A thermodynamical framework is presented that describes the solidification of molten polymers to an amorphous as well as to a semicrystalline solid-like state. This framework fits into a general structure developed for materials undergoing a large class of entropy producing processes. The molten polymers are usually isotropic in nature and certain polymers crystallize, with the exception of largely atactic polymers, which solidify to an amorphous solid, to an anisotropic solid. The symmetry of the crystalline structures in the semicrystalline polymers is dependent upon the thermomechanical process to which the polymer is subjected to. The framework presented takes into account that the natural configurations associated with the polymer melt (associated with the breaking and reforming of the polymer network) and the solid evolve in addition to the evolving material symmetry associated with these natural configurations. The functional form of the various primitives such as how the material stores, dissipates energy and produces entropy are prescribed. Entropy may be produced by a variety of mechanisms such as conduction, dissipation, solidification, rearragement of crystalline structures due to annealing and so forth. The manner in which the natural configurations evolve is dictated by the maximization of the rate of dissipation. Similarly, the crystallization and glass transition kinetics may be obtained by maximization of their corresponding entropy productions. The restrictions placed by the second law of thermodynamics, frame indiference, material symmetry and incompressibility allows for a class of constitutive equations and the maximization of the rate of entropy production is invoked to select a constitutive equation from an allowable class of constitutive equations. Using such an unified thermodynamic approach, the popular crystallization equations such as Avrami equation and its various modifications such as Nakamura and Hillier and Price equations are obtained. The predictions of the model obtained using this framework are compared with the spinline data for amorphous and semicrystalline polymers.

Neste trabalho foi avaliada a influência da adição de PbF2 em várias propriedades, de interesse geral e específico, de vidros oxifluoroboratos de chumbo. As amostras estudadas foram sintetizadas seguindo a fórmula 50BO1,5-(50-x)PbO-xPbF2 (BPP), com x = 0, 5, 10, 15, 20 e 30 (% catiônica), e usando o método convencional de fusão seguida de resfriamento rápido (quenching). A modificação da estrutura local destes vidros BPP, causada pela introdução do PbF2, foi avaliada por Espectroscopia no Infravermelho (FTIR). Além do mais, as implicações destas mudanças estruturais sobre as propriedades ópticas, térmicas e elétricas foram monitoradas através das técnicas de Absorção Óptica no Ultravioleta-Visível (UV-Vis), Calorimetria Exploratória Diferencial (DSC) e Espectroscopia de Impedância (EI), respectivamente. As amostras vítreas foram também submetidas à ação de campos elétricos, observando-se um fenômeno de cristalização não espontânea da fase β-PbF2, mesmo abaixo da temperatura de transição vítrea. A partir de um estudo sistemático deste fenômeno, foi possível associar o seu desenvolvimento a um processo de redução: Pb2+ + e- → Pb+, atuando como força motriz da nucleação dos cristais. Esta reação catódica pôde ser validada após constatação, por Difratometria de raios X (DRX), da presença de Pb0 em amostras eletricamente tratadas durante tempos longos, o que implica supor a seguinte reação adicional: Pb+ + e- → Pb0. Por outro lado, para completude do processo de oxirredução, foi proposta a ocorrência da reação F- → e- + ½F2(g)↑ no ânodo. A validação desta reação foi obtida através de ensaios sistemáticos de cristalização com células eletroquímicas do tipo Pt,Ag/BPP/YSZ:PbF2/Ag,Pt, onde YSZ:PbF2. representa um compósito condutor iônico, o qual foi usado para garantir um controle, através de um mecanismo percolativo, do grau de liberdade da migração dos íons F- em direção ao ânodo. Completam esta investigação estudos elétricos no domínio do tempo, tendo sido possível estimar, para os processos de polarização ocorrentes durante a cristalização na interface material-eletrodo, capacitâncias características de reações eletroquímicas (~ 10-3 F), corroborando com a interpretação dada, neste trabalho, para a indução elétrica de cristalização nestes vidros. Por fim, em termos de características microestruturais, notou-se que a fase cristalina formada (β-PbF2) apresentou uma morfologia ramificada (dendrítica), o que é, de fato, típico de cristalização na presença de campo elétrico, o fenômeno passando por reações do tipo redox e envolvendo, segundo a literatura científica, processos eletroconvectivos nos sistemas estudados. / The influence of PbF2 addition in various properties, of general and particular interest, of lead oxyfluoroborate glasses was evaluated in this work. The studied samples were prepared by the melt-quenching technique following the formula 50BO1,5-(50-x)PbO-xPbF2 (BPP), with x = 0, 5, 10, 15, 20 and 30 cationic %. The BPP structural modification, caused by PbF2 introduction into the glass matrix, was evaluated by Fourier Transform Infrared Spectroscopy (FTIR). Moreover, the implications of these structural changes on the optical, thermal and electrical properties were monitored, respectively, through Ultraviolet-Visible Optical Absorption (UV-Vis), Differential Scanning Calorimetry (DSC) and Impedance Spectroscopy techniques. For the electric field-treated glassy samples, a non-spontaneous crystallization phenomenon was observed, resulting in β-PbF2 phase formation, surprisingly even below the glass transition temperature. From a systematic study, it was possible to associate the development of this phenomenon with a reduction process: Pb2+ + e- Pb+, which acts as the driving force for crystals nucleation. This cathodic reaction was validated after noting, through X-ray Difratometry (XRD), presence of metallic lead (Pb0) in those samples electrically treated during long times, what implies to infer the following additional reaction: Pb+ + e- → Pb0. On the other hand, for completeness of the redox process, occurrence of the anodic reaction F- → e- + ½F2(g)↑ was proposed. This reaction was validated through systematic crystallization experiments with electrochemical cells of type Pt,Ag/BPP/YSZ:PbF2/Ag,Pt, where YSZ:PbF2 represents composite-like mixtures used in order to guarantee a control, through a percolative mechanism, of the degree of freedom for fluoride migration towards the anode. This investigation is completed by electrical studies in the time domain, from which it was possible to estimate, for processes occurring at the material-electrodes interface, capacitance values (~ 10-3 F) which are characteristic of electrochemical reactions, in agreement with the interpretation given, in this work, for the electrically-induced crystallization in these glasses. Finally, in terms of (micro)structural aspects, it was noted that the formed crystalline phase (β-PbF2) appears with a branched (dendritic) morphology, what is usual during crystallization phenomena in presence of an electric field, these phenomena being likewise a result of redox-type reactions involving, according to scientific literature, electroconvective processes in the studied systems.

Devido às suas potenciais aplicações tecnológicas (células solares, transistores de filme fino TFT, etc.), o estudo do silício amorfo (a-Si) tem despertado o interesse da comunidade científica desde o final da década de 70. Mais recentemente, este interesse foi renovado com o desenvolvimento da técnica de cristalização induzida por metal (Metal-induced Crystallization MIC), por causa do considerável interesse na obtenção do silício cristalino (c-Si) a baixas temperaturas. Dentre as principais abordagens adotadas para o estudo da MIC, destaca-se aquela realizada em estruturas consistindo de camadas alternadas de silício amorfo e filmes metálicos, por exemplo. Conseqüentemente, concluiu-se que a difusão de átomos do semicondutor para o metal (e/ou vice-versa) é o mecanismo responsável pela cristalização. Esta explicação fenomenológica, entretanto, não considera os mecanismos microscópicos que provocam a cristalização à baixa temperatura. Tendo isto por base, este trabalho diz respeito a uma abordagem diferente e complementar para a investigação do processo de MIC, através da inserção de uma quantidade controlada e homogeneamente distribuída de átomos de metal na rede amorfa. Para este estudo, filmes de silício amorfo dopados com diferentes concentrações de Ni e possuindo diferentes espessuras, depositados em substratos de c-Si, c-Ge, quartzo cristalino e vidro foram preparados pela técnica de sputtering de rádio freqüência, em uma atmosfera controlada de argônio. Com o objetivo de se investigar a influência exercida pela estrutura atômica nos mecanismos de cristalização destes filmes, todos foram submetidos a tratamentos térmicos cumulativos até 1000 oC. Para isto, os filmes foram caracterizados pelas técnicas de espalhamento Raman, transmissão óptica, EDS (energy dispersive spectrometry) e microscopia eletrônica de varredura (SEM). Os resultados experimentais indicam que a quantidade de Ni, a espessura e a natureza do substrato determinam a temperatura para o qual se inicia a cristalização dos filmes de a-Si, e que a espessura e a presença de Ni têm efeito direto sobre as propriedades ópticas dos filmes. Estudos preliminares utilizando-se as técnicas de microscopia de força atômica (AFM) e Extended X-ray Absorption Fine Structure (EXAFS) também foram feitos. / Due to their great technological potential (solar cells, thin film transistors, etc.), the study of amorphous silicon (a-Si) is attracting the attention of the scientific community since the 70s. More recently, such interest was renewed with the development of the Metal-induced Crystallization (MIC) technique, because of considerable interest in low-temperature formation of crystalline silicon (c-Si). Amongst the principal approaches to the study of MIC, stand out that performed on structures consisting of alternating layers of amorphous silicon and metal films, for example. Consequently, they conclude that the diffusion of semiconductor atoms into the metal (and/or vice-versa) is the mechanism responsible for the crystallization. This phenomenological explanation, however, does not consider the microscopic mechanisms that provoke the low temperature crystallization. Based on the above ideas, this work refers to a different and complementary approach to investigate the MIC process, by the insertion of a controlled and homogeneously distributed amount of metal atoms in the amorphous network. For this study, amorphous silicon films doped with different Ni concentrations and having different thicknesses, deposited on c-Si, c-Ge, crystalline quartz and glass substrates were prepared by the radio frequency sputtering technique in a controlled atmosphere of argon. In order to investigate the influence exerted by the atomic structure on the crystallization mechanisms of these films, all of them have been submitted to cumulative thermal annealing treatments up to 1000 C. To that aim, the films were investigated by Raman scattering, optical transmission, energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM). The experimental results indicate that the Ni content, the thickness and the nature of the substrate determines the crystallization temperature onset of the a-Si films, and that the thickness and the presence of Ni have direct effect on the optical properties of the films. Preliminary studies using the atomic force microscopy (AFM) and Extended X-ray Absorption Fine Structure (EXAFS) techniques have also been carried out.

There are two main goals of this thesis: to investigate the flow-induced crystallization behaviour of Polybutene-1 (PB-1 samples, and to study the effects of molecular parameters on the crystallization behaviour While flow-induced crystallization is not a new area in polymer research, well-defined experimental methods that allow access to high flow rate range comparable to that encountered in real processing are still lacking. Two types of flow are considered: shear and uniaxial elongational. Regarding the second aim, several molecular parameters considered are: molecular weight, molecular weight distribution, isotacticity, presence of nucleating agents, and copolymer content. For this purpose an array of PB-1 samples were used. It is found that each of these parameters can have significant effect on the crystallization behaviour. Mainly rheological methods were utilized to conduct the flow-induced crystallization experiments. Crystallization onset time is define d from the change in viscosity or other related parameters. The experiments begin with low shear rate range, to ensure that the results are comparable with literature data. In this range we encounter the quasi-quiescent onset time at very small. shear rates, which draws an interesting comparison with another physical parameter, the gel time. Beyond a critical flow rate a decrease in the onset time is seen, and a plateau-and-slope trend is evident for a curve of onset time vs. shear rate. Using a combination of three experimental methods, shear rates ranging from Q0001 - 500 s-1 are successfully achieved, and a good agreement between these methods is observed. Furthermore, a normalization procedure is introduced, which yields temperature-invariant curves for the mentioned range of shear rate. For the uniaxial elongation flow, the Elongational Viscosity Fixture (EVF) is employed, with the strain rate ranging from 0.0001 - 10 s'. A greater reduction in onset time as compared to shear (at the same shear/strain r ate) is observed, and the difference in the onset times for shear and elongation already reaches more than one decade for a flow rate of 10 5. This quantitative comparison is particularly important; since not so many data on elongation-induced crystallization are available in the literature. Finally, the thesis compares several flow induced crystallization models that can be useful as prediction tools and selects one of these models to be compared with the experimental data. A qualitative agreement is found, however, for better quantitative prediction the model still needs to be.

This study indicate that the chemical inter-diffusion between the Cr-doped glass/glass ceramic and quartz (SiO2) influence the fluorescence properties of glass, mainly because of Cr4+ replacing by tetrahedral of Si4+. Cr4+ fluorescence intensity was reduced and its emission band was shifted to longer wavelength (red shift). We selected the SiO2-based glass composition: Mg2SiO4 glass-ceramic and reduced a ratio of SiO2 sintered into the ceramic powder. This paper used diffusion characteristics of quartz (SiO2) to compensate for reduced SiO2 in the ceramic powder. After diffusing with quartz (SiO2), ceramics powder changed into glasses. The intensity of fluorescence and the crystal field had been improved. The center of Cr4+ fluorescence is about 1100nm belonging to Cr4+:Mg2SiO4 crystal. The ratio of Cr4+ in Mg2SiO4 crystal/Cr4+ in MgO-SiO2 glass increases from 0.33 to 1.74. The goal is to develop a novel glass which is resistant to SiO2 inter-diffusion degradation during fiber fabrication, and provide the new fiber technology to avoid the influence of inter-diffusion This study provides new types of treatment: Laser induced crystallization. Laser heat-treatment can more quickly induce crystals in glass during seconds, than traditional heat-treatment which require several hours. This study also indicate that one step laser heat-treatment induce micro-crystals, but one step laser heat-treatment induce nano-crystals. We successfully produced nano-crystallization during seconds.

Devido às suas potenciais aplicações tecnológicas (células solares, transistores de filme fino TFT, etc.), o estudo do silício amorfo (a-Si) tem despertado o interesse da comunidade científica desde o final da década de 70. Mais recentemente, este interesse foi renovado com o desenvolvimento da técnica de cristalização induzida por metal (Metal-induced Crystallization MIC), por causa do considerável interesse na obtenção do silício cristalino (c-Si) a baixas temperaturas. Dentre as principais abordagens adotadas para o estudo da MIC, destaca-se aquela realizada em estruturas consistindo de camadas alternadas de silício amorfo e filmes metálicos, por exemplo. Conseqüentemente, concluiu-se que a difusão de átomos do semicondutor para o metal (e/ou vice-versa) é o mecanismo responsável pela cristalização. Esta explicação fenomenológica, entretanto, não considera os mecanismos microscópicos que provocam a cristalização à baixa temperatura. Tendo isto por base, este trabalho diz respeito a uma abordagem diferente e complementar para a investigação do processo de MIC, através da inserção de uma quantidade controlada e homogeneamente distribuída de átomos de metal na rede amorfa. Para este estudo, filmes de silício amorfo dopados com diferentes concentrações de Ni e possuindo diferentes espessuras, depositados em substratos de c-Si, c-Ge, quartzo cristalino e vidro foram preparados pela técnica de sputtering de rádio freqüência, em uma atmosfera controlada de argônio. Com o objetivo de se investigar a influência exercida pela estrutura atômica nos mecanismos de cristalização destes filmes, todos foram submetidos a tratamentos térmicos cumulativos até 1000 oC. Para isto, os filmes foram caracterizados pelas técnicas de espalhamento Raman, transmissão óptica, EDS (energy dispersive spectrometry) e microscopia eletrônica de varredura (SEM). Os resultados experimentais indicam que a quantidade de Ni, a espessura e a natureza do substrato determinam a temperatura para o qual se inicia a cristalização dos filmes de a-Si, e que a espessura e a presença de Ni têm efeito direto sobre as propriedades ópticas dos filmes. Estudos preliminares utilizando-se as técnicas de microscopia de força atômica (AFM) e Extended X-ray Absorption Fine Structure (EXAFS) também foram feitos. / Due to their great technological potential (solar cells, thin film transistors, etc.), the study of amorphous silicon (a-Si) is attracting the attention of the scientific community since the 70s. More recently, such interest was renewed with the development of the Metal-induced Crystallization (MIC) technique, because of considerable interest in low-temperature formation of crystalline silicon (c-Si). Amongst the principal approaches to the study of MIC, stand out that performed on structures consisting of alternating layers of amorphous silicon and metal films, for example. Consequently, they conclude that the diffusion of semiconductor atoms into the metal (and/or vice-versa) is the mechanism responsible for the crystallization. This phenomenological explanation, however, does not consider the microscopic mechanisms that provoke the low temperature crystallization. Based on the above ideas, this work refers to a different and complementary approach to investigate the MIC process, by the insertion of a controlled and homogeneously distributed amount of metal atoms in the amorphous network. For this study, amorphous silicon films doped with different Ni concentrations and having different thicknesses, deposited on c-Si, c-Ge, crystalline quartz and glass substrates were prepared by the radio frequency sputtering technique in a controlled atmosphere of argon. In order to investigate the influence exerted by the atomic structure on the crystallization mechanisms of these films, all of them have been submitted to cumulative thermal annealing treatments up to 1000 C. To that aim, the films were investigated by Raman scattering, optical transmission, energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM). The experimental results indicate that the Ni content, the thickness and the nature of the substrate determines the crystallization temperature onset of the a-Si films, and that the thickness and the presence of Ni have direct effect on the optical properties of the films. Preliminary studies using the atomic force microscopy (AFM) and Extended X-ray Absorption Fine Structure (EXAFS) techniques have also been carried out.

Neste trabalho foi avaliada a influência da adição de PbF2 em várias propriedades, de interesse geral e específico, de vidros oxifluoroboratos de chumbo. As amostras estudadas foram sintetizadas seguindo a fórmula 50BO1,5-(50-x)PbO-xPbF2 (BPP), com x = 0, 5, 10, 15, 20 e 30 (% catiônica), e usando o método convencional de fusão seguida de resfriamento rápido (quenching). A modificação da estrutura local destes vidros BPP, causada pela introdução do PbF2, foi avaliada por Espectroscopia no Infravermelho (FTIR). Além do mais, as implicações destas mudanças estruturais sobre as propriedades ópticas, térmicas e elétricas foram monitoradas através das técnicas de Absorção Óptica no Ultravioleta-Visível (UV-Vis), Calorimetria Exploratória Diferencial (DSC) e Espectroscopia de Impedância (EI), respectivamente. As amostras vítreas foram também submetidas à ação de campos elétricos, observando-se um fenômeno de cristalização não espontânea da fase β-PbF2, mesmo abaixo da temperatura de transição vítrea. A partir de um estudo sistemático deste fenômeno, foi possível associar o seu desenvolvimento a um processo de redução: Pb2+ + e- → Pb+, atuando como força motriz da nucleação dos cristais. Esta reação catódica pôde ser validada após constatação, por Difratometria de raios X (DRX), da presença de Pb0 em amostras eletricamente tratadas durante tempos longos, o que implica supor a seguinte reação adicional: Pb+ + e- → Pb0. Por outro lado, para completude do processo de oxirredução, foi proposta a ocorrência da reação F- → e- + ½F2(g)↑ no ânodo. A validação desta reação foi obtida através de ensaios sistemáticos de cristalização com células eletroquímicas do tipo Pt,Ag/BPP/YSZ:PbF2/Ag,Pt, onde YSZ:PbF2. representa um compósito condutor iônico, o qual foi usado para garantir um controle, através de um mecanismo percolativo, do grau de liberdade da migração dos íons F- em direção ao ânodo. Completam esta investigação estudos elétricos no domínio do tempo, tendo sido possível estimar, para os processos de polarização ocorrentes durante a cristalização na interface material-eletrodo, capacitâncias características de reações eletroquímicas (~ 10-3 F), corroborando com a interpretação dada, neste trabalho, para a indução elétrica de cristalização nestes vidros. Por fim, em termos de características microestruturais, notou-se que a fase cristalina formada (β-PbF2) apresentou uma morfologia ramificada (dendrítica), o que é, de fato, típico de cristalização na presença de campo elétrico, o fenômeno passando por reações do tipo redox e envolvendo, segundo a literatura científica, processos eletroconvectivos nos sistemas estudados. / The influence of PbF2 addition in various properties, of general and particular interest, of lead oxyfluoroborate glasses was evaluated in this work. The studied samples were prepared by the melt-quenching technique following the formula 50BO1,5-(50-x)PbO-xPbF2 (BPP), with x = 0, 5, 10, 15, 20 and 30 cationic %. The BPP structural modification, caused by PbF2 introduction into the glass matrix, was evaluated by Fourier Transform Infrared Spectroscopy (FTIR). Moreover, the implications of these structural changes on the optical, thermal and electrical properties were monitored, respectively, through Ultraviolet-Visible Optical Absorption (UV-Vis), Differential Scanning Calorimetry (DSC) and Impedance Spectroscopy techniques. For the electric field-treated glassy samples, a non-spontaneous crystallization phenomenon was observed, resulting in β-PbF2 phase formation, surprisingly even below the glass transition temperature. From a systematic study, it was possible to associate the development of this phenomenon with a reduction process: Pb2+ + e- Pb+, which acts as the driving force for crystals nucleation. This cathodic reaction was validated after noting, through X-ray Difratometry (XRD), presence of metallic lead (Pb0) in those samples electrically treated during long times, what implies to infer the following additional reaction: Pb+ + e- → Pb0. On the other hand, for completeness of the redox process, occurrence of the anodic reaction F- → e- + ½F2(g)↑ was proposed. This reaction was validated through systematic crystallization experiments with electrochemical cells of type Pt,Ag/BPP/YSZ:PbF2/Ag,Pt, where YSZ:PbF2 represents composite-like mixtures used in order to guarantee a control, through a percolative mechanism, of the degree of freedom for fluoride migration towards the anode. This investigation is completed by electrical studies in the time domain, from which it was possible to estimate, for processes occurring at the material-electrodes interface, capacitance values (~ 10-3 F) which are characteristic of electrochemical reactions, in agreement with the interpretation given, in this work, for the electrically-induced crystallization in these glasses. Finally, in terms of (micro)structural aspects, it was noted that the formed crystalline phase (β-PbF2) appears with a branched (dendritic) morphology, what is usual during crystallization phenomena in presence of an electric field, these phenomena being likewise a result of redox-type reactions involving, according to scientific literature, electroconvective processes in the studied systems.

Les caoutchoucs naturels chargés sont largement utilisés pour leurs excellentes propriétés mécaniques comme matériaux structurels dans les pneumatiques. Leurs excellentes performances sont souvent associées à leur capacité à cristalliser sous tension. Dans le cas de la fatigue cyclique, la dissipation induite par la création et fusion de cristallites est souvent donnée comme responsable de la bonne résistance des caoutchoucs naturel à la propagation de fissures. Ce travail de doctorat s'est focalisé sur les divers mécanismes dissipatifs qui sont activé par les grandes déformations rencontrées près d'une pointe de fissure. La diffusion des rayons X a été utilisée pour caractériser les changements de structure à des échelles sub-microniques, tels que la cristallisation sous tension, la création de nano-cavités, ou la réorganisation de la charge. Un premier volet de l'étude s'est focalisé sur des tests uniaxiaux, afin d'étudier l'effet d'un changement de formulation du matériau (taux de charge, densité de réticulation), d'un vieillissement thermique, ou encore d'une élévation de la température sur ces modification de structure. Dans une seconde partie, une caractérisation complète de fissures de fatigue a été effectuée. La corrélation d'image numérique a été utilisée pour mesurer les déformations locales au voisinage d'une pointe de fissure, et les rayons X ont permis d'y associer une mesure locale de la structure du matériau. Les propriétés de fatigue de ces matériaux ont été mit en regard des structures observées afin de discuter leur relation. Il a été mis en évidence que le rôle de la cristallisation dépassait largement sa contribution à la dissipation locale. / Filled natural rubbers are widely used in structural parts such as tires for their outstanding mechanical properties. Their exceptional behavior is often associated to the ability of natural rubber chains to form a crystalline structure under tension. In the case of cyclic fatigue cracking, the dissipation added through crystallization and melting at the crack tip is often seen as the main reinforcing mechanism that reduces fatigue crack growth. This PhD work focused on all the dissipative mechanisms activated by the strain amplification near a crack tip. An extensive use of X-ray scattering was made to investigate sub-micronic changes in structure (strain-induced crystallization, cavitation, filler network). A study was made in uniaxial tension to understand the effects of material composition and test environment on these structure changes. The effect of filler volume fraction, crosslink density, thermal ageing and test temperature were considered. This study was followed by a complete description of several fatigue crack-tips. Digital image correlation was used to map the strain fields at the vicinity of the cracks, while X-ray mapping of the process zone gave information on the local changes in structure. The cyclic fatigue properties of the materials were then discussed through the knowledge acquired both in uniaxial tension and near crack-tips. It showed that the effect of strain induced-crystallization far outweigh the dissipation added.

A new cluster tool for in situ real-time processing and depth-resolved compositional, structural and optical characterization of thin films at temperatures from -100 to 800 °C is described. The implemented techniques comprise magnetron sputtering, ion irradiation, Rutherford backscattering spectrometry, Raman spectroscopy and spectroscopic ellipsometry. The capability of the cluster tool is demonstrated for a layer stack MgO/ amorphous Si (~60 nm)/ Ag (~30 nm), deposited at room temperature and crystallized with partial layer exchange by heating up to 650°C. Its initial and final composition, stacking order and structure were monitored in situ in real time and a reaction progress was defined as a function of time and temperature.

Chalcogenide glasses are well known to have good transparency into the infrared spectrum. These glasses though tend to have low thresholds as compared to oxide glasses for photo-induced changes and thermally-induced changes. Material modification such as photo-induced darkening, bleaching, refractive index change, densification or expansion, ablation of crystallization have been demonstrated, and are typically induced by a thermal furnace-based heat treatment, an optical source such as a laser, or a combination of photo-thermal interactions. Solely employing laser-based heating has an advantage over a furnace, since one has the potential to be able to spatially modify the materials properties with much greater precision by moving either the beam or the sample. The main properties of ChG glasses investigated in this study were the light-induced and thermally-induced modification of the glass through visible microscopy, white light interferometry, and Raman spectroscopy. Additionally computational models were developed in order to aid in determining what temperature rise should be occurring under the conditions used in experiments. It was seen that ablation, photo-expansion, crystallization, and melting could occur for some of the irradiation conditions that were used. The above bandgap energy simulations appeared to overestimate the maximum temperature that should have been reached in the sample, while the below bandgap energy simulations appeared to underestimate the maximum temperature that should have been reached in the sample. Ultimately, this work produces the ground work to be able to predict and control dose, and therefore heating, to induce localized crystallization and phase change.