The aim of the presented work was to deposit cubic boron nitride thin films by magnetron sputtering under simultaneous stress relaxation by ion implantation. An in situ instrument based on laser deflectometry on cantilever structures and in situ ellipsometry, was used for in situ stress measurements. The characteristic evolution of the instantaneous stress during the layered growth of cBN films observed in IBAD experiments, could be reproduced for magnetron sputter deposition. To achieve simultaneous stress relaxation by ion implantation, a complex bipolar pulsed substrate bias source was constructed. This power supply enables the growth of cBN thin films under low energy ion irradiation (up to 200 eV) and, for the first time, the simultaneous implantation of ions with an energy of up to 8 keV during high voltage pulses. It was demonstrated that the instantaneous stress in cBN thin films can be released down to -1.1 GPa by simultaneous ion bombardment during the high voltage pulses. A simultaneous stress relaxation during growth is possible in the total investigated ion energy range between 2.5 and 8 keV. These are the lowest ion energies reported for the stress relaxation in cBN. Since such a substrate bias power supply is easy to integrate in existing process lines, this result is important for industrial deposition of thin films, not only for cubic boron nitride films. It was found that the amount of stress relaxation depends on the number of atomic displacements (displacements per atom: dpa) that are induced by the high energy ion bombardment and is therefore dependent on the ion energy and the high energy ion flux. In practise, this means that the stress relaxation is controlled by the product of the pulse voltage and the pulse duty cycle or frequency. The cantilever bending measurements were complemented on microscopic scale by x-ray diffraction (XRD). The analysis of the cBN (111) lattice distances revealed a pronounced biaxial compressive state of stress in a non-relaxed cBN film with d(111) being larger in out-of-plane than in in-plane direction. Post deposition annealing at 900 ° C of a sample with an ion induced damage of 1.2 dpa, resulted in a complete relaxation of the lattice with equal in-plane and out-of-plane lattice parameters. In the case of medium-energy ion bombardment, the in-plane and out-of-plane lattice parameters approach the value of the annealed sample with increasing ion damage. This is a clear evidence for stress relaxation within the cBN lattice. The stability of cBN under ion bombardment was investigated by IR spectroscopy and XRD. The crystalline cBN was found to be very stable against ion irradiation. However a short-range ordered, sp3/sp2 - mixed phase may exist in the films, which could be preferably converted to a sp2 -phase at high damage values. From the analysis of the near surface region by XANES, it can be concluded the stress relaxation by the energetic ion bombardment is less at the surface than in the bulk film. This is explained with the dynamic profile of the ion induced damage, that reaches the stationary bulk value in 15-20 nm depth, whereas it is decreasing towards the surface. This fits with the results that the stress relaxation is dependent on the amount of ion induced damage. Comparing the results from substrate curvature measurement, XRD, XANES, and IR spectroscopy possible mechanisms of stress relaxation are discussed. Concluding the results, it can be stated that using simultaneous ion implantation for stress relaxation during the deposition it is possible to produce BN films with a high amount of the cubic phase and with very low residual stress.

O aço maraging é conhecido pela sua alta resistência mecânica proveniente da formação de precipitados intermetálicos como Ni3Ti e Fe2Mo durante o envelhecimento, porém com subsequente perda de tenacidade à fratura. Existe uma vasta literatura sobre este tipo de aço, o qual é submetido a diversos tratamentos térmicos. Normalmente dois tratamentos térmicos são aplicados: uma homogeneização inicial para solubilização dos precipitados, sendo a recomendação geral 820 °C/1 h, e posteriormente o tratamento de envelhecimento, variando a temperatura de 455 °C a 510 °C e o tempo de 3 a 12 h. No entanto, pode haver variações no tratamento, como aquecimento após homogeneização numa faixa de temperatura intercrítica ou abaixo da Ac1 visando a reversão da martensita em austenita e o refino de grão. Até o presente momento, não está bem definida a influência da temperatura/tempo em tratamentos de temperaturas inter ou subcríticas que visam o refinamento da estrutura e o aumento da austenita retida/reversa. A literatura mostra tratamentos na liga maraging 300 por meio de estudos mais antigos, da década de 70 e 80, utilizando aquecimentos curtos e cíclicos para reversão e estabilização da austenita reversa. Estudos mais recentes de outras ligas utilizaram tratamentos isotérmicos para difusão e reversão da martensita em austenita. Nesta proposta serão pesquisadas as duas rotas de tratamento, cíclica e isotérmica, para avaliar a reversão martensita-austenita. Os tratamentos cíclicos foram caracterizados por EBSD, MEV e difração de raio-X ex-situ. Os tratamentos isotérmicos foram caracterizados por EBSD e difração de raio-X de fonte sincrotron in-situ, ou seja, medida em tempo real durante o tratamento. Ambas as condições foram avaliadas mecanicamente por meio de ensaios de flexão de 3 pontos. / Maraging steel is known for its high mechanical strength resulting from the formation of intermetallic precipitates such as Ni3Ti and Fe2Mo during aging heat treatment, with subsequent loss of fracture toughness. There is a vast literature on this type of steel, which is subjected to various thermal treatments. Normally two heat treatments are applied: an initial homogenization for solubilization of the precipitates, the general recommendation being 820 ° C/1 h, and later the aging treatment, varying temperature from 455 ° C to 510 ° C and time of treatment from 3 to 12 hours. However, there may be applied other heat treatments, such as heating after homogenization in an intercritical temperature range or below Ac1 for the reversion of martensite-to-austenite and grain refinement. To date, the influence of temperature and time on inter- or subcritical temperature treatments aiming at grain refinement and martensite-to-austenite reversion is not well defined. The literature shows treatments in the maraging 300 alloy, from the 70s and 80s, using short and cyclic heat treatment for reversion and stabilization of austenite. Recent studies of other alloys have used isothermal treatments for diffusion and martensite-to-austenite revresion. In this study, two heat treatment routes, cyclical and isothermal, were investigated to evaluate the martensite-to-austenite reversion. Cyclic treatments were characterized by EBSD, SEM and ex-situ X-ray diffraction. The isothermal treatments were characterized by EBSD and X-ray diffraction of synchrotron source in-situ, that is, measured in real time during the treatment. Both conditions were mechanically evaluated by 3-point-bending tests.

O presente trabalho apresenta o desenvolvimento de metodologias baseadas no sistema de Análise por Injeção Seqüencial (SIA) para a determinação de fosfato e silicato, nitrito e nitrato, assim como a especiação de Fe(II) e Fe(III) em amostras de interesse ambiental, com ênfase para sistemas aquáticos. Para todas as determinações utilizou-se a espectrofotometria de absorção molecular na região do visível como técnica de detecção. A determinação de fosfato e silicato foi baseada na reação de ambos os ânions com molibdato de amônio em meio ácido e posterior redução do Mo(VI) à Mo(V) com ácido ascórbico. O procedimento SIA foi desenvolvido para contornar a interferência mútua das duas espécies explorando o efeito de complexação do molibdato pelo ácido oxálico. A determinação de nitrito foi baseada na reação de diazotação com sulfanilamida e diclorato de N-1 naftil etilenodiamina (NED), enquanto a determinação de Fe(II) baseou-se na sua complexação com 1,10 fenantrolina. A determinação de nitrato e Fe(III) foi efetuada pelas mesmas reações após a redução a nitrito e Fe(II) em colunas de cádmio e zinco amalgamado, respectivamente. A estabilidade das curvas analíticas foi avaliada em diferentes dias de trabalho, obtendo-se variações não superiores a 5% durante um período de 4 dias. O sistema de injeção seqüencial foi explorado também no sentido de regenerar as colunas redutoras no intervalo de tempo entre duas amostras. A estabilidade das curvas analíticas, a viabilidade de regeneração das colunas redutoras e a possibilidade de realizar a amostragem através de filtração tangencial, permitindo a realização de análises com características de tempo real, sugerem que o sistema de injeção seqüencial tem grande potencial para ser implementado em estações automáticas de monitoramento da fração solúvel de indicadores de poluição em águas naturais e residuais. / The present work presents the development of analytical methodologies based on Sequential Injection Analysis (SIA) for determination of phosphate and silicate, nitrite and nitrate, as well as speciation Fe(II)/Fe(III) in environmental samples with emphasis for aquatic environments. All determinations were performed using molecular absorption spectrophotometry at the visible range of the spectrum as the detection technique. The determination of phosphate and silicate was based on the reaction of both anions with ammonium molybdate in acidic medium, followed by reduction of Mo(VI) to Mo(V) with ascorbic acid. The SIA procedure was developed to avoid the mutual interference of both species exploiting the complexation of the molybdate by oxalic acid. The determination of nitrite was based on the diazotation reaction with sulfanilamide and N-l naphtyl ethylenediamine dihydrochlorine (NED), while the determination of Fe(II) were based on the complexation with 1,10 phenantroline. The determination of nitrate and Fe(III) were based on the same reactions, performed after their reduction to nitrite and Fe(II) in reducing columns containing cooperized cadmium and amalgamated zinc, respectively. The stability of the analytical curves was evaluated in different working days, in which no variations greater than 5% were observed during a period of 4 consecutive days. The sequential injection analysis was exploited to regenerate the reducing columns in the time interval between two sample. The stability of the analytical curves, the easy and automatic regeneration of the reducing columns, as well as the possibility to perform sampling through tangential filtration, which permits the analysis to be performed in real time, are characteristics that show the potential application of the sequential injection systems in automatic stations for monitoring the soluble fraction of pollution indicators in natural waste waters.

O presente trabalho apresenta o desenvolvimento de metodologias baseadas no sistema de Análise por Injeção Seqüencial (SIA) para a determinação de fosfato e silicato, nitrito e nitrato, assim como a especiação de Fe(II) e Fe(III) em amostras de interesse ambiental, com ênfase para sistemas aquáticos. Para todas as determinações utilizou-se a espectrofotometria de absorção molecular na região do visível como técnica de detecção. A determinação de fosfato e silicato foi baseada na reação de ambos os ânions com molibdato de amônio em meio ácido e posterior redução do Mo(VI) à Mo(V) com ácido ascórbico. O procedimento SIA foi desenvolvido para contornar a interferência mútua das duas espécies explorando o efeito de complexação do molibdato pelo ácido oxálico. A determinação de nitrito foi baseada na reação de diazotação com sulfanilamida e diclorato de N-1 naftil etilenodiamina (NED), enquanto a determinação de Fe(II) baseou-se na sua complexação com 1,10 fenantrolina. A determinação de nitrato e Fe(III) foi efetuada pelas mesmas reações após a redução a nitrito e Fe(II) em colunas de cádmio e zinco amalgamado, respectivamente. A estabilidade das curvas analíticas foi avaliada em diferentes dias de trabalho, obtendo-se variações não superiores a 5% durante um período de 4 dias. O sistema de injeção seqüencial foi explorado também no sentido de regenerar as colunas redutoras no intervalo de tempo entre duas amostras. A estabilidade das curvas analíticas, a viabilidade de regeneração das colunas redutoras e a possibilidade de realizar a amostragem através de filtração tangencial, permitindo a realização de análises com características de tempo real, sugerem que o sistema de injeção seqüencial tem grande potencial para ser implementado em estações automáticas de monitoramento da fração solúvel de indicadores de poluição em águas naturais e residuais. / The present work presents the development of analytical methodologies based on Sequential Injection Analysis (SIA) for determination of phosphate and silicate, nitrite and nitrate, as well as speciation Fe(II)/Fe(III) in environmental samples with emphasis for aquatic environments. All determinations were performed using molecular absorption spectrophotometry at the visible range of the spectrum as the detection technique. The determination of phosphate and silicate was based on the reaction of both anions with ammonium molybdate in acidic medium, followed by reduction of Mo(VI) to Mo(V) with ascorbic acid. The SIA procedure was developed to avoid the mutual interference of both species exploiting the complexation of the molybdate by oxalic acid. The determination of nitrite was based on the diazotation reaction with sulfanilamide and N-l naphtyl ethylenediamine dihydrochlorine (NED), while the determination of Fe(II) were based on the complexation with 1,10 phenantroline. The determination of nitrate and Fe(III) were based on the same reactions, performed after their reduction to nitrite and Fe(II) in reducing columns containing cooperized cadmium and amalgamated zinc, respectively. The stability of the analytical curves was evaluated in different working days, in which no variations greater than 5% were observed during a period of 4 consecutive days. The sequential injection analysis was exploited to regenerate the reducing columns in the time interval between two sample. The stability of the analytical curves, the easy and automatic regeneration of the reducing columns, as well as the possibility to perform sampling through tangential filtration, which permits the analysis to be performed in real time, are characteristics that show the potential application of the sequential injection systems in automatic stations for monitoring the soluble fraction of pollution indicators in natural waste waters.

Lastwechseltests stellen eine standardisierte und etablierte Methode zur Zuverlässigkeitsbewertung und Produktqualifizierung in der Leistungselektronik dar. Sie basieren auf der Applikation von wiederkehrenden Laststromimpulsen, welche im Leistungsbauelement in zyklischen Temperaturschwankungen umgesetzt werden. Die dabei induzierten thermo-mechanischen Spannungen, hervorgerufen durch die unterschiedlichen Werkstoffeigenschaften der im Verbundsystem beteiligten Fügepartner, führen letztendlich zu den typischen Versagensmechanismen in der Aufbau- und Verbindungstechnik. Herkömmliche Lastwechseltests bilden allerdings die komplexen Belastungssituationen unter Feldbedingungen, in welchen unterschiedliche Lastfaktoren simultan auftreten, nur ungenügend nach. Im Kontext der Einführung neuartiger Bauelement- und Package-Technologien, rauer werdenden Umgebungsbedingungen sowie steigenden Zuverlässigkeits- und funktionalen Sicherheitsanforderungen ergibt sich somit der Bedarf an verbesserten Methoden zur Zuverlässigkeitstestbewertung. Ein möglicher Ansatz besteht in der Kombination verschiedener Belastungsarten, mit dem Ziel, Testeffizienz sowie Testabdeckung zu erhöhen. Im Rahmen dieser Arbeit wurden daher unter Verwendung eines selbstentwickelten Lastwechselteststandes systematische Lastwechseltestuntersuchungen, sowohl in standardmäßiger Ausführung als auch mit überlagerten passiven Temperaturzyklen, an diskreten Leistungsbauelementen durchgeführt. Neben der Untersuchung unterschiedlicher Sperrschichttemperaturprofile erfolgte auch ein Vergleich unterschiedlicher Bauelementtypen. Auf Basis einer qualitativen und quantitativen Testauswertung wurden belastungsbasierte Lebensdauermodelle aufgestellt. Dabei zeigte sich, dass die den Standard-Lastwechseltests zugrunde-liegenden Lebensdauermodelle nicht die Testergebnisse der überlagerten Lastwechseltests vorhersagen konnten. Die Ursache dafür lag im temperaturabhängigen Werkstoffverhalten der Moldmasse begründet, welches Einfluss auf den dominierenden Fehlermodus Bonddrahtabheber hat. Daher wird die Verwendung von fall-sensitiven Lebensdauermodellen vorgeschlagen, da somit die veränderte Schädigungsphysik beim Überschreiten des Glasüberganges der Moldmasse berücksichtigt werden kann. Darüber hinaus wird in dieser Arbeit eine neue Methode zur optischen in-situ-Untersuchung von Leistungsbauelementen vorgestellt, welche zukünftig die Untersuchung von thermisch-transienten sowie thermo-mechanischen Vorgängen unter aktiver Belastung erlaubt.:Symbol- und Abkürzungsverzeichnis Danksagung Kurzfassung Abstract 1 Einleitung 1.1 Motivation 1.2 Fokus und Ziel der Arbeit 2 Grundlagen zur Leistungselektronik und zu ihrer Zuverlässigkeitsbewertung 2.1 Aufbau typischer Leistungselektronikkomponenten und Module 2.1.1 Leistungsklassen und klassische Aufbauvarianten 2.1.2 Leistungshalbleiter 2.1.3 Substrattechnologien für Leistungsmodule 2.1.4 Verbindungstechniken in Leistungselektronikmodulen 2.1.4.1 Chipflächen- und Baugruppenkontaktierung 2.1.4.2 Chipanschlusskontaktierung 2.1.4.3 Kühlkörperanbindung 2.1.5 Verkapslungskonzepte 2.1.6 Kühlkonzepte in der Leistungselektronik 2.2 Typische Fehlermodi und -mechanismen 2.3 Lebensdauerbewertung von Leistungselektronik0 2.3.1 Globale Ansätze zur Produktqualifizierung und Zuverlässigkeitsbewertung0 2.3.2 Lebensdauertests in der Leistungselektronik 2.3.2.1 Überblick und Einordnung von Lastwechseltests 2.3.2.2 Testkonzepte und -strategien 2.3.3 Lebensdauermodellierung 3 Neue methodische Ansätze und Prüfstandsentwicklung 3.1 Überlagerung von aktiven Lastwechseln mit passiven Temperaturzyklen 3.2 Entwicklung und Aufbau eines Lastwechselprüfstandes zur Untersuchung von überlagerten Belastungstests 3.2.1 Konzeption 3.2.2 Kühlkörper-Design 3.2.3 Steuer- und Auswertesoftware 3.2.4 Lastwechselteststand 3.2.5 Messprozedur 3.2.6 Validierung der Tvj-basierten Temperaturmessung 3.3 Optisches In-situ-Monitoring während Lastwechseltests 3.3.1 Testaufbau und Probenpräparation 3.3.2 IR-Messungen an angeschliffenem Prüfling 4 Prüfgegenstände, Testplanung und Testdurchführung 4.1 Auswahl und Übersicht der Prüflinge 4.2 Testkonzeption und Versuchsplanung 4.2.1 Lastwechseltests 4.2.2 Temperaturschocktests 4.3 Testaufbau und -durchführung 4.3.1 Lastwechseltests 4.3.2 Temperaturschocktests 5 Testergebnisse 5.1 Messdatenanalyse und Auswerteprozedur 5.2 Statistische Testauswertung 5.2.1 Übersicht über Testergebnisse 5.2.2 Weibull-Verteilungen 5.3 Fehleranalytik 5.3.1 Bonddrahtausfälle 5.3.2 Lotdegradation 5.4 Optische In-situ-Analyse während aktiver Belastung 5.4.1 Methodik 5.4.2 Verschiebungsfelder in Abhängigkeit von ∆Tvj und Tvj,m 5.4.3 Einfluss der Einschaltzeit ton auf Verschiebungsfelder 5.4.4 Ableitung der Dehnungsfelder und Ergebnisdiskussion 6 Lebensdauermodellierung 6.1 Belastungsbasierte Lebensdauermodelle 6.1.1 Lebensdauerdiagramme und -einflussfaktoren 6.1.2 Multiple lineare Regression 6.1.3 Berücksichtigung der effektiven Temperatur T(v)j,eff 6.1.4 Vergleich der Lebensdauermodelle mit überlagerten Testergebnissen 6.1.5 Zusammenfassung 146 6.1.6 Einordnung der ermittelten Lebensdauermodelle 6.2 FE-Analyse zur Validierung der Ergebnisse aus der Lebensdauermodellierung 7 Zusammenfassung und Ausblick Literaturverzeichnis Abbildungsverzeichnis Tabellenverzeichnis / Active power cycling tests represent a standardized and well-established method for reliability evaluation and product qualification in power electronics. They are based on the application of recurring load current pulses, which are converted into cyclic temperature swings in the power component. The thereby induced thermo-mechanical stress, caused by the different material properties of the joining partners involved in the composite system, ultimately leads to the typical failure modes and mechanisms in the devices. However, these conventional tests do not sufficiently stimulate the complex load schemes in field operations in which different load factors occur simultaneously. In the context of the introduction of novel device and package technologies, increasingly harsh environmental operation conditions as well as increasing reliability and functional safety requirements, there is a need for improved reliability test methods. One possible approach is the combination of different load factors in order to increase test efficiency and test coverage. Within the scope of this thesis, systematic reliability investigations, including standard power cycling tests as well as power cycling tests superimposed with passive thermal cycles, were therefore carried out on discrete power components using a self-developed test rig. In addition to the investigation of different junction temperature profiles, a comparison of different component types was performed. On the basis of a qualitative and quantitative test evaluation, load-based lifetime models were derived. It was found that the lifetime models determined on the basis of the standard power cycling tests could not predict the test results of the superimposed power cycling tests. The reason for this was the influence of the temperature-dependent material behaviour of the moulding com-pound, which has an influence on the failure mode wire-bond lift-off. Based on these findings, the use of case-sensitive lifetime models is suggested that are able to take the changed damage physics into account. In addition, a new method for the optical in-situ investigation of moulded power devices is presented, which allows the investigation of thermal-transient as well as thermo-mechanical processes in the package under active loading conditions.:Symbol- und Abkürzungsverzeichnis Danksagung Kurzfassung Abstract 1 Einleitung 1.1 Motivation 1.2 Fokus und Ziel der Arbeit 2 Grundlagen zur Leistungselektronik und zu ihrer Zuverlässigkeitsbewertung 2.1 Aufbau typischer Leistungselektronikkomponenten und Module 2.1.1 Leistungsklassen und klassische Aufbauvarianten 2.1.2 Leistungshalbleiter 2.1.3 Substrattechnologien für Leistungsmodule 2.1.4 Verbindungstechniken in Leistungselektronikmodulen 2.1.4.1 Chipflächen- und Baugruppenkontaktierung 2.1.4.2 Chipanschlusskontaktierung 2.1.4.3 Kühlkörperanbindung 2.1.5 Verkapslungskonzepte 2.1.6 Kühlkonzepte in der Leistungselektronik 2.2 Typische Fehlermodi und -mechanismen 2.3 Lebensdauerbewertung von Leistungselektronik0 2.3.1 Globale Ansätze zur Produktqualifizierung und Zuverlässigkeitsbewertung0 2.3.2 Lebensdauertests in der Leistungselektronik 2.3.2.1 Überblick und Einordnung von Lastwechseltests 2.3.2.2 Testkonzepte und -strategien 2.3.3 Lebensdauermodellierung 3 Neue methodische Ansätze und Prüfstandsentwicklung 3.1 Überlagerung von aktiven Lastwechseln mit passiven Temperaturzyklen 3.2 Entwicklung und Aufbau eines Lastwechselprüfstandes zur Untersuchung von überlagerten Belastungstests 3.2.1 Konzeption 3.2.2 Kühlkörper-Design 3.2.3 Steuer- und Auswertesoftware 3.2.4 Lastwechselteststand 3.2.5 Messprozedur 3.2.6 Validierung der Tvj-basierten Temperaturmessung 3.3 Optisches In-situ-Monitoring während Lastwechseltests 3.3.1 Testaufbau und Probenpräparation 3.3.2 IR-Messungen an angeschliffenem Prüfling 4 Prüfgegenstände, Testplanung und Testdurchführung 4.1 Auswahl und Übersicht der Prüflinge 4.2 Testkonzeption und Versuchsplanung 4.2.1 Lastwechseltests 4.2.2 Temperaturschocktests 4.3 Testaufbau und -durchführung 4.3.1 Lastwechseltests 4.3.2 Temperaturschocktests 5 Testergebnisse 5.1 Messdatenanalyse und Auswerteprozedur 5.2 Statistische Testauswertung 5.2.1 Übersicht über Testergebnisse 5.2.2 Weibull-Verteilungen 5.3 Fehleranalytik 5.3.1 Bonddrahtausfälle 5.3.2 Lotdegradation 5.4 Optische In-situ-Analyse während aktiver Belastung 5.4.1 Methodik 5.4.2 Verschiebungsfelder in Abhängigkeit von ∆Tvj und Tvj,m 5.4.3 Einfluss der Einschaltzeit ton auf Verschiebungsfelder 5.4.4 Ableitung der Dehnungsfelder und Ergebnisdiskussion 6 Lebensdauermodellierung 6.1 Belastungsbasierte Lebensdauermodelle 6.1.1 Lebensdauerdiagramme und -einflussfaktoren 6.1.2 Multiple lineare Regression 6.1.3 Berücksichtigung der effektiven Temperatur T(v)j,eff 6.1.4 Vergleich der Lebensdauermodelle mit überlagerten Testergebnissen 6.1.5 Zusammenfassung 146 6.1.6 Einordnung der ermittelten Lebensdauermodelle 6.2 FE-Analyse zur Validierung der Ergebnisse aus der Lebensdauermodellierung 7 Zusammenfassung und Ausblick Literaturverzeichnis Abbildungsverzeichnis Tabellenverzeichnis

Tato doktorská práce je zaměřena na vývoj algoritmu ke zpracování dat naměřených zařízením pro spektrometrii laserem indukovaného plazmatu (angl. LIBS). Zařízení LIBS s tímto algoritmem by mělo být následně schopno provést třídění vzorků a kvantitativní analýzu analytu in-situ a v reálném čase. Celá experimentální část této práce byla provedena ve Spolkovém institutu pro materiálový výzku a testování (něm. BAM) v Berlíně, SRN, kde byl sestaven elementární LIBS systém. Souběžně s experimentílní prací byl vytvořen přehled literárních zdrojů s cílem podat ucelený pohled na problematiku chemometrických metod používaných k analýze LIBS měření. Použití chemometrických metod pro analýzu dat získaných pomocí LIBS měření je obecně doporučováno především tehdy, jsou-li analyzovány vzorky s komplexní matricí. Vývoj algoritmu byl zaměřen na kvantitativní analýzu a třídění vyvřelých hornin na základě měření pomocí LIBS aparatury. Sada vzorků naměřených použitím metody LIBS sestávala z certifikovaných referenčních materiálů a vzorků hornin shromážděných přímo na nalezištích mědi v Íránu. Vzorky z Íránu byly následně na místě roztříděny zkušeným geologem a množství mědi v daných vzorcích bylo změřeno na Univerzitě v Clausthalu, SRN. Výsledné kalibrační křivky byly silně nelineární, přestože byly sestaveny i z měření referenčních vzorků. Kalibrační křivku bylo možné rozložit na několik dílčích tak, že závislost intenzity měděné čáry na množství mědi se nacházela v jiném trendu pro jednotlivé druhy hornin. Rozdělení kalibrační křivky je zpravidla přisuzováno tzv. matričnímu jevu, který silně ovlivňuje měření metodou LIBS. Jinými slovy, pokud určujeme množství analytu ve vzorcích s různou matricí, je výsledná kalibrační křivka sestavená pouze z jedné proměnné (intenzity zvolené spektrální čáry analytu) nepřesná. Navíc, normalizace takto vytvořených kalibračních křivek k intenzitě spektrální čáry matrčního prvku nevedla k výraznému zlepšení linearity. Je obecně nemožné vybrat spektrální čáru jednoho matričního prvku pokud jsou analyzovány prvky s komplexním složením matric. Chemometrické metody, jmenovitě regrese hlavních komponent (angl. PCR) a regrese metodou nejmenších čtverců (angl. PLSR), byly použity v multivariační kvantitatvní analýze, tj. za použití více proměnných/spektrálních čar analytu a matričních prvků. Je potřeba brát v potaz, že PCR a PLSR mohou vyvážit matriční jev pouze do určité míry. Dále byly vzorky úspěšně roztříděny pomocí analýzy hlavních komponent (angl. PCA) a Kohonenových map na základě složení matričních prvků (v anglické literatuře se objevuje termín ‚spectral fingerprint‘) Na základě teorie a experimentálních měření byl navržen algoritmus pro spolehlivé třídění a kvantifikaci neznámých vzorků. Tato studie by měla přispět ke zpracování dat naměřených in-situ přístrojem pro dálkovou LIBS analýzu. Tento přístroj je v současnosti vyvíjen v Brně na Vysokém učení technickém. Toto zařízení bude nenahraditelné při kvantifikaci a klasifikaci vzorků pouze tehdy, pokud bude použito zároveň s chemometrickými metodami a knihovnami dat. Pro tyto účely byla již naměřena a testována část knihoven dat v zaměření na aplikaci metody LIBS do těžebního průmyslu.