GLS:Nd), Erbium doped Germanium Gallium Sulfide (GeGaS:Er) and Erbium doped Fluorochlorozirconate (FCZ:Er). The transmission spectra, T(λ), was used in identifying the absorption transitions of rare earth ions from the ground level to the various excited levels and in obtaining the optical absorption coefficient, α(λ). This in turn was used in determining the Judd-Ofelt parameters, which were then used in obtaining radiative lifetimes of the energy levels of interest. Photoluminescence emission bands were also identified and their shapes were investigated. Finally, a comparison of the Judd-Ofelt lifetime with the experimental decay time was also done. From which, the major decay mechanism of the rare earth ions from the energy level under investigation was concluded.

Metal chalcogenide nanomaterials are interesting due to their size dependent properties and potential use in numerous types of devices or applications. The synthetic methods of binary phase metal chalcogenide nanoparticles are well established, but finding simple ways to make even more complex nanostructures is important. To this end, two techniques were studied: the cation exchange of metal chalcogenide nanocrystals, CdE → MxEy (E = S, Se, Te; M = Pd, Pt) and the solution phase synthesis of ternary chalcogenide nanoparticles. The effects of cation solvation and the volume change (Delta V) of reaction on the equilibrium and the morphology change in the cation-exchange reactions of CdE → MxEy were investigated. A two-phase solvent environment was particularly efficient in increasing the thermodynamic driving force. The effect of Delta V of reaction on the morphology of the product nanocrystals was also investigated. Depending on the stress developed in the lattice during the reaction, product nanocrystals underwent varying degrees of morphological changes, such as void formation and fragmentation, in addition to the preservation of the original morphology of the reactant nanocrystals. The knowledge of the effect of ion solvation and Delta V of reaction on the equilibrium and product morphology provides a new strategy and useful guide to the application of cation-exchange reactions for the synthesis of a broader range of inorganic nanocrystals. Using a solution phase method, the morphology of CuInSe2 nanoparticles could be tuned from small 10 nm spheres to micron length nanowires by varying the relative amount of strong and weak surfactants passivating the surface. Oleylamine and trioctylphosphine oxide were chosen as the strong and weak surfactants, respectively. Small isotropic structures were formed when the oleylamine was the only surfactant with the size of the nanospheres increasing as the amount of oleylamine decreased. For the CuInSe2 nanowires, weakly-binding dioctylphosphine oxide (DOPO), an impurity in the TOPO, was found to be the key surfactant that enables the anisotropic one-dimensional growth. Detailed analysis of the structure of the nanowires indicated that they grow perpendicular to (112) planes, with twinning around the growth axis by ~60 degree rotation. The nanowires exhibit a saw-tooth surface morphology resembling a stack of truncated tetrahedral.