Well know therapies for the treatment of osteoporosis, syndrome characterized by increased bone fragility and fracture consist primarily of drugs which prevent bone losses, such as bisphosphonates. Among them, alendronate (PO3)-(OH)-C-((CH2)3 NH3)-(PO3) is one of the chosen treatments in the clinic, IC50 = 50 nM. In this work a study of the molecular alendronate and three of its crystals (sodium alendronate trihydrate and anhydrous and calcium alendronate ) is performed in the scope of Density Functional Theory (DFT). In the first case, the focus is the lowest energy conformations of the molecular alendronate in vacuum, in an aqueous medium in accordance with the model of polarization continuum (PCM), and interacting with three molecules of water of a sodium atom based on the characteristics structural relevadas diffraction X-ray crystal alendrontao sodium trihydrate; their vibrational infrared and Raman spectra are calculated to explain in detail the abundant signatures of the phosphate group in the frequency range 400-1400 cm −1 with the assignments of the most important vibrational modes. In the case of crystals, their structural, electronic and optical properties are obtained in the generalized gradient approximation taking into account the description of the term correlation and exchange Tchatschenko (GGA+TS ); Hirshfeld population analysis in which verified is presented alendronate is that the three crystals is in zwitterionic state. From the calculation of the band structure was obtained GAPs with very close values for the three crystals, however, with the density of states and characteristic for each crystal. The effective masses, dielectric function and theoretical optical absorptions for all crystals are presented. / Terapias estabelecidas para o tratamento da osteosporose, sÃndrome caracterizada por aumento na fragilidade Ãssea e fraturas, consistem primariamente de drogas que previnem a perda Ãssea, como os bisfosfonatos. Entre eles, o alendronato (PO3)-(OH)-C-((CH2)3 NH3)-(PO3) à um dos tratamentos escolhidos na clÃnica, pois possui o IC50=50 nM. Neste trabalho à realizado um estudo do alendronato molecular e de trÃs de seus cristais (alendronato de sÃdio trihidratado e anidro, e alendronato de cÃlcio) utilizando da Teoria do Funcional da Densidade (DFT). No primeiro caso, o foco sÃo os confÃrmeros de menor energia do alendronato molecular no vÃcuo, em meio aquoso de acordo com o modelo contÃnuo polarizÃvel (PCM), e interagindo com trÃs molÃculas de Ãgua e um Ãtomo de sÃdio de acordo com as caracterÃsticas estruturais reveladas por difraÃÃo de raios-X do cristal do alendrontao de sÃdio trihidratado; seus espectros vibracionais no infravermelho e Raman sÃo calculados para explicar com detalhes as abundantes assinaturas do grupo fosfato no intervalo de frequÃncia 400-1400 cm−1, com as atribuiÃÃes dos modos vibracionais mais importantes. No caso dos cristais, sÃo obtidas suas propriedades estruturais, eletrÃnicas e Ãpticas na aproximaÃÃo da gradiente generalizado levando-se em conta a descriÃÃo do termo de correlaÃÃo e troca de Tchatschenko (GGA+TS); à apresentada a anÃlise populacional de Hirshfeld na qual verificou-se que o alendronato nos trÃs cristais encontra-se no estado zwitterionico. A partir do cÃlculo de estrutura de banda, foi obtido GAPs com valores muito prÃximos para os trÃs cristais, porÃm, com densidade de estados bem caracterÃstica para cada cristal. SÃo apresentadas as massas efetivas, funÃÃo dielÃtrica e absorÃÃes Ãpticas teÃricas para todos os cristais.

Made available in DSpace on 2014-10-09T12:32:59Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:11Z (GMT). No. of bitstreams: 0 / Estudos recentes demonstram que o sistema cerâmico zircônia-escândia-céria (ScCeSZ) apresenta-se promissor para aplicações como eletrólito sólido em células a combustível de óxido sólido de temperaturas intermediárias de operação (600 a 800 °C). Neste trabalho, foi realizada a sinterização convencional, de duas etapas e assistida por campo elétrico do ZrO2 contendo 10% em mol de Sc2O3 e 1% em mol de CeO2 comercializado pela Fuel Cell Materials visando melhorar a densificação com reduzido tamanho médio de grãos. A condutividade elétrica de amostras densas de ScCeSZ sinterizadas pelos diferentes métodos foi investigada por espectroscopia de impedância. Diferentes condições de sinterização foram analisadas. A taxa de retração dos compactos é máxima a 1180 °C, determinada pela análise de dilatometria. Foi confirmado por difração de raios X que a adição de céria à zircônia-escândia promove a estabilização da fase cúbica à temperatura ambiente. No entanto, dependendo das condições de sinterização pode haver a formação de fases secundárias, as quais foram detectadas por difração de raios X e espectroscopia Raman. A sinterização assistida por campo elétrico promoveu a formação das fases cúbica e tetragonal. Considerando os métodos convencional e de duas etapas, para a obtenção do material cúbico monofásico é necessária uma seleção cuidadosa das condições de sinterização. Os valores de condutividade elétrica estão de acordo com as condutividades do ScCeSZ reportadas na literatura. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Este trabalho visa o estudo de processos de degradação fotocatalítica e fotoeletrocatalítica de corantes sobre dióxido de titânio. O enfoque está voltado ao uso de técnicas espectroscópicas, com especial destaque para o desenvolvimento de metodologias de espectroscopia vibracional Raman intensificada. Nesse sentido, tem-se em vista a investigação dos mecanismos envolvidos nos processos de fotodegradação e fotoeletrodegradação de corantes, através da identificação de intermediários e produtos de processos de degradação por técnicas de espectroscopia eletrônica e Raman. Os estudos de fotocatálise são também expandidos para ambientes eletroquímicos. Nos chamados processos fotoeletrocatalíticos, a combinação de processos eletroquímicos e fotoquímicos mostra-se bastante promissora para a degradação de poluentes orgânicos. O primeiro desafio no desenvolvimento desse trabalho foi construir o fotorreator adequado que permitisse a obtenção de amostras para serem analisadas por espectroscopia Raman, e apresentasse boa eficiência nos processos de fotocatálise e também fotoeletrocatálise. Encontrado o fotorreator adequado, investigamos o comportamento cinético dos processos foto(eletro)degradação de corantes, buscando verificar a dependência com o potencial eletroquímico aplicado, o efeito do eletrólito suporte, e a identificação de intermediários formados durante o processo de degradação. Analisamos também aspectos relacionados aos mecanismos de adsorção de corantes sobre a superfície do dióxido de titânio. Tais aspectos podem ser de significativa relevância no desenvolvimento de técnicas eficazes para o tratamento de poluentes orgânicos. Nossos estudos estiveram principalmente centrados em dois corantes: o azocorante verde de Janus e o corante antraquinônico alizarina vermelha S. Os resultados obtidos nos estudos da cinética dos processos fotoeletrocatalíticos sugerem que o efeito do potencial aplicado depende de maneira significativa da natureza química do corante. Observou-se uma tendência dos processos fotoeletrocatalíticos serem mais eficientes na remoção da coloração da solução corante do verde de Janus quando comparados aos fotocatalíticos. Tal tendência não foi observada para o corante alizarina vermelha S. Essa diferença de comportamento pôde ser relacionada à natureza das interações específicas de entre cada corante e a superfície do catalisador. Nossos estudos a respeito dos mecanismos envolvidos nos processos de degradação do verde de Janus revelaram que as primeiras etapas dos processos de fotodegradação e fotoeletrodegradação seguem mecanismos diferentes. Os resultados obtidos mostram que a degradação do verde de Janus em suspensão de TiO2 envolve entre suas etapas modificações na ligação azo desse corante (N=N), resultando na formação de um composto intermediário derivado da fenossafranina. No processo fotoeletrocatalítico, por outro lado, observa-se um mecanismo diferenciado o qual não envolve em suas etapas iniciais a quebra da ligação azo do corante / This work focuses on the study of photocatalytic and photoelectrocatalytic degradation processes of dyes over titanium dioxide. The main approach is based on the use of spectroscopic techniques, with special emphasis to methodologies based on surface-enhanced Raman spectroscopy. Within this context, the mechanisms involved in the photodegradation and photoelectrodegradation of dyes are investigated by the identification of degradation intermediates through vibrational and electronic spectroscopies. In the so-called photoelectrocatalytic processes, the combination of electrochemical and photochemical processes is an interesting and promising approach for the degradation of a wide variety of organic pollutants. The first step in the development of the present work was to build a photo reactor that allowed the analysis of samples through Raman spectroscopy and presented a good efficiency for both photocatalytic and photoelectrocatalytic processes. We then investigated the kinetic behavior of the photo(electro)degradation of dyes in order to verify the dependence upon the electrochemical applied potential, the effect of the supporting electrolyte, and the identification of intermediate products formed during the degradation process. We also analyzed aspects related to the adsorption mechanisms of the dyes on the titanium dioxide surface. Such aspects can be relevant to the understanding and to the development of efficient techniques for the remediation of organic pollutants. Our studies focused mainly on two dyes: the azo dye Janus green and the anthraquinonic dye alizarin red S. The results obtained in the kinetic study of the photoelectrocatalytic processes suggest that the effect of the applied electrochemical potential strongly depends on the chemical nature of the investigated dye. We have observed that the decolorization of Janus green is favored for photoelectrocatalytic process as compared to the photocatalytic degradation. Such behavior was not observed for the anthraquinonic dye alizarin red S. This difference was related to the nature of the specific interactions between each dye and the catalyst surface. Our studies regarding the mechanisms of degradation revealed that the first steps of the photocatalytic and photoelectrocatalytic processes of Janus green followed different routes. The obtained results indicate that the degradation of Janus green in aqueous TiO2 suspension involves changes in the azo bond (N=N), resulting in the formation of an intermediate compound a derived from the phenosafranine structure, whereas for the photoelectrocatalytic process there are evidences of a different mechanism that does not involve the cleavage of the azo bond.

O Grafeno tem sido estudado há 60 anos, mas só foi desde sua primeira obtenção mediante esfoliação de grafite em 2004 por Novoselov, que obteve grande interesse por parte de pesquisadores, pois tem uma série de notáveis propriedades físicas e químicas que dificilmente são encontradas num mesmo material, o que o torna uma ferramenta de primeira ordem em muitas aplicações de diversos campos. Além disso, sua produção se limita a pequenas folhas, com defeitos e empilhadas formando multicamadas, o qual não permite seu uso em nível industrial. Isso demanda não só que o grafeno seja produzido em grande escala, mas também conservando suas propriedades. O presente trabalho reporta o estudo e estabelecimento de condições para o crescimento de folhas de grafeno, utilizando técnicas de deposição química na fase de vapor a pressão ambiente (APCVD) catalítica, e deposição química na fase vapor assistida por plasma (PECVD), também catalítica, com filmes finos de Níquel e Cobre como metais catalisadores, visto que são as técnicas e metais que tem reportado melhores resultados. Desta forma, esta pesquisa foi encaminhada a um ajuste das variáveis que intervém nas duas técnicas, tais como os gases, seus fluxos e relação entre eles, a temperatura, o tempo de deposição e as espessuras do catalisador. No caso do PECVD, a potência de RF para a geração do plasma e a pressão. Os filmes foram caracterizados por microscopia Raman, que permite ter uma avaliação aproximada do número de camadas e os defeitos presentes no material, e por microscopia eletrônica de varredura (MEV), que permite observar a morfologia das amostras e a possível presença de grafeno, e assim ter certeza da qualidade do grafeno enquanto a continuidade e tamanho das folhas. Além disso, mediante Espectroscopia de raios X por dispersão de energia (EDS), instrumento associado ao MEV, é possível identificar os elementos presentes na amostra em pontos específicos e sua porcentagem. Estes análises revelaram que o grafeno obtido foi de grande área (1 cm2) com alta cristalinidade e poucos defeitos pontuais. / Graphene has been studied for 60 years, but was only since its first achievement by graphite exfoliation in 2004 by Novoselov that got great interest by researches, because it has remarkable physical and chemical properties which are hardly found in a single material, which makes it a first-order tool for many applications in several fields. Besides that, its production is limited to small sheets with defects and stacked in multilayers, which does not allow its use at industrial level, that requires not only a large scale production of graphene but also conservation of its properties. This work reports the study and find suitable conditions for the growth of graphene sheets, using catalytic atmospheric pressure chemical vapor deposition (APCVD) and plasma enhanced chemical vapor deposition (PECVD) techniques and thin nickel and copper films as catalysts. This choice is based on the fact that both, these techniques and the metals had lead to better reported results. Thus, this research is focused on the adjustment of the parameters that intervene in the two techniques, such as precursor gases, their flows and the relationship among them, temperature, deposition time and the catalyst thickness. In the case of the PECVD, the RF power to generate the plasma and the deposition pressure. The films were characterized by Raman spectroscopy, which allows an approximate evaluation of the number of layers and the defects in the material, and by Scanning Electron Microscopy (SEM), which allows to observe the morphology of the deposited layers, and thus to ensure the quality of the graphene as far as the continuity and size of the sheets are concerned. In addition, energy dispersive X-ray spectroscopy (EDS) associated to the SEM instrument was utilized to identify the elements present in particular locations of the sample as well as their percentage. These group of analyses revealed that the obtained graphene achieved areas about 1 cm2 with high crystallinity and low punctual defects.

Dephasing vibracional de dissulfeto de carbono líquido em diferentes pressões foi estudado por dinâmica molecular. Teoria de pertubação permite estudar relaxação vibracional com o método bem estabelecido de dinâmica molecular de equilíbrio de moléculas rígidas. Além do potencial intermolecular efetivo do tipo Lennard-Jones usado para a simulação de CS2 , é também assumido um potencial efetivo de acoplamento entre os graus de liberdade vibracional, translacional e rotacional. É discutido em detalhes a importância dos termos repulsivo e atrativo neste potencial, assim como a anisotropia das interações. As simulações reproduzem satisfatoriamente a dependência com a densidade observada experimentalmente para a função de correlação vibracional e para o desvio de frequência vibracional entre as fases líquida e gasosa. As simulações indicam pequena correlação entre relaxação vibracional e reorientacional, a qual pode ser mostrada como resultante do acoplamento desses graus de liberdade com movimento translacional. Um modelo estocástico entre as é desenvolvido para investigar a correlação funções de correlação vibracional e reorientacional, e resultados similares são obtidos por simulação e teoria. As simulações por dinâmica molecular também mostraram que a função de correlação de flutuação de frequência vibracional de CS2 não é uma simples exponencial. Então, a conhecida fórmula de Kubo para a função de correlação vibracional não é válida, e é sugerido um modelo duplo-exponencial para a função memória vibracional. / Vibrational dephasing of liquid carbon disulfide at different pressures is investigated by molecular dynamics simulation. Pertubation theory allows one to use the well-stablished method of equilibrium molecular dynamics of rigid molecules in studying vibrational dephasing. Besides the effective three-centre Lennard-Jones intermolecular potential for the simulation of CS2 , an effective coupling potential between vibrational, translational and rotational degrees of freedom is also assumed. The role of repulsive and attractive terms in this potential, as well as anisotropy, is discussed. The experimental trends of the average vibrational frequency shift between gas and liquid phase and vibrational correlation function with density are well reproduced by molecular dynamics. The simulations indicate a small correlation between vibrational and reorientational relaxations, which can be shown as the result of the coupling of these degrees of freedom with translational motion. A stochastic model is developed to investigate the correlation between vibrational and reorientational correlation functions. Very similar correlation is obtained from both theory and computer simulation. The simulations also showed that correlation functions of vibrational frequency fluctuations of CS2 are not a single exponential. Thus, the well known Kubo\'s formula for the vibrational correlation function is not valid for CS2 , and a double exponential model for the memory function is introduced.

Detection of explosives has always been a challenging issue all over the world. Different analytical techniques and instrumentation methods have been explored to obtain a 100% fail proof detector. Some technologies have matured and have been deployed in the field already. However, active research is still being pursued to make the ultimate explosive detection device. The present thesis broadly addresses the development of Raman spectroscopy based techniques for the detection of explosives. Although Raman spectroscopy has technologically developed and has become a regular tool for chemical identification, its use in the field of detection of explosives has been limited. Two aspects of detection were addressed in this thesis. The first part consists of the detection of minute quantities or traces of explosives using a Raman based method. In order to approach this problem, surface enhanced Raman spectroscopy (SERS), an offshoot of Raman spectroscopy was explored. Chapters 2-4 deal with developing efficient SERS substrates. In this endeavour, the first and the most obvious choice as SERS substrates were silver (Ag) nanoparticles (NPs). However, we were exploring methods that could be simple one-pot synthesis methods, cost-effective and without employing strong reducing agents (green). Therefore, Ag NPs were synthesized using biosynthetic route. These nanoparticles were used to study their SERS efficiency. Sub-nano molar concentration of dye as well explosive like trinitrotoluene (TNT) and hexanitrohexaazaisowurtzitane (CL-20) could be obtained for both the clove reduced as well as pepper Ag nanoparticles. Hence Ag NPs are very efficient SERS substrates. In the second part of the work on SERS, bimetallic nanoparticles with core-shell (Agcore-Aushell) architecture were synthesized, characterized and tested for SERS activity. After successful synthesis and characterization of the bimetallic nanoparticles, these were tested for their SERS activities using a dye molecule and an explosive molecule. SERS spectra could be obtained for the bimetallic nanoparticles. It was observed that the sensitivity of these NPs were almost at par with the mono-metallic Ag NPs. In order to bring SERS from laboratory to field, a more practical approach was to prepare solid SERS substrates or SERS substrates on solid platform. In the next chapter, we ventured into the most abundant material which forms the backbone of the organic world, carbon. Various carbonaceous materials ranging from chemically synthesized graphene, graphene oxide, multi-walled carbon nanotube (MWCNT), graphite and activated charcoal were explored as potential substrates for surface enhanced Raman spectroscopic applications. The analytes chosen for this particular study were some fluorescent molecules such as rhodamine B (RB), rhodamine 6G (R6G), crystal violet (CV), Nile blue A (NBA) and a non-fluorescent molecule acetaminophen, commonly known as paracetamol. Enhanced Raman signals were observed for the fluorescent molecules, especially for the molecules whose absorbance maxima are near the excitation wavelength of the laser (514.5 nm). The most interesting outcome of this work was obtaining enhanced Raman signals of nanomolar concentration of R6G on activated charcoal. However, for the non-fluorescent molecule, paracetamol, Raman spectra could not be observed beyond -5 10M concentration for all the carbon substrates including chemically synthesized graphene and MWCNT. This study was crucial in our quest for an ideal SERS substrate. Our observations let us to conclude that chemically synthesized graphene was not the only candidate for the preparation of SERS substrates. Since carbon materials efficiently adsorb and also provide a separate channel for energy decay (fluorescence quenching), even activated charcoal could be employed as a SERS platform. However, carbon alone could not provide an effective solution for the preparation of SERS substrates. Therefore, combining the plasmonic effect of the metal nanoparticles with the efficient adsorption and fluorescence quenching of carbon materials would be ideal. In the next part of the carbon studies, graphene-Ag composites which were either prepared by in situ reduction process or physically mixed were studied for SERS activity. An ideal SERS substrate should possess the following properties: (i) Support plasmon, thereby provide SERS enhancement (ii) Easy to fabricate or synthesize (large scale/bulk) (iii) Ensure high reproducibility and sensitivity (iv) Low false alarm from matrix chemicals (v) Cost effective (vi) Solid substrate (in the form of chip, pellet, slide etc.) Hence, as a final study, carbon silver based composites were explored. R6G was chosen as an analyte again and SERS experiments were conducted. Raman signals at low concentration could be obtained for the carbon-Ag composites as well. In addition, feasibility experiments were also conducted for an explosive molecule, FOX-7. From these preliminary experiments we observed that carbon-metal NP composites can be efficient, cost-effective SERS substrates that will overcome the current issue. The previous chapters dealt with the trace detection of explosives. The next part of the thesis deals with the development of the Raman spectroscopic methods for non-invasive detection of concealed objects. Chapters 4 and 5 primarily focus on explosives detection. Spatially offset Raman spectroscopy (SORS) instrumentation was developed in the laboratory for non-invasive detection solid and liquid explosives. Several experiments were carried out to detect concealed materials inside high density polyethylene (HDPE) containers, coloured glass bottles, envelopes etc. with this technique, Raman signals of materials could be retrieved even within 4 mm thick outer-layer. SORS imaging experiments were also performed on bilayered compounds, tablets etc. However, while performing the SORS experiments, it was observed that due to the restriction in geometry imposed by the method, the signals from the inner-layers could be obtained only up to a certain depth. This posed a serious limitation of SORS for practical scenarios, where the thickness of the outer layer may be tens of mm. In such situation, SORS may not be an effective method. We then performed Raman experiments using a transmission geometry using a series of samples. The transmission Raman (TR) experiments yielded better SNR for the inner (concealed) material as compared to the outer material. Although transmission Raman experiments yielded better signal but these experiments were again geometry dependent, hence, less flexible and TR experiments did not provide information about the position of the underlying materials. In order to obtain complete information, it was necessary to understand photon migration in a multiple scattering medium. It is known that a photon in a multiple scattering medium may be approximated to undergo a random-walk. Statistically, the photon that undergoes multiple scattering in a medium loses its sense of origin (direction), hence, there is a finite probability to observe the exiting photon in any direction. Rayleigh and NIR based imaging modalities have been conducted using this model. Diffuse optical tomographic (DOT) measurements also deal with measuring the photons that have exited the sample after undergoing multiple scattering in a turbid medium. If it was possible to collect the Rayleigh photons or the diffuse photons in DOT experiments, in principle, Raman photons could also be collected from several directions. It was then proposed that if Rayleigh scattered photons can exit at 4π solid angle from a sample, then it can be assumed that some Rayleigh photons may convert to Raman photons, which in turn, shall have a finite probability to exit the sample from all the sides (4π solid angles). This idea of collecting Raman photons has never been discussed before! Thus, as expected based on the above principles, we were able to record Raman scattered photons at all angles and on all sides. This new technique has been termed as ‘Universal Multiple Angle Raman Spectroscopy (UMARS)’. Monte Carlo simulation studies were also performed to understand the distribution of photons in a multiple scattering medium. Simulation studies also revealed that Raman photons exited from all sides of the medium at varying percentages. Hence, several fiber optic probes were designed for illumination and collection to perform the UMARS experiments for samples concealed at depths beyond 20 mm. UMARS was not only applied successfully for the detection of concealed explosives, but also for biologically relevant samples as well. In fact a pharmaceutical tablet as thick as 7 mm was also tested with UMARS and signals could be successfully obtained. Since the UMARS signals were obtained from all possible angles, imaging experiments were also conducted to obtain sample specific information. Frequency-specific images of bilayer materials could be obtained. In the case where one material was concealed within another, the reconstruction of the frequency-specific intensities in a contour plot revealed the position of the concealed layer. One of the most challenging and exciting studies that was conducted was to use UMARS to obtain shapes of hidden materials. Several shapes such as dumbbell, ellipsoid etc were fabricated (made of glass) and were filled with a test chemical, trans-stilbene (TS). This shape was placed inside an outer material like ammonium nitrate (AN) that was taken in a glass beaker. The diameter of the beaker was varied from 25 mm to 60 mm. A series of UMARS measurement was carried out with 10 collection fiber optic probes. The spatial resolution (vertical) was varied from 200 μm to 1 mm. Series of UMARS images were obtained which were then processed and the intensity of the individual fibers were averaged (CCD row pixels) based on the image of the individual fiber on the CCD. The frequency specific intensity of the materials was utilized to reconstruct 2D or a 3D shape. The shapes of the objects could be clearly discerned using UMARS imaging. This marks a major step for the development of UMARS as a 3D imaging modality. UMARS experiments conducted so far have affirmed our belief that this technology can be used as an effective technique for screening solid and liquid samples at airports, railway stations and other entry points. 3D imaging for biomedical diagnostics will provide molecular information in addition to the location and shape of an object inside a tissue such as calcified masses and bones. In the final part of the thesis, 2D Raman correlation spectroscopic method was applied to understand the dynamics of a system that was subjected to external perturbation. In the field of explosive processing and formulations, large batches are generally prepared. However, it is very difficult to ascertain the molecular or structural changes that occur during the processing of these formulations in situ. Analytical methods to monitor the changes online are limited. Raman spectroscopy can be an effective technique for such measurements. This process however, generates a large number of spectra. In such cases, it becomes cumbersome to handle such large number of data and obtain meaningful information. 2D correlation spectroscopy can be applied under such situations. 2D correlation analysis generates essentially two maps, synchronous and asynchronous. In this study, 2D Raman correlation spectroscopy was applied to ammonium nitrate that was subjected to temperature variations. 2D maps were constructed to obtain information about the structural changes associated with temperature. The synchronous map reveals the overall similarity of the intensity changes. Whereas, the 2D asynchronous maps provide the sequence of changes that occur. Based on the set of well defined rules proposed by Isao Noda, the synchronous and the asynchronous correlation maps were analysed. Hence, generalized 2D correlation spectroscopy can be extended to any kind of perturbation and will prove useful in understanding the structural dynamics. The objective of the thesis was to explore various facets of Raman spectroscopy that would be useful in the field of high energy materials specifically in the detection of explosives. Attempts were made for the development of trace detection of explosives using Raman based technique, SERS. In addition, bulk detection of concealed explosives was performed non-invasively using SORS and UMARS. In the field of high energy materials, these techniques will find immense applications. Raman spectroscopy, as we saw is a very important technique that can be used as a stand-alone method and can also be interfaced with other analytical or imaging modalities. This treatise is an example where the strength of this powerful spectroscopic method has been explored to some extent.

Copper zinc tin selenide (Cu2ZnSnSe4 or CZTSe) is a quaternary compound semiconductor material that has attained more and more attention for thin film photovoltaic applications. CZTSe is only comprised of abundant and non-toxic elements. People have concerns about availability and cost of indium from CIGS and tellurium from CdTe, also about cadmium’s toxicity. These concerns have promoted CZTSe as an alternative thin film solar cell material. The major issues about CZTSe absorber fabrication are: tin loss during selenization process and existence of secondary phases. Recent improvements of CZTSe absorber have increased the efficiency of CZTSe thin film solar cell to 9.7% in laboratory, and this was accomplished by using H2Se as selenium source in a “two-stage” process. [1] However “one-stage” vacuum co-evaporation technique is still the most popular technique for CZTSe thin-film solar cells fabrication. In this research, Cu2ZnSnSe4 thin-film solar cells have been fabricated by using a two-step rapid thermal selenization process. The first step selenization is operated at 375℃, a relatively low annealing temperature, which helps avoiding the most common issue of tin loss. The second step selenization is carried out at a higher annealing temperature, 400℃ to 500℃, at where the formation of CZTSe quaternary compound can be completed, and fewer secondary phases remain in the CZTSe absorber bulk. A specially designed metallic precursor stacks deposition order has been developed to inhibit tin loss and zinc loss during selenization. Vacuum co-evaporation technique is not feasible to mass production, due to facility difficulty and bad uniformity. And H2Se is toxic and dangerous. We have developed these metallic precursor stacks vacuum deposition process and two-step selenium vapor selenization process. We believe this technique is more suitable for potential mass production in future. The properties of CZTSe thin-films and the performance of CZTSe thin-film solar cells have been characterized using techniques, including J-V, Raman spectroscopy, spectral response, and SEM/EDS. The best performance CZTSe thin-film solar cell that have been accomplished, has an open circuit voltage of 0.42 volt, shirt circuit current densities of 14.5 mA/cm2, fill factor of 47%, and efficiency of 2.86%.

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The interfacial micromechanics of both high modulus and low modulus carbon fibres have been investigated using Raman spectroscopy. The innovative step was to make low modulus carbon fibres more Raman active by coating them with SWNTs to act as as a strain sensor. Two types of SWNTs have been employed; namely HiPCO SWNTs and COOH SWNTs. Single fibre deformation tests were carried out and the Raman band shift rates with respect to fibre strain have been determined. Meanwhile, different SWNTs coating methods have been investigated. The method of adding COOH SWNTs into the silane layer and within a hot cured epoxy layer was found to generate the highest band shift rates. Furthermore, an investigation of the effect of SWNTs on the strength of the interface was also carried out. A coating of COOH SWNTs was found to significantly improve the interfacial shear strength. Micromechanical tests have been carried out and the stress transfer between the carbon fibres and an epoxy resin was monitored using three different model composite geometries; namely microdroplet-fibre, a film-fibre and a standard fragmentation approach. The result of interfacial shear stress determined from microdroplet-fibre method varied and was found to be highly dependent on the droplet size and shape; this gave the lowest values of interfacial shear stress (ISS). The method of film-fibre obtained an intermediate ISS value which is between that from the microdroplet model test and the fragmentation test. The standard fragmentation test using Raman technique gives the highest ISS and HiPCO SWNTs were found to be a better strain sensor without affecting the original interfacial properties.

Due to its exceptional mechanical and electrical properties, graphene (one layer sheet of carbon atoms) has attracted a lot of attention since its discovery in 2004. The purpose of this research is to compare the Raman spectra of graphene with plasma treated graphene sheets which have been treated by changing the different parameters affecting the plasma treatment like gas flow, power and pressure and treatment time. The graphene we used for our high pressure studies are 4-5 layer CVD deposited graphene samples prepared by our collaborators in Dr. W. B. Choi’s group. First we report a Raman spectroscopy study of graphene on copper substrate at high pressures. Diamond anvil cell (DAC) was used to generate pressure. In situ Raman spectra were collected at pressures up to 10 GPa. The results indicate that the G band of graphene shifts with pressure significantly (about 5 cm-1/GPa) whereas the 2D band changes very little. The plasma treated samples were loaded into DAC. Raman spectrum was captured. Parts of the spectrum which were not related to the grapheme peak position were eliminated. The background was reduced. Peaks were found and fitted using FITYK software and the shift of each peak compared to its last position was observed when the pressure was increased. Next we studied plasma treated graphene samples treated with different partial pressure treatments under high pressure and compared them to each other using zirconia anvil cell with the same method.