This thesis describes investigations into the properties of -phase BEDT-TTF charge transfer salts. Charge transfer salts are mainly studied as they are very useful test beds for fundamental physics due to the tuneability of their proper- ties and ground states. The effects of temperature and pressure on such systems have been studied, as these allow access to a wide range of different states and properties. Transport properties of these systems have been studied to obtain information about the Fermi surface and effective mass, and the effect of deuter- ation and also change of pressure media will be discussed. The interaction of infrared radiation with these systems has also been investigated and simultaneous pressure and temperature measurements will be presented, something not greatly studied due to the large technical challenges. The techniques and approaches for overcoming these are also discussed. Chapter 1 provides an introduction to the organic materials themselves with particular emphasis on the actual compounds studied. Chapter 2 provides the necessary theoretical background for studying organic charge transfer salts using magnetic quantum oscillations and their infrared re- ectivity. Chapter 3 covers the experimental techniques and also discusses some of the challenges encountered and their solutions to aid others working in this area. Chapter 4 describes an investigation into the transport properties of - (ET)2Cu(SCN)2 by studying Shubnikov-de Haas oscillations using both deuter- ated and normal samples and using two different pressure media, and comparing it to work done using a third. Chapter 5 presents an investigation into the pressure dependence of selected phonon modes in -(ET)2Cu(SCN)2 using infrared radiation on a deuterated sam- ple. Chapter 6 presents what is believed to be the first pressure and temperature dependent infrared study of an organic molecular material. In this case the or- ganic molecular material is d8--(ET)2Cu[N(CN)2]Br, but the techniques should be readily transferable to other materials.

O desenvolvimento e validação de métodos analíticos é um procedimento necessário quando um método não normalizado é utilizado por um laboratório de ensaios. A validação de métodos também é um requisito específico da norma ABNT NBR ISO/IEC 17025, que determina os requisitos gerais para a competência dos laboratórios de ensaio e calibração. O objetivo da validação é demonstrar que o método analítico, nas condições em que é executado, produz resultados com a exatidão requerida. O Laboratório de Corrosão, Proteção e Reciclagem de Materiais (LACOR), da UFRGS, tem o ensaio de determinação de metais por fluorescência de raios X, acreditado pelo CGCRE/INMETRO, conforme ABNT NBR ISO/IEC 17025. O ensaio é feito usando o método de espectrometria de fluorescência de raios X por dispersão de energia (EDXRF). Este método, contudo, não é normalizado e, portanto, o mesmo foi validado, neste trabalho de pesquisa, para atender a este requisito. A validação foi feita com base no documento orientativo DOQ-CGCRE-08 e no guia EURACHEM. Os parâmetros de validação, para o ensaio quantitativo por EDXRF, que foram calculados neste trabalho são: seletividade; limite de detecção (LD) e limite de quantificação (LQ); linearidade e faixa de trabalho; veracidade de medição (tendência, erro normalizado, Z-score e comparação com método de referência) e precisão (repetibilidade, precisão intermediária e reprodutibilidade). Além disso, foi desenvolvida uma metodologia de cálculo de incerteza de medição para o ensaio por EDXRF Os resultados obtidos neste estudo demonstram que o método EDXRF, usado na determinação de metais em aços, é um método não normalizado validado e compatível com os resultados obtidos com os métodos de referência: espectrometria de fluorescência de raios X por dispersão de comprimento de onda (WDXRF), fotométricos e espectrometria de absorção atômica (AAS). Inclusive, o WDXRF é um método de referência usado em muitas normas internacionais, que descrevem métodos de análise de aços por fluorescência de raios X, como ASTM E572 ou ASTM E1085. O estudo desenvolvido nesta dissertação permitiu que o LACOR mantivesse sua acreditação no ensaio de determinação de metais por fluorescência de raios X, na avaliação do CGCRE/INMETRO, no presente ano. Outros frutos deste trabalho foram a confecção das curvas de calibração do espectrômetro NITON XL3t GOLDD+ e a revisão do procedimento de ensaio, onde esses novos conhecimentos sobre a técnica EDXRF foram aplicados. Futuramente, este trabalho pode ser usado por outros pesquisadores para desenvolver estudos em outras matrizes metálicas, como cobre, alumínio, titânio ou níquel, e, também, em outras áreas de aplicação como jóias, reciclagem de materiais metálicos ou, até mesmo, para análise elementar de resíduos retidos em membranas de troca iônica. / The development and validation of analytical methods is a required procedure when a non-standard method is used by a testing laboratory. Method validation is also a specific requirement of the ABNT NBR ISO / IEC 17025, which determines the general requirements for the competence of testing and calibration laboratories. The purpose of validation is to demonstrate that the analytical method, under the conditions in which it is performed, produces results with the required accuracy. The Corrosion, Protection and Recycling Materials Laboratory (LACOR), at UFRGS, has the X-ray fluorescence metal analysis, accredited by CGCRE / INMETRO, according to ABNT NBR ISO / IEC 17025. The test is performed using Energy Dispersive X-Ray Fluorescence spectrometry, EDXRF method. This method, however, is not standardized; therefore, it was validated in this research to meet this requirement. The validation was based on the DOQ-CGCRE-08 document and the EURACHEM guide. The method performance calculated in this study for quantitative testing by EDXRF are: selectivity; limit of detection (LOD) and limit of quantification (LOQ); linearity and working range; trueness (bias, normalized error, Z-score and comparison with reference method) and precision (repeatability, intermediate precision and reproducibility). In addition, a measurement uncertainty calculation methodology was developed for the EDXRF testing The results obtained in this study demonstrate that the EDXRF method, used in the determination in the chemical analysis of steels, is a validated non-standard method and compatible with the results obtained with the reference methods: Wavelength Dispersive X-Ray Fluorescence spectrometry (WDXRF), photometric and atomic absorption spectrometry (AAS). In addition, WDXRF is a reference method used in many international standards, which describes analysis of steels by X-ray fluorescence spectrometry such ASTM E572 or ASTM E1085. The study developed in this dissertation allowed LACOR to maintain its accreditation in the test of metal by X-ray fluorescence analysis, in the CGCRE / INMETRO audit, this year. Other fruits of this work were the preparation of calibration curves of NITON XL3t GOLDD + spectrometer and complete revision of testing procedure, where this new knowledge about the EDXRF technique was applied. In the future, this work can be used by other researchers to develop studies in other base metals such as copper, aluminum, titanium or nickel, and also in other areas of application such as jewelry, recycling of metallic materials or even for analysis elemental residues retained in ion exchange membranes.

O desenvolvimento e validação de métodos analíticos é um procedimento necessário quando um método não normalizado é utilizado por um laboratório de ensaios. A validação de métodos também é um requisito específico da norma ABNT NBR ISO/IEC 17025, que determina os requisitos gerais para a competência dos laboratórios de ensaio e calibração. O objetivo da validação é demonstrar que o método analítico, nas condições em que é executado, produz resultados com a exatidão requerida. O Laboratório de Corrosão, Proteção e Reciclagem de Materiais (LACOR), da UFRGS, tem o ensaio de determinação de metais por fluorescência de raios X, acreditado pelo CGCRE/INMETRO, conforme ABNT NBR ISO/IEC 17025. O ensaio é feito usando o método de espectrometria de fluorescência de raios X por dispersão de energia (EDXRF). Este método, contudo, não é normalizado e, portanto, o mesmo foi validado, neste trabalho de pesquisa, para atender a este requisito. A validação foi feita com base no documento orientativo DOQ-CGCRE-08 e no guia EURACHEM. Os parâmetros de validação, para o ensaio quantitativo por EDXRF, que foram calculados neste trabalho são: seletividade; limite de detecção (LD) e limite de quantificação (LQ); linearidade e faixa de trabalho; veracidade de medição (tendência, erro normalizado, Z-score e comparação com método de referência) e precisão (repetibilidade, precisão intermediária e reprodutibilidade). Além disso, foi desenvolvida uma metodologia de cálculo de incerteza de medição para o ensaio por EDXRF Os resultados obtidos neste estudo demonstram que o método EDXRF, usado na determinação de metais em aços, é um método não normalizado validado e compatível com os resultados obtidos com os métodos de referência: espectrometria de fluorescência de raios X por dispersão de comprimento de onda (WDXRF), fotométricos e espectrometria de absorção atômica (AAS). Inclusive, o WDXRF é um método de referência usado em muitas normas internacionais, que descrevem métodos de análise de aços por fluorescência de raios X, como ASTM E572 ou ASTM E1085. O estudo desenvolvido nesta dissertação permitiu que o LACOR mantivesse sua acreditação no ensaio de determinação de metais por fluorescência de raios X, na avaliação do CGCRE/INMETRO, no presente ano. Outros frutos deste trabalho foram a confecção das curvas de calibração do espectrômetro NITON XL3t GOLDD+ e a revisão do procedimento de ensaio, onde esses novos conhecimentos sobre a técnica EDXRF foram aplicados. Futuramente, este trabalho pode ser usado por outros pesquisadores para desenvolver estudos em outras matrizes metálicas, como cobre, alumínio, titânio ou níquel, e, também, em outras áreas de aplicação como jóias, reciclagem de materiais metálicos ou, até mesmo, para análise elementar de resíduos retidos em membranas de troca iônica. / The development and validation of analytical methods is a required procedure when a non-standard method is used by a testing laboratory. Method validation is also a specific requirement of the ABNT NBR ISO / IEC 17025, which determines the general requirements for the competence of testing and calibration laboratories. The purpose of validation is to demonstrate that the analytical method, under the conditions in which it is performed, produces results with the required accuracy. The Corrosion, Protection and Recycling Materials Laboratory (LACOR), at UFRGS, has the X-ray fluorescence metal analysis, accredited by CGCRE / INMETRO, according to ABNT NBR ISO / IEC 17025. The test is performed using Energy Dispersive X-Ray Fluorescence spectrometry, EDXRF method. This method, however, is not standardized; therefore, it was validated in this research to meet this requirement. The validation was based on the DOQ-CGCRE-08 document and the EURACHEM guide. The method performance calculated in this study for quantitative testing by EDXRF are: selectivity; limit of detection (LOD) and limit of quantification (LOQ); linearity and working range; trueness (bias, normalized error, Z-score and comparison with reference method) and precision (repeatability, intermediate precision and reproducibility). In addition, a measurement uncertainty calculation methodology was developed for the EDXRF testing The results obtained in this study demonstrate that the EDXRF method, used in the determination in the chemical analysis of steels, is a validated non-standard method and compatible with the results obtained with the reference methods: Wavelength Dispersive X-Ray Fluorescence spectrometry (WDXRF), photometric and atomic absorption spectrometry (AAS). In addition, WDXRF is a reference method used in many international standards, which describes analysis of steels by X-ray fluorescence spectrometry such ASTM E572 or ASTM E1085. The study developed in this dissertation allowed LACOR to maintain its accreditation in the test of metal by X-ray fluorescence analysis, in the CGCRE / INMETRO audit, this year. Other fruits of this work were the preparation of calibration curves of NITON XL3t GOLDD + spectrometer and complete revision of testing procedure, where this new knowledge about the EDXRF technique was applied. In the future, this work can be used by other researchers to develop studies in other base metals such as copper, aluminum, titanium or nickel, and also in other areas of application such as jewelry, recycling of metallic materials or even for analysis elemental residues retained in ion exchange membranes.

O desenvolvimento e validação de métodos analíticos é um procedimento necessário quando um método não normalizado é utilizado por um laboratório de ensaios. A validação de métodos também é um requisito específico da norma ABNT NBR ISO/IEC 17025, que determina os requisitos gerais para a competência dos laboratórios de ensaio e calibração. O objetivo da validação é demonstrar que o método analítico, nas condições em que é executado, produz resultados com a exatidão requerida. O Laboratório de Corrosão, Proteção e Reciclagem de Materiais (LACOR), da UFRGS, tem o ensaio de determinação de metais por fluorescência de raios X, acreditado pelo CGCRE/INMETRO, conforme ABNT NBR ISO/IEC 17025. O ensaio é feito usando o método de espectrometria de fluorescência de raios X por dispersão de energia (EDXRF). Este método, contudo, não é normalizado e, portanto, o mesmo foi validado, neste trabalho de pesquisa, para atender a este requisito. A validação foi feita com base no documento orientativo DOQ-CGCRE-08 e no guia EURACHEM. Os parâmetros de validação, para o ensaio quantitativo por EDXRF, que foram calculados neste trabalho são: seletividade; limite de detecção (LD) e limite de quantificação (LQ); linearidade e faixa de trabalho; veracidade de medição (tendência, erro normalizado, Z-score e comparação com método de referência) e precisão (repetibilidade, precisão intermediária e reprodutibilidade). Além disso, foi desenvolvida uma metodologia de cálculo de incerteza de medição para o ensaio por EDXRF Os resultados obtidos neste estudo demonstram que o método EDXRF, usado na determinação de metais em aços, é um método não normalizado validado e compatível com os resultados obtidos com os métodos de referência: espectrometria de fluorescência de raios X por dispersão de comprimento de onda (WDXRF), fotométricos e espectrometria de absorção atômica (AAS). Inclusive, o WDXRF é um método de referência usado em muitas normas internacionais, que descrevem métodos de análise de aços por fluorescência de raios X, como ASTM E572 ou ASTM E1085. O estudo desenvolvido nesta dissertação permitiu que o LACOR mantivesse sua acreditação no ensaio de determinação de metais por fluorescência de raios X, na avaliação do CGCRE/INMETRO, no presente ano. Outros frutos deste trabalho foram a confecção das curvas de calibração do espectrômetro NITON XL3t GOLDD+ e a revisão do procedimento de ensaio, onde esses novos conhecimentos sobre a técnica EDXRF foram aplicados. Futuramente, este trabalho pode ser usado por outros pesquisadores para desenvolver estudos em outras matrizes metálicas, como cobre, alumínio, titânio ou níquel, e, também, em outras áreas de aplicação como jóias, reciclagem de materiais metálicos ou, até mesmo, para análise elementar de resíduos retidos em membranas de troca iônica. / The development and validation of analytical methods is a required procedure when a non-standard method is used by a testing laboratory. Method validation is also a specific requirement of the ABNT NBR ISO / IEC 17025, which determines the general requirements for the competence of testing and calibration laboratories. The purpose of validation is to demonstrate that the analytical method, under the conditions in which it is performed, produces results with the required accuracy. The Corrosion, Protection and Recycling Materials Laboratory (LACOR), at UFRGS, has the X-ray fluorescence metal analysis, accredited by CGCRE / INMETRO, according to ABNT NBR ISO / IEC 17025. The test is performed using Energy Dispersive X-Ray Fluorescence spectrometry, EDXRF method. This method, however, is not standardized; therefore, it was validated in this research to meet this requirement. The validation was based on the DOQ-CGCRE-08 document and the EURACHEM guide. The method performance calculated in this study for quantitative testing by EDXRF are: selectivity; limit of detection (LOD) and limit of quantification (LOQ); linearity and working range; trueness (bias, normalized error, Z-score and comparison with reference method) and precision (repeatability, intermediate precision and reproducibility). In addition, a measurement uncertainty calculation methodology was developed for the EDXRF testing The results obtained in this study demonstrate that the EDXRF method, used in the determination in the chemical analysis of steels, is a validated non-standard method and compatible with the results obtained with the reference methods: Wavelength Dispersive X-Ray Fluorescence spectrometry (WDXRF), photometric and atomic absorption spectrometry (AAS). In addition, WDXRF is a reference method used in many international standards, which describes analysis of steels by X-ray fluorescence spectrometry such ASTM E572 or ASTM E1085. The study developed in this dissertation allowed LACOR to maintain its accreditation in the test of metal by X-ray fluorescence analysis, in the CGCRE / INMETRO audit, this year. Other fruits of this work were the preparation of calibration curves of NITON XL3t GOLDD + spectrometer and complete revision of testing procedure, where this new knowledge about the EDXRF technique was applied. In the future, this work can be used by other researchers to develop studies in other base metals such as copper, aluminum, titanium or nickel, and also in other areas of application such as jewelry, recycling of metallic materials or even for analysis elemental residues retained in ion exchange membranes.

The role of clusters in planetary atmospheres and the interstellar medium is potentially important. Investigating such a role requires basic experimental information, however lacking. The goal of this thesis was to develop an efficient experimental set-up to produce clusters in the laboratory in concentrations large enough to allow their high resolution spectra to be recorded, thus providing the necessary data allowing the physico-chemical properties of the clusters to be studied.<p>The study of this subject however suffers from the lack of basic experimental data. The goal is therefore to produce clusters in the laboratory in concentration large enough to record their high resolution spectrum. This is the initial aim of the present thesis.<p>During this work, we have built and extensively tested a new experimental set-up called FANTASIO (``Fourier trANsform, Tunable diode and quadrupole mAss spectrometers interfaced to a Supersonic expansIOn'). With the help of this new device, various experiments on jet-cooled species have been performed.<p>The cartography of the supersonic expansion was established, using the mass spectrometer as a moving pressure probe. This enabled us to characterize the geometrical properties of the supersonic jet produced by circular and slit nozzles and to determine the position of the virtual nozzle. The effect of the axisymmetric expansion geometry on the R(0) lineshape in the nu_3 band of N_2O, recorded by FTIR, was also investigated.<p>The rotational temperature of the jet-cooled molecules was determined to be a few K by measuring the intensity of lines in spectra recorded by FTIR spectroscopy.<p>Vibrational energy transfer occuring in the expansion between N_2O molecules and different collision partners was investigated on the nu_2+nu_3-nu_2 band of N_2O, again using FTIR spectroscopy. The trend of these transfers was found to be related to the energy difference between the v_2=1 level of N_2O and the closest vibrational state in the collision partner, with the largest population.<p>The sensitivity of the set-up was enhanced by a factor of 5 by increasing the absorption path length, using a multipass system. A procedure to remove the residual gas contribution from the IR spectra was developped, based on the mass spectrometer. Thanks to this sensitivity increase, broadband absorption features of clusters were observed for a C_2H_2-Ar mixture in circular and slit expansions.<p>The optical sensitivity of FANTASIO was again increased by the implementation of the CW-CRDS system. The enhancement over FTIR was calculated to be over a factor 750. Thanks to this drastic improvement, spectral signatures of various clusters were recorded, such as C_2H_2-Ar, C_2H_2 multimers, C_2H_2-N_2O and C_2H_2-CO_2, at high resolution.<p>The role of clustering in generating unusual line shapes of acetylene in an axisymmetric expansion was investigated. We demonstrated that C_2H_2 aggregates produced in the expansion are responsible for central dips observed in the monomer absorption. These acetylene clusters thus appear to be formed in the centre of the expansion, while, unexpectedly, acetylene-Ar complexes are formed at the edge of the conical expansion.<p>Various research prospects were explored during this thesis thanks to the FANTASIO device, opening new research directions. FANTASIO is today operational and defines a useful tool to achieve the study of small clusters by infrared spectroscopy./<p><p>Le rôle des agrégats dans les atmosphères planétaires et dans le milieu interstellaire est potentiellement important. Cependant, les études sur ce sujet souffrent du manque de données expérimentales. Le but de cette thèse était de développer un dispositif expérimental efficace pour produire au laboratoire des agrégats en quantité suffisante pour permettre l'enregistrement de leur spectre infrarouge à haute résolution et donc l'étude de leurs propriétés physico-chimiques.<p>Durant ce travail, nous avons construit et testé un nouveau dispositif expérimental appelé FANTASIO, basé sur un jet supersonique couplé à un spectromètre de masse, un spectromètre à transformée de Fourier et un système CRDS. Grâce à cet appareillage, différentes expériences sur des molécules à basse température ont été menées.<p>L'expansion supersonique a été cartographiée en utilisant le spectromètre de masse comme une sonde de pression mobile. Cette cartographie nous a permis d'établir les propriétés géométriques des jets supersoniques produits par les orifices circulaire et de type fente, et de déterminer la position de l'orifice virtuel. L'effet de la géométrie de l'expansion sphérique sur le profil de la raie R(0) de la bande nu_3 de N_2O, enregistré par FTIR, a aussi été étudié.<p>Une température rotationnelle de quelques K a été déterminée pour les molécules refroidies en jet supersonique par mesure de la distribution d'intensité de raies dans les spectres enregistrés par FTIR.<p>Le transfert d'énergie vibrationnelle entre des molécules de N_2O et différents partenaires collisionnels a été étudié en analysant l'intensité de la bande nu_2+nu_3-nu_2 de N_2O, enregistré également par spectroscopie FTIR. Il a été trouvé que la tendance de ces transferts est liée à la différence d'énergie entre le niveau v_2=1 de N_2O et l'état vibrationnel le plus proche et le plus peuplé du partenaire collisionnel.<p>La sensibilité du dispositif a été augmentée d'un facteur 5 dû à l'allongement du chemin d'absorption, grâce à l'utilisation d'un système multipassage. Une procédure basée sur l'utilisation du spectromètre de masse et visant à enlever la contribution du gaz chaud résiduel dans les spectres infrarouges a été mise au point. Grâce à cette augmentation de sensibilité, des structures d'absorption non résolues d'agrégats ont été observées dans des expansions en trou et en fente d'un mélange de C_2H_2-Ar.<p>La sensibilité optique de FANTASIO a encore été augmentée par l'ajout au dispositif d'un système CW-CRDS. L'amélioration par rapport au spectromètre à transformée de Fourier a été calculée comme étant supérieure à un facteur 750. Grâce à cette importante amélioration, les signatures spectrales de divers agrégats, tels que C_2H_2-Ar, des multimères de C_2H_2, C_2H_2-N_2O et C_2H_2-CO_2, ont été enregistrées à haute résolution.<p>Le rôle de l'agrégation dans la génération de profils de raie inhabituels dans une expansion en trou de l'acétylène a été étudié. Nous avons démontré que les agrégats de C_2H_2 produits dans le jet supersonique sont responsables des creux observés dans le profil d'absorption du monomère. Ces agrégats apparaissent donc comme étant formés au centre de l'expansion, tandis que, de manière inattendue, les agrégats de C_2H_2-Ar sont formés aux bords de l'expansion conique.<p>Plusieurs idées de recherche ont été explorées durant cette thèse grâce au dispositif FANTASIO, ouvrant de nouvelles directions de recherche. FANTASIO est aujourd'hui opérationnel et se présente comme un outil utile dans l'étude des petits agrégats par spectroscopie infrarouge. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

This thesis presents HELIOS, an in-house laboratory for time-resolved pump-probe spectroscopy with extreme-ultraviolet (XUV) probe radiation. A wide span of pump wavelengths can be generated using commercial laser equipment while XUV probe radiation is generated via a high harmonic generation process in a noble gas delivering probe photons with energies between 20 eV and 72 eV. The XUV beam path features a time-preserving monochromator and was constructed and built in-house. HELIOS features an overall time resolution of about 50 fs when using 800 nm pump and 41 eV probe photons. An energy resolution of 110 meV at 41 eV photon energy can be achieved. HELIOS features two beamlines. One µ-focus beamline with an XUV focal size of about 20 µm can be used with experiments that require such a small XUV focal size as well as with different end stations. The other beamline features a semi-permanently mounted end station for angle-resolved photoelectron spectroscopy under ultra-high vacuum conditions. Experiments demonstrating the usability of HELIOS and the two beamlines are presented. A pump-probe measurement on graphene demonstrates the capability of determining a large part of the k-space in only one measurement due to the use of an ARTOF angle-resolved time-of-flight electron spectrometer. A non-angle-resolved pump-probe measurement on the conducting polymer PCPDTBT demonstrates the high signal-to-noise ratio achievable at this beamline in non-angle-resolved photoelectron-spectroscopy pump-probe measurements. The usability of the µ-focus beamline is demonstrated with time-resolved measurements on magnetic samples employing an in-house-designed spectrometer. These experiments allow the retrieval of element-specific information on the magnetization within a sample employing the transversal magneto-optical Kerr effect (T-MOKE). Additionally, a Fourier transform spectrometer for the XUV is presented, the concept was tested at a synchrotron and it was used to determine the longitudinal coherence of the XUV radiation at HELIOS.

近年來微機電系統之技術與產品發展迅速，所衍生之微型光譜儀技術與產品，具有架構簡單、元件數少、輕薄短小、性價比高等特點，可以解決傳統光譜分析儀器之應用困境，並可應用至諸多領域，受到各方重視。微機電產業與半導體產業相容的特性，被視為下階段成長動力；2003年光譜分析儀器產業發生兩件併購案，可見微小化光譜儀的技術與市場，備受光電與醫藥集團重視與期待。在此產業環境與時空背景下，微型光譜儀技術是否具有市場價值，其產品應用領域是否具有成長潛力，而其技術價值是否得以評估與衡量，是一個具有技術與市場意義的研究主題。 透過技術文獻與專利資料之搜尋，本研究追溯光譜分析儀器的技術沿革與演進、光柵設計與製程的改善，討論微型光譜儀之技術特點與發展趨勢；其次並蒐集主要應用領域產業之市場資訊，包含光電、環境、生醫、農業、色彩等產業，分析各主要應用市場規模與相關產業概況；最後根據技術生命週期與技術評價方法，以假設條件建立價值分析模型，並與產業研究報告及國際併購案例進行比較分析。 研究結果發現，微型光譜儀之技術趨勢包括光學架構力求簡化與扁平設計，先進的凹面繞射光柵採向量電磁波法演算與可量產之微機電製程，而訊號處理能力與偵測器特性將成為新技術競爭之關鍵；專利搜尋結果透露大型光譜儀廠商尚未積極切入，而掌握應用領域且具有關鍵製程能力者，將主導技術市場。 本研究也發現在微型光譜儀的應用市場中，生醫感測與環境檢測最具爆發潛力，十年內之市場規模分別可達到新台幣200億及100億元；農業食品與色彩管理之應用市場也具有相當吸引力，若能開發低價且方便使用之消費性檢測裝置，其市場規模皆可達到新台幣60億以上；而光電量測主要屬產業設備應用，屬於穩定成長市場，規模大約維持在10億以內。總和微型光譜儀之五大應用市場，其規模在2015年預估約為新台幣150億，並將於2020年成長一倍至新台幣300億元。 經由技術評價文獻、研究報告併購案例與分析結果，本研究認為微型光譜儀產業屬於成長期階段，適合採用淨現金流量折現法評估技術價值；而近十年之微小光譜儀產業之併購案例，除展現綜效外，其併購規模與內容也反映了其技術價值與評價方式所隱含之技術生命週期認定。 最後，本研究假設一具有關鍵技術之新創公司模型，並以淨現金流量折現法計算其技術價值，在技術貢獻度（研發費用比例）接近40 % 條件下，技術價值約末與長期稅後純益相當，且與專利貢獻度及營收成長幅度呈現高度正相關。 基於以上研究發現，本研究建議國內相關研發機構與學術單位，加強微型光譜儀相關技術人才之培育，以及應用市場之保護措施，並且積極經由產學合作，建立專利或其他智慧財產防護壁壘，同時鼓勵企業投資與新創事業，以建立產業聯盟、加強獎勵措施與租稅優惠等方式，讓我國的半導體、光電、微電子與微機電等高科技產業，共同在新的微型光譜儀產業與市場競爭中取得先機。 / Because of the advantages of simple structures, less components, lower price, light weight and compact size, micro spectrometers apply to more and more fields which need optical spectrum detection and overcome the drawback of conventional spectrometers, which shows great market potential and business opportunities. Since MEMS fabrication is highly compatible to semiconductor industry and plays important role in the product and technology evolution of micro spectrometer, the development and applications of micro spectrometer are expected as a moving force of MEMS industrial growth. Two M&A cases in 2003 also indicate the market potential and technology value of miniature spectrometers are highly appreciated by the photonic enterprises and biomedical industry. Therefore, the topic of technology development and applied market value of miniature spectrometers is worth investigated. Spectrometer can analyze physical and chemical properties in material, which the used wavelength will depend on applications. The features of spectrum detection include: non-invasion, non-destruction, chemical discrimination, wavelength flexibility, high sensitivity and fast analysis speed. Apparently even with wide range of application, its popularity is not big enough. The main reasons come that conventional spectrometer uses the scanning mechanical design with long measurement time, high unit price and bulky size as well as inconvenient movement, complicated daily maintenance and wavelength calibration, so will substantially limit the industrial scale and growth. By analyzing the technical literatures and related patents, the technology trend of miniature spectrometers include: less components and simplified system designing, the advanced optical algorithm to cancel aberration of wavelength dispersion, and mass- productive MEMS fabrication. Signal processing and the characteristic of detector will be the key competitiveness of next evolving stage. Players who know the applications well and own the fabrication of key components will dominate the market. The applied markets of miniature spectrometer are also investigated in this thesis. The biomedical and environmental uses have most market potential, and the market value target 600M USD and 350M USD respectively. The market value of application in agricultural foods and color management are also target 200M USD and 180M USD once consumer-type devices with low price entering the markets. In the photonic instrument industry and optical measurement application, the market value will stably growing up and maintain the size around 30M USD. The sum total of five main applications of miniature spectrometers will target 450M USD in 2015 and 1000M USD in 2020. Regarding the studies on literature, market reports and M&A cases, the industry of miniature spectrometer can be identified in the growth stage, which discounted cash flow (DCF) method is most suitable for technical value analysis. The size and terms of two M&A cases of miniature spectrometer industry in 2003 also echo the evaluation, market value estimation and the identification of growth state in technical life cycle. A business model of a start-up company with key technology in miniature spectrometer is build and analyzed in this thesis. By DCF method and under the circumstance when R&D cost ratios 40 % of total cost, the technical vale equals long-term net annual profit and is highly related to R&D cost ratio and net profit size. By the investigation of this thesis, we suggest domestic research and academic institutes put more effects on technical development and talent education of miniature spectrometer. The preferential treatment to local firms and intellectual property barrier should be build as soon as possible. In such a way, the advantageous of semiconductor, opto-electronic, micro-electronic and MEMS industries in Taiwan will take more preference and business opportunity in miniature spectrometer market competition in the near future.

<p>Испитана је тачност методе мерења<br />апсолутне активности гама емитера помоћу једног<br />гама спектрометра на већим брзинама бројања. У<br />оквиру истраживања нађен је једноставан<br />поступак за корекцију спектралних података на<br />случајне коинциденције.<br />&nbsp;&nbsp; Принцип коинцидентне технике и корекције<br />сумарног врха и врхова пуне енергије помоћу<br />врхова у спектру насталим само услед случајних<br />коинциденција примењен је на радиоизотопе са<br />једноставном и веома сложеном шемом. Изведене<br />су једноставне формуле за мерења активности са и<br />без корекције на ефективне угаоне корелације у<br />којима фигуришу подаци само из једног гама<br />спектра чиме је постигнута знатна једноставност у<br />техници мерења.<br />&nbsp;&nbsp; Резултати овог истраживања показали су да<br />се активност двофотонских гама емитера може<br />измерити помоћу HPGe детектора и дигиталне<br />спектроскопске јединице са тачношћу испод 1% на<br />разним брзинама бројања само помоћу једног<br />спектра. Резултати за изотопе са сложеном шемом<br />добијени једноставном техником указују да се<br />техника може применити на рутинска мерења где<br />грешка не превазилази 10%</p> / <p>Ispitana je tačnost metode merenja<br />apsolutne aktivnosti gama emitera pomoću jednog<br />gama spektrometra na većim brzinama brojanja. U<br />okviru istraživanja nađen je jednostavan<br />postupak za korekciju spektralnih podataka na<br />slučajne koincidencije.<br />&nbsp;&nbsp; Princip koincidentne tehnike i korekcije<br />sumarnog vrha i vrhova pune energije pomoću<br />vrhova u spektru nastalim samo usled slučajnih<br />koincidencija primenjen je na radioizotope sa<br />jednostavnom i veoma složenom šemom. Izvedene<br />su jednostavne formule za merenja aktivnosti sa i<br />bez korekcije na efektivne ugaone korelacije u<br />kojima figurišu podaci samo iz jednog gama<br />spektra čime je postignuta znatna jednostavnost u<br />tehnici merenja.<br />&nbsp;&nbsp; Rezultati ovog istraživanja pokazali su da<br />se aktivnost dvofotonskih gama emitera može<br />izmeriti pomoću HPGe detektora i digitalne<br />spektroskopske jedinice sa tačnošću ispod 1% na<br />raznim brzinama brojanja samo pomoću jednog<br />spektra. Rezultati za izotope sa složenom šemom<br />dobijeni jednostavnom tehnikom ukazuju da se<br />tehnika može primeniti na rutinska merenja gde<br />greška ne prevazilazi 10%</p> / <p>It has been investigated the accuracy of absolute<br />activity measurement of gamma emitters with a single<br />gamma spectrometer at higher count rates. In this<br />research it has been found relatively simple procedure<br />for random summing correction of spectral data.<br />Principle of coincidence technique and random<br />summing correction of sum peaks and full energy<br />peaks using pile up peaks is applied to measure<br />absolute activity of simple and complicated decay<br />scheme radioisotopes. Simple equations were deduced<br />for absolute activity measurements with and without<br />correction for effective angular correlations. Variables<br />in these equations are spectral data only. Great<br />simplicity is achieved in coincidence technique of<br />absolute activity measurement.<br />It was shown that absolute activity of<br />radioisotopes emitting simultaneously two gamma<br />photons can be measured with accuracy below 1% at<br />high count rates using HPGe detector and DSP<br />spectroscopy unit. Measurements of complicated<br />decay scheme radioisotopes shown that simple<br />technique is able to bring satisfactory results with<br />accuracies below 10%</p>

Les rendements de fission sont des données importantes pour les applications nucléaires ainsi que pour les modèles théoriques qui cherchent à reproduire ces distributions. Les rendements des produits de fission légers pour de nombreux noyaux ont été mesurés par le passé sur le spectromètre Lohengrin. Mais la méthode expérimentale utilisée, détection par chambre à ionisation, ne permet pas la séparation des isotopes pour les produits de fission lourds. Pour valider la méthode dans cette région et compléter les bibliothèques, les rendements isobariques de l’235U(nth,f), du 239Pu(nth,f) et du 241Pu(nth,f) ont été mesurés. La mise en place d’un nouveau dispositif de détection gamma sur le spectromètre a permis de déterminer les rendements isotopiques du 239Pu(nth,f). De plus les distributions en charge ionique et en énergie cinétique des produits de fission ont été étudiées, et ont mis en évidence la présence d'isomères nanosecondes pour certains de ces noyaux. / In spite of the huge amount of fission yield data available in different libraries, more accurate values are still needed for nuclear energy applications and to improve our understanding of the fission process. Thus measurements of fission yields were performed at the mass spectrometer Lohengrin at the Institut Laue-Langevin in Grenoble, France. The mass separator Lohengrin is situated at the research reactor of the institute and permits the placement of an actinide layer in a high thermal neutron flux. It separates fragments according to their atomic mass, kinetic energy and ionic charge state by the action of magnetic and electric fields. Coupling with a high resolution ionization chamber the experiment was used to investigate the mass and isotopic yields in the light mass region. Almost all fission yields of isotopes from Th to Cf have been measured at Lohengrin with this method. It has been extended in this work to the heavy mass region for the reactions 235U(nth,f), 239Pu(nth,f) and 241Pu(nth,f). For these higher masses an isotopic separation is no longer possible. That is why a new method was undertaken with the reaction 239Pu(nth,f) to determine the isotopic yields by gamma spectrometry. During these experiments the ionic charge state and kinetic energy distributions have been measured. Nanosecond isomers have been discovered for some nuclei thanks to a non gaussian charge state distribution. The kinetic energy distributions present very interesting structures which have been also discussed.

Les collisions d’ions lourds ultrarelativistes ont pour objectif principal l'étude des propriétés de la matière nucléaire soumise à températures et densités d'énergie extrêmes. La chromodynamique quantique (QCD) prédit, dans ces conditions, l’existence d’une nouvelle phase de la matière dans laquelle les constituants des hadrons sont déconfinés en un plasma de quarks et gluons (QGP). Les saveurs lourdes (charme et beauté) sont produites lors de processus durs aux premiers instants des collisions, avant de traverser le milieu. Par conséquent, la mesure des quarkonia (mésons cc et bb) est particulièrement intéressante pour l'étude du QGP : leur dissociation, due notamment à l’écrantage de couleur, est sensible à la température initiale du système. Les mesures effectuées au SPS et RHIC ont permis de mettre en évidence plusieurs caractéristiques du milieu produit, mais ont aussi laissé plusieurs questions sans réponse. Avec une énergie 14 fois supérieure à celle du RHIC, l’accélérateur LHC (Large Hadron Collider) au CERN, entré en fonctionnement fin 2009, a ouvert une nouvelle ère pour l'étude des propriétés du QGP. ALICE (A Large Ion Collider Experiment) est une des quatre grandes expériences fonctionnant auprès du LHC et dont le but principal est l'étude du plasma de quarks et gluons produit dans les collisions d'ions plomb à une énergie de 2.76 TeV par nucléon. Elle enregistre aussi des collisions pp afin de fournir la référence indispensable pour l'étude des collisions noyau-noyau et proton-noyau et de tester les calculs perturbatifs de QCD dans la région des faibles valeurs de la variable d'échelle x de Bjorken. Les quarkonia, ainsi que les saveurs lourdes ouvertes et les mésons légers, sont mesurés dans ALICE suivant leur mode de désintégration muonique avec le spectromètre à muons situé à petit angle polaire. Il est constitué d'un ensemble d’absorbeurs, d’un dipôle chaud, de cinq stations de trajectographie (Muon Tracking) et de deux stations de déclenchement (Muon Trigger). Le travail présenté dans cette thèse a été réalisé de 2011 à 2013 pendant les premières années de prise de données dans l’expérience ALICE. Après une introduction à la physique des ions lourds à hautes énergies et une description du setup expérimental, une étude des performances du Muon Trigger en Pb-Pb est proposée. En particulier, la stabilité dans le temps du détecteur et son efficacité de fonctionnement sont contrôlées. Le cluster size, correspondant au nombre moyen de voies adjacentes touchées par particule détectée, est étudié en fonction des différents variables. Les valeurs expérimentales sont comparées à des simulations afin de fournir une paramétrisation de cet effet. Finalement, la production du méson Ç en collisions Pb-Pb est analysée en détail et comparée à celle en collisions pp à la même énergie. Les résultats obtenus sont comparés aux mesures du J/ψ par ALICE, aux mesures par CMS et à des prédictions de modèles théoriques. / The main goal of ultrarelativistic heavy-ion collisions is the study of the properties of the matter at very high temperatures and energy densities. Quantum chromodynamics (QCD) predicts in these conditions the existence of a new phase of the matter whose components are deconfined in a Quark-Gluon Plasma (QGP). Heavy quarks (charm e bottom) are produced in the first stages of the collisions, before to interact with the medium. Therefore, the measurement of the quarkonia (cc and bb mesons) is of particular interest for the study of the QGP: their dissociation mainly due to the colour screening is sensible to the initial temperature of the medium. Previous measurements at the SPS and RHIC allowed to understand some characteristics of the system produced, but they also opened many questions. With an energy 14 times higher than RHIC, the LHC (Large Hadron Collider) at CERN opened a new era for the study of the QGP properties. ALICE (A Large Ion Collider Experiment) is the LHC experiment fully dedicated to the study of the Quark-Gluon Plasma produced in Pb-Pb collisions at an energy of 2.76 TeV per nucleon. The experiment also participates to the proton-proton data taking in order to obtain the fundamental reference for the study of ion-ion and proton-ion collisions and for testing the predictions at very small Bjorken-x values of the perturbative QCD. Quarkonia, D and B mesons and light vector mesons are measured at forward rapidity by a Muon Spectrometer exploiting their (di)muonic decay. This detector is composed of a front absorber, a dipole magnet, five stations of tracking (Muon Tracking) and two stations of trigger (Muon Trigger). The work presented in this thesis has been carried out from 2011 to 2013 during the first period of data taking of ALICE. After a detailed introduction of the heavy-ion physics and a description of the experimental setup, the performance of the Muon Trigger in Pb–Pb collisions are shown. A particular attention is devoted to the stability of the detector during the time and to the trigger effectiveness. Moreover, the cluster size, corresponding to the number of adjacent strips hit by a particle, is studied as a function of different variables. The experimental results will be compared to simulations in order to obtain a good parametrization of this phenomenon. Finally, the Ç production in Pb-Pb collisions is carefully analysed and compared to that in pp collisions at the same energy. The results are then compared to the J/ψ measurements obtained by ALICE, to the CMS results and to some theoretical predictions.