Zugl.: Hamburg, Techn. Univ., Diss., 2008

Techn. Hochsch., Diss., 2005--Aachen.

Este trabalho investigou o sistema (1 - x )PZT - x PMN, avaliando a influência da composição química e dos parâmetros de sinterização na microestrutura e propriedades elétricas dos corpos cerâmicos obtidos pelo método convencional de mistura de óxidos. Os óxidos usados foram o Nb2O5, ZrO2, TiO2, PbO e MgCO3, cominuídos e homogeneizados em moinho de bolas, por 3 horas. Para o 0,65PZT - 0,35PMN, utilizou-se 28,58% de Nb2O5, 38,93% de ZrO2, 23,29% de TiO2 e 9,2% de MgCO3; para o 0,75PZT-0,25PMN, utilizou-se 20,9% de Nb2O5, 45,34% de ZrO2, 27,13% de TiO2 e 6,62% de MgCO3 e para o 0,85PZT-0,15PMN, usa-se 12,71% de Nb2O5, 52,09% de ZrO2, 31,16% de TiO2 e 4,04% de MgCO3. O pó obtido foi submetido a calcinação a 1200°C por 4 h e, então, acrescentado PbO com um excesso de 2% em massa.à mistura, a qual foi submetida a uma nova calcinação a 800°C durante 2 horas. O pó resultante da calcinação foi conformado por prensagem, utilizando uma prensa uniaxial a 190 MPa, na forma de discos medindo 10 mm de diâmetro e 1,5 mm de espessura. A curva de queima dos corpos cerâmicos consistiu em um novo patamar a 500°C por 4h (e/ou a 800°C por 2h) e outro consecutivo a 1200°C por 4h. As amostras foram caracterizadas pela sua densidade e porosidade aparente (método de Arquimedes), composição de fases (por difração de raio-X), Microscopia Eletrônica de Varredura (MEV) e caracterização elétrica (constante dielétrica e capacitância). Os corpos cerâmicos correspondentes à composição 0,75PZT-0,25PMN alcançaram a maior densidade (7,09 ± 0,18 g/cm³) quando calcinados sucessivamente a 500°C e a 800°C, com os maiores valores de capacitância (210 pF a 200 KHz) e de constante dielétrica (1000 na frequência de 1 KHz), com menor evidência de formação de pirocloro e maior de perovskita. Os valores de constante dielétrica encontrados estão dentro do esperado para materiais cerâmicos piezoelétricos do tipo PZT - PMN, aproximadamente 1000 para freqüências de 1KHz. / This work investigated the system (1 - x )PZT - x PMN, evaluating the influence of the chemical composition and the sintering parameters on the microstructure and the electric properties of ceramic bodies obtained by the conventional method of mixture of oxides. The used oxides were Nb2O5, ZrO2, TiO2, PbO e MgCO3, squeezed and homogenized in mill of balls, for 3 hours. For the 0.65PZT-0.35PMN, it was used 28.58% of Nb2O5, 38.93% of ZrO2, 23.29% of TiO2 and 9.2% of MgCO3; for the 0.75PZT-0.25PMN, it was used 20.9% of Nb2O5, 45.34% of ZrO2, 27.13% of TiO2 and 6.62% of MgCO3 and for the 0.85PZT-0.15PMN, it is used 12.71% of Nb2O5, 52.09% of ZrO2, 31.16% of TiO2 and 4.04% of MgCO3. The obtained powder was submitted the calcination for 1200°C for 4 h and, then, increased PbO with an excess of 2% in mass, which was submitted to a new calcination to 800°C for 2 hours. The calcinated powder was conformed by pressing, using a uniaxial press to 190 MPa, in the form of disks measuring a diameter of 10mm and 1.5 mm of thickness. The curve of the burning of the ceramic bodies consisted in a new calcination to 500°C for 4h (and/or to 800°C for 2h) and other consecutive to 1200°C for 4h. The samples were characterized by density and apparent porosity (Method of Arquimedes), composition of phases (by X - rays diffraction), Scanning Electric Microstructure (SEM) and electrical properties characterization (dielectric constant and capacitance). The ceramic bodies corresponding to the composition 0.75PZT-0.25PMN reached the largest density (7.09 ± 0.18 g/cm³) when calcined successively to 500°C and 800°C, with the largest values of capacitance (210 pF to 200 KHz) and dielectric constant (1000 in the frequency of 1 KHz), with smaller evidence of pyrochlore formation and larger of perovskte. The values of dielectric constant found are inside of the expected for the piezoelectric ceramics of the type PZT- PMN, approximately 1000 by frequencies of 1KHz.

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-12-15Bitstream added on 2014-06-13T19:12:25Z : No. of bitstreams: 1 paes_c_me_ilha.pdf: 1124164 bytes, checksum: b30843e958a40bb7c8b7ff4142f19d31 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho tem como objetivo estudar, através de investigações de espectros no infravermelho (FTIR), as transições de fases estruturais do sistema ferroelétrico titanato zirconato de chumbo, PbZr1-xTixO3 (PZT) no Contorno de Fase Morfotrópico (Morphotropic Phase Boundary, conhecido como MPB), região em que as propriedades elétricas desse material são máximas. Foram analisadas as soluções sólidas PbZr0,53Ti0,47O3 e PbZr0,54Ti0,46O3, que à temperatura ambiente encontram-se no interior do MPB e PbZr0,55Ti0,45O3, composição no limite da região do MPB, entre a fase monoclínica e a fase romboédrica, região ainda não bem definida e sob intensa investigação. Estudos estão centrados na freqüência e na meia largura dos modos stretching nos octaedros (BO6) da estrutura perovskita (ABO3) em função da temperatura. Anomalias encontradas para amostras com 47 e 46 mol % de PbTiO3 sugerem as transições da fase monoclínica de baixa para alta temperatura ( LT M F ? HT M F ), da fase monoclínica de alta temperatura para a coexistência da fase monoclínica com a fase tetragonal ( M F ? M F + T F ), e da coexistência da fase monoclínica com a tetragonal para a fase cúbica ( M F + T F ? C F ). Na amostra com 45 mol % de PbTiO3 foram encontradas anomalias que podem também estar associadas às transições de fases, mas que não foram possíveis de serem identificadas nas fases envolvidas. / The present work studies, through investigations of the spectra in infrared (FTIR), the transitions of structural phases of the ferroelectric system lead zirconate titanate, PbZr1- xTixO3 (PZT), in the Morphotropic Phase Boundary (MPB), region where the electrical properties of this material are at its maxiumun. We analyzed the solid solutions PbZr0,53Ti0,47O3 and PbZr0,54Ti0,46O3, which at room temperature are found within the MPB and also the composition PbZr0,55Ti0,45O3, that is located on the limit of the MPB - between the monoclinic and the rhombohedral phases - a not-yet defined region under intense investigation. Studies are concentrating on frequency and half width of the stretching modes in octahedrons (BO6) of the perovskite structure (ABO3) regarding temperature. Anomalies found in samples with 47 and 46 mol % of PbTiO3 suggest transitions in the monoclinic phase from low to high temperature ( LT M F ? HT M F ), from monoclinic phase of high temperature to the coexistence between the monoclinic phase with the tetragonal phase ( M F ? M F + T F ), and the coexistence between the monoclinic phase with tetragonal for the cubic phase ( M F + T F ? C F ). In the sample with 45 % mol of PbTiO3 we have found anomalies that can also be associated with phase transitions. Such transitions have not been possible to identify during the stages of this work.

Este trabalho investigou o sistema (1 - x )PZT - x PMN, avaliando a influência da composição química e dos parâmetros de sinterização na microestrutura e propriedades elétricas dos corpos cerâmicos obtidos pelo método convencional de mistura de óxidos. Os óxidos usados foram o Nb2O5, ZrO2, TiO2, PbO e MgCO3, cominuídos e homogeneizados em moinho de bolas, por 3 horas. Para o 0,65PZT - 0,35PMN, utilizou-se 28,58% de Nb2O5, 38,93% de ZrO2, 23,29% de TiO2 e 9,2% de MgCO3; para o 0,75PZT-0,25PMN, utilizou-se 20,9% de Nb2O5, 45,34% de ZrO2, 27,13% de TiO2 e 6,62% de MgCO3 e para o 0,85PZT-0,15PMN, usa-se 12,71% de Nb2O5, 52,09% de ZrO2, 31,16% de TiO2 e 4,04% de MgCO3. O pó obtido foi submetido a calcinação a 1200°C por 4 h e, então, acrescentado PbO com um excesso de 2% em massa.à mistura, a qual foi submetida a uma nova calcinação a 800°C durante 2 horas. O pó resultante da calcinação foi conformado por prensagem, utilizando uma prensa uniaxial a 190 MPa, na forma de discos medindo 10 mm de diâmetro e 1,5 mm de espessura. A curva de queima dos corpos cerâmicos consistiu em um novo patamar a 500°C por 4h (e/ou a 800°C por 2h) e outro consecutivo a 1200°C por 4h. As amostras foram caracterizadas pela sua densidade e porosidade aparente (método de Arquimedes), composição de fases (por difração de raio-X), Microscopia Eletrônica de Varredura (MEV) e caracterização elétrica (constante dielétrica e capacitância). Os corpos cerâmicos correspondentes à composição 0,75PZT-0,25PMN alcançaram a maior densidade (7,09 ± 0,18 g/cm³) quando calcinados sucessivamente a 500°C e a 800°C, com os maiores valores de capacitância (210 pF a 200 KHz) e de constante dielétrica (1000 na frequência de 1 KHz), com menor evidência de formação de pirocloro e maior de perovskita. Os valores de constante dielétrica encontrados estão dentro do esperado para materiais cerâmicos piezoelétricos do tipo PZT - PMN, aproximadamente 1000 para freqüências de 1KHz. / This work investigated the system (1 - x )PZT - x PMN, evaluating the influence of the chemical composition and the sintering parameters on the microstructure and the electric properties of ceramic bodies obtained by the conventional method of mixture of oxides. The used oxides were Nb2O5, ZrO2, TiO2, PbO e MgCO3, squeezed and homogenized in mill of balls, for 3 hours. For the 0.65PZT-0.35PMN, it was used 28.58% of Nb2O5, 38.93% of ZrO2, 23.29% of TiO2 and 9.2% of MgCO3; for the 0.75PZT-0.25PMN, it was used 20.9% of Nb2O5, 45.34% of ZrO2, 27.13% of TiO2 and 6.62% of MgCO3 and for the 0.85PZT-0.15PMN, it is used 12.71% of Nb2O5, 52.09% of ZrO2, 31.16% of TiO2 and 4.04% of MgCO3. The obtained powder was submitted the calcination for 1200°C for 4 h and, then, increased PbO with an excess of 2% in mass, which was submitted to a new calcination to 800°C for 2 hours. The calcinated powder was conformed by pressing, using a uniaxial press to 190 MPa, in the form of disks measuring a diameter of 10mm and 1.5 mm of thickness. The curve of the burning of the ceramic bodies consisted in a new calcination to 500°C for 4h (and/or to 800°C for 2h) and other consecutive to 1200°C for 4h. The samples were characterized by density and apparent porosity (Method of Arquimedes), composition of phases (by X - rays diffraction), Scanning Electric Microstructure (SEM) and electrical properties characterization (dielectric constant and capacitance). The ceramic bodies corresponding to the composition 0.75PZT-0.25PMN reached the largest density (7.09 ± 0.18 g/cm³) when calcined successively to 500°C and 800°C, with the largest values of capacitance (210 pF to 200 KHz) and dielectric constant (1000 in the frequency of 1 KHz), with smaller evidence of pyrochlore formation and larger of perovskte. The values of dielectric constant found are inside of the expected for the piezoelectric ceramics of the type PZT- PMN, approximately 1000 by frequencies of 1KHz.

Este trabalho investigou o sistema (1 - x )PZT - x PMN, avaliando a influência da composição química e dos parâmetros de sinterização na microestrutura e propriedades elétricas dos corpos cerâmicos obtidos pelo método convencional de mistura de óxidos. Os óxidos usados foram o Nb2O5, ZrO2, TiO2, PbO e MgCO3, cominuídos e homogeneizados em moinho de bolas, por 3 horas. Para o 0,65PZT - 0,35PMN, utilizou-se 28,58% de Nb2O5, 38,93% de ZrO2, 23,29% de TiO2 e 9,2% de MgCO3; para o 0,75PZT-0,25PMN, utilizou-se 20,9% de Nb2O5, 45,34% de ZrO2, 27,13% de TiO2 e 6,62% de MgCO3 e para o 0,85PZT-0,15PMN, usa-se 12,71% de Nb2O5, 52,09% de ZrO2, 31,16% de TiO2 e 4,04% de MgCO3. O pó obtido foi submetido a calcinação a 1200°C por 4 h e, então, acrescentado PbO com um excesso de 2% em massa.à mistura, a qual foi submetida a uma nova calcinação a 800°C durante 2 horas. O pó resultante da calcinação foi conformado por prensagem, utilizando uma prensa uniaxial a 190 MPa, na forma de discos medindo 10 mm de diâmetro e 1,5 mm de espessura. A curva de queima dos corpos cerâmicos consistiu em um novo patamar a 500°C por 4h (e/ou a 800°C por 2h) e outro consecutivo a 1200°C por 4h. As amostras foram caracterizadas pela sua densidade e porosidade aparente (método de Arquimedes), composição de fases (por difração de raio-X), Microscopia Eletrônica de Varredura (MEV) e caracterização elétrica (constante dielétrica e capacitância). Os corpos cerâmicos correspondentes à composição 0,75PZT-0,25PMN alcançaram a maior densidade (7,09 ± 0,18 g/cm³) quando calcinados sucessivamente a 500°C e a 800°C, com os maiores valores de capacitância (210 pF a 200 KHz) e de constante dielétrica (1000 na frequência de 1 KHz), com menor evidência de formação de pirocloro e maior de perovskita. Os valores de constante dielétrica encontrados estão dentro do esperado para materiais cerâmicos piezoelétricos do tipo PZT - PMN, aproximadamente 1000 para freqüências de 1KHz. / This work investigated the system (1 - x )PZT - x PMN, evaluating the influence of the chemical composition and the sintering parameters on the microstructure and the electric properties of ceramic bodies obtained by the conventional method of mixture of oxides. The used oxides were Nb2O5, ZrO2, TiO2, PbO e MgCO3, squeezed and homogenized in mill of balls, for 3 hours. For the 0.65PZT-0.35PMN, it was used 28.58% of Nb2O5, 38.93% of ZrO2, 23.29% of TiO2 and 9.2% of MgCO3; for the 0.75PZT-0.25PMN, it was used 20.9% of Nb2O5, 45.34% of ZrO2, 27.13% of TiO2 and 6.62% of MgCO3 and for the 0.85PZT-0.15PMN, it is used 12.71% of Nb2O5, 52.09% of ZrO2, 31.16% of TiO2 and 4.04% of MgCO3. The obtained powder was submitted the calcination for 1200°C for 4 h and, then, increased PbO with an excess of 2% in mass, which was submitted to a new calcination to 800°C for 2 hours. The calcinated powder was conformed by pressing, using a uniaxial press to 190 MPa, in the form of disks measuring a diameter of 10mm and 1.5 mm of thickness. The curve of the burning of the ceramic bodies consisted in a new calcination to 500°C for 4h (and/or to 800°C for 2h) and other consecutive to 1200°C for 4h. The samples were characterized by density and apparent porosity (Method of Arquimedes), composition of phases (by X - rays diffraction), Scanning Electric Microstructure (SEM) and electrical properties characterization (dielectric constant and capacitance). The ceramic bodies corresponding to the composition 0.75PZT-0.25PMN reached the largest density (7.09 ± 0.18 g/cm³) when calcined successively to 500°C and 800°C, with the largest values of capacitance (210 pF to 200 KHz) and dielectric constant (1000 in the frequency of 1 KHz), with smaller evidence of pyrochlore formation and larger of perovskte. The values of dielectric constant found are inside of the expected for the piezoelectric ceramics of the type PZT- PMN, approximately 1000 by frequencies of 1KHz.

Abstract Nd-modified lead-zirconate-titanate (PNZT) thin films were deposited on MgO(100), Si(100) and Al2O3(1102) single-crystal substrates using the pulsed-laser-ablation technique with a XeCl excimer laser. The post-annealing heat-treatment technique was used for the crystallisation of the films. The structural characterization, microstructure and the chemical composition of the thin films and of the ceramic Pb0.97Nd0.02(Zr0.55Ti0.45)O3 targets after ablation were studied using x-ray diffraction, scanning electron microscopy and energy-dispersive x-ray spectroscopy, respectively. The formation of the particulates on the target surface during the ablation process and the effect of the particulates on the quality of the thin films were studied. Typically, the ferroelectric PNZT thin films for the capacitor structures were deposited at the laser-beam fluence of around 1.0 J/cm2 and annealed at the temperatures from 600 to 700 °C. The dielectric and, especially, the polarization properties and the residual macroscopic stress state of the PNZT thin films were studied. The relationship between the electrical properties of the films and the nature of the stress state was also investigated. The average growth rate of the PNZT films increased linearly with increasing laser-beam fluence above the threshold value of around 0.4 J/cm2. The composition of the PNZT films varied strongly with the deposition laser-beam fluence and annealing temperature. The phase structure of PNZT films ablated from Pb0.97Nd0.02(Zr0.55Ti0.45)O3 targets could be adjusted between tetragonal and rhombohedral structures by changing the incident laser-beam fluence on the target surface. The surface of the target after ablation was covered by the laser-cone structure and the topmost layer of the target was amorphous having TiO2 and ZrO2 structures with separate segregated lead droplets. On MgO substrates, values of the relative dielectric constant er from 430 to 560 and of the remanent polarization εr of the order of 18 μC/cm2 were achieved in PNZT films which were under a compressive stress of the order of 300 MPa. On silicon substrates, εr was around 100 and the polarization properties of the films were modest due to a strong tensile stress of the order of 400 MPa. The Poole-Frenkel conduction mechanism with the activation energy of around 0.2 eV was found responsible for the leakage conductivity in the capacitor structures with PNZT films.

The development of a polyimide and metals multi-user surface micro-machining process for Micro-electro-mechanical Systems (MEMS) is presented. The process was designed to be as general as possible, and designed to be capable to fabricate different designs on a single silicon wafer. The process was not optimized with the purpose of fabricating any one specific device but can be tweaked to satisfy individual needs depending on the application. The fabrication process uses Polyimide as the structural material and three separated metallization layers that can be interconnected depending on the desired application. The technology allows the development of out-of-plane compliant mechanisms, which can be combined with six variations of different physical principles for actuation and sensing on a single processed silicon wafer. These variations are: electrostatic motion, thermal bimorph actuation, capacitive sensing, magnetic sensing, thermocouple-based sensing and radio frequency transmission and reception.

Im Rahmen der vorliegenden Arbeit wurde untersucht, wie sich organisch polymerisierbare Titan(IV)- und Zirkonium(IV)komplexe, die bei der Synthese anorganisch-organischer Hybrid-polymere verwendet werden, in Precursor-Solen für anorganische Beschichtungen verhalten. Dabei sollte ein Konzept zur Herstellung photochemisch strukturierter, anorganischer Dünnschichten erarbeitet werden. Als Beispiel für das anorganische Dünnschichtmaterial wurde Bleizirkonattitanat (PZT) und für die polymerisierbaren Liganden Methacrylsäure gewählt. Der Schwerpunkt der Arbeit lag dabei besonders auf den Untersuchungen der photochemischen Polymerisation mittels UV-lithographischer und Mehrphotonenpolymerisation sowie der in situ Untersuchung während der Pyrolyse des polymerisierten Materials und der Reaktion zur anorganischen Dünnschicht. Der Prozess zur Herstellung photostrukturierter, anorganischer Dünnschichten kann in zwei Schritte eingeteilt werden. Nach der Synthese des Precursor-Sols erfolgten zunächst die licht-induzierte organische Polymerisation und die Entfernung der nicht polymerisierten Bereiche mit Hilfe eines Entwicklerbads. Im Anschluss daran wurden im zweiten Schritt die organischen Bestandteile durch eine thermische Behandlung entfernt und die Reaktion zum anorganischen Oxidmaterial induziert. Die homogensten Schichten wurden dabei mit einem n Butanol-basierten, methacrylat¬funktionalisierten PZT-Sol mit 25 Gew. % Feststoffgehalt auf Stahlsubstraten bei Pyrolyse¬bedingungen ab 500 bis 700 °C mit einer Heizrate von 5 K/min erreicht. An diesen Schichten konnte ferroelektrisches Verhalten nachgewiesen werden. Allerdings reichen die Eigenschaften noch nicht an in der Literatur beschrieben ferro- und piezoelektrische Dünnschichten heran, die ebenfalls aus PZT-Solen hergestellt wurden. Dies liegt zum einen an den zu geringen Schichtdicken und der damit verbundenen erhöhten Durchschlagsgefahr dieser Sol-Gel-basierten PZT-Schichten. Zum anderen reduzieren Grenzflächenreaktionen des chromhaltigen Substrats und der PZT-Solschicht zu Pb2(CrO4)O sehr drastisch die ferroelektrischen Eigenschaften, indem sich nicht-ferroelelektrische Oxidschichten mit niedrigen Permittivitäten bilden und die Beweglichkeit der Domänenwände durch Diffusion von Cr3+-Akzeptorionen in die PZT-Schicht verringert wird. Zunächst wurde die PZT-Solsynthese untersucht. Dabei konnte gezeigt werden, dass die Nebenproduktbildung von verschiedenen Estern vermieden werden kann, wenn die leicht flüchtigen Bestandteile nach der Ligandenaustauschreaktion von Alkoxid gegen Methacrylsäure bei reduziertem Druck und damit verbundenen niedrigeren Reaktionstemperaturen, erfolgte. Die Bindung der Methacrylatliganden ist in jedem Fall bidentat. Bei den n Butanol-basierten PZT-Solen konnte trotz höherer Siedetemperatur und niedrigerem Dampfdruck ein größerer Anteil an Alkohol entfernt werden, als bei n-Propanol-basierten PZT-Solen. Dies wurde auf den etwas höheren +I Effekt des n Butanols und in der Folge der bevorzugten Ligandenaustauschreaktion von Methacryl¬säure gegen den n Butanol im Vergleich zu n Propanol zurückgeführt. Die Größe der PZT-Cluster war langzeitstabil, reproduzierbar herstellbar und betrug ca. 2,0 – 2,5 nm. Aus der Partikelgröße und dem spektros¬kopischen Nachweis von Metalloxobindungen konnte ein Strukturvorschlag basierend auf den zugrundeliegenden Titan- und Zirkoniumkomplexen erstellt werden. Dabei bilden MO6 Komplexe das Grundgerüst stäbchenförmiger, heterometallischer Cluster. Die polymerisierbaren Methacrylatliganden befinden sich auf der Oberfläche und sind gut zugänglich für die Polymerisationsreaktion. Die mittlere Anzahl an Methacrylatliganden pro PZT-Cluster wurde zu 5 - 25 je nach Gewichtung abgeschätzt. Bei der UV-lithographischen Strukturierung ergaben sich zwei unerwartete Effekte. Zum einen trat nach der Schichtherstellung eine reversible Trübung des PZT-Sols auf, welches auf konzentrations¬bedingte Phasenseparation zurückgeführt werden konnte. Zum anderen setzte sich unter N2 Atmosphäre die lichtinduzierte radikalische Kettenreaktion in den methacrylat-funktionalisierten PZT-Solschichten auch in die unbelichteten Bereiche fort. Dieser Effekt wird sonst in dieser Deutlichkeit nur von kationischen Polymerisationsreaktionen beobachtet und auf lange Radikal¬lebensdauern zurückgeführt und wurde mittels Photo-Differentialkalorimetrie weitergehend untersucht. Allerdings konnte aufgrund der Probengeometrie der Einfluss der Atmosphäre mit der Photo-DSC-Methode nicht eindeutig geklärt werden. Die Qualität der pyrolysierten PZT-Schichten konnte durch Variation der Feststoffgehalte und der Pyrolysebedingungen optimiert werden. So wurden durch die Verdünnung der PZT-Sole auf 25 Gew. % Feststoffgehalt bei ansonsten analogen Pyrolyse¬bedingungen dichtere und homogenere Schichten erhalten, wohingegen PZT-Solschichten mit einem Feststoffgehalt von 31 Gew.-% eine xerogelartige Struktur durch agglomerierte Partikel zeigten. Die untersuchten Substrate wiesen einen deutlichen Einfluss auf die nach der Pyrolyse erhaltenen PZT-Schichten auf. Unmetallisierte Silizium-Wafer eigneten sich zwar zur Untersuchung der UV-lithographischen Herstellung strukturierter Solschichten, bei der Pyrolyse bildeten sich jedoch unerwünschte Bleisilicat¬schmelzen, die der PZT-Bildung entgegen wirkten. Weiterhin wurden platinierten Silizium-Wafer mit Titanhaftvermittler¬schicht und SiO2-Sperrschicht verwendet. Diese Substrate zeigten eine durch die hohen Pyrolyse¬temperaturen induzierten Diffusion der Haftvermittlerschicht in die Platinmetallisierung und in der Folge eine Delamination aufgrund hoher Druckspannung in der PZT-Schicht, welche durch die Entfernung der organischen Bestandteile aus der Solschicht resultierte. In der Folge entstanden mechanisch instabile Proben. Die Delamination konnte durch Zwischensinterschritte bei 360 °C bzw. durch die Pyrolyse auf Heizplatten reduziert, jedoch nicht vollständig vermieden werden. Aus diesem Grund konnten keine ferroelektrischen Eigenschaften der PZT-Schichten auf diesen Substraten ermittelt werden. Lediglich auf Stahlsubstraten konnten elektrisch dichte Schichten hergestellt werden. Die Polymerisationsreaktion eines ausgesuchten PZT-Sols, welches bei den Strukturierungs- und Pyrolyseuntersuchungen die besten Ergebnisse zeigte, wurde näher untersucht, um ein Verständnis zu den ablaufenden Reaktionen zu erhalten. Die Reaktion zeigt den für radikalische Kettenpolymerisationen typischen Trommsdorf- bzw. Gel-Effekt. Durch die Verdünnung der PZT-Cluster konnten trotz hoher Anzahl an C=C-Bindungen pro Monomer, d. h. stark quervernetzender Spezies, sehr hohe Umsetzungsgrade erreicht werden. Die initiator¬gehalts-abhängige Steigerung der Reaktionsenthalpie während der Belichtung konnte mit steigenden Umsetzungs¬graden korreliert werden. Dieses Verhalten wird in der Literatur für eine Vielzahl an methacrylatbasierten Monomeren beschrieben. Der empirische Zusammenhang zwischen der Reaktionsrate und der Initiatorkonzentration konnte für das methacrylat¬funktionalisierte PZT-Sol zu bestimmt werden. Die Gesamtaktivierungenergie konnte ebenfalls in Abhängigkeit vom Reaktionsumsatz ermittelt werden. Die Polymerisation eines konzentrierten PZT-Sols mit difunktionellen Monomeren zeigte höhere Umsetzungsgrade als die entsprechenden Reinsubstanzen und ein späteres Eintreten des Gelpunkts. Dies wird zurückgeführt auf die niedrigere Viskosität sowie die geringere Molekülgröße des Reaktivverdünners und die in der Folge bessere Infiltration des durch das PZT-Sol aufgespannten Netzwerks mit zusätzlichen kleinen und beweglichen Monomeren. Da bei der thermischen Behandlung der polymerisierten PZT-Schichten die experimentellen Bedingungen, wie z. B. Heizrate oder Anfangstemperatur der Pyrolyse, einen signifikanten Einfluss besitzen, wurden energiedispersive in-situ-Röntgenbeugungsexperimente mit Hilfe von Synchrotron¬strahlung durch¬geführt. Hierbei konnte vor allem der Einfluss der organischen Polymerisation und der Anfangstemperatur der Pyrolyse auf die Phasenentwicklung des Precursor-Sols untersucht werden. Dabei zeigte sich besonders deutlich, dass die PZT-Bildungstemperatur durch die Belichtung der Probe und damit der Bildung des organischen Netzwerks steigt. Dies wird auf das starke organische Netzwerk und den erhöhten Energiebedarf zur Reorganisation zurückgeführt. Durch eine erhöhte Anfangstemperatur der Pyrolyse von 500 °C kann die in der Literatur beschriebene Verringerung der unerwünschten Pyrochlor-Phase beobachtet werden. Zudem ist die PZT-Bildungstemperatur hierbei niedriger als bei Pyrolysen ab Raumtemperatur. Dies wird mit einer durch den geringeren Anteil an Pyrochlor-Phase erhöhten Triebkraft zur PZT-Bildung erklärt. Die konsekutive Phasenumwandlung von Pyrochlor in die erwünschte PZT-Phase ist bei Pyrolysen ab Raumtemperatur später abgeschlossen als bei Pyrolysen ab 500 °C. Dies kann mit dem geringeren Anteil an Pyrochlor-Phase erklärt werden, da sich ab 500 °C bereits die PZT-Phase zu bilden beginnt. Der Vergleich der Halbwertsbreiten des intensitätsstarken Reflexes bei 31 ° zeigte, dass die Belichtung der Solschichten zu größeren Kristalliten führt, was auf eine niedrigere Nukleationsrate während der Kristallisation zurückzuführen ist. Bei der Auswertung und Diskussion der Ergebnisse der im Rahmen dieser Arbeit untersuchten Thematik ergaben sich einige Ansatzpunkte für weitere Untersuchungen, die jedoch nicht im zeitlichen und thematischen Rahmen dieser Arbeit betrachtet werden konnten. So wäre es interessant weitere Substrate auf ihre Eignung bei der, für die Herstellung strukturierten PZT-Schichten notwendigen, hohen thermischen Belastung zu testen, da die hier untersuchten platinierten Silizium-Wafer bzw. die Stahlsubstrate deutliche Nachteile zeigten. Des Weiteren können neben den hier behandelten polymerisierbaren Carbonsäureliganden weitere mehrzähnige Liganden und dessen Einfluss auf die Precursormaterialien für die Herstellung strukturierter anorganischer Schichten untersucht werden. β-Diketone, Aminoalkohole und auch Phosphonate bilden ebenfalls stabile Metall-Ligand-Bindungen und könnten so die Integration polymerisierbarer Gruppen in die PZT-Cluster analog zu der im Rahmen dieser Arbeit verwendeten Carbonsäure ermöglichen. Das hier erarbeitete Konzept könnte neben den untersuchten ferroelektrischen Schichtmaterialien ebenfalls auf andere dielektrische oder magnetische Materialklassen, wie z. B. Bariumtitanat oder Magnetit übertragen werden. Die Herstellung photostrukturierbarer anorganischer Schichten durch den Einbau polymerisierbarer Liganden eignet sich für zahlreiche Materialklassen, die über flüssige Sol-Gel-Vorstufen synthetisiert werden können. Darüber hinaus können weitere Pyrolysebedingungen mit den hier vorgestellten Analysemethoden untersucht werden. So könnten z. B. verschiedene Atmosphären oder unterschiedliche Heizraten innerhalb eines Pyrolysezyklus variiert werden, um ihren Einfluss auf die Herstellung rissfreier und phasenreiner Schichten zu untersuchen. Dazu müsste der hier vorgestellte experimentelle Aufbau dahingehend erweitert werden, dass eine Gaszufuhr während der Pyrolyse möglich ist. / The broad objective of this study was to investigate the properties of photopolymerizable precursor sols using organically polymerizable titan(IV) and zirconium(IV) complexes, which are commonly used in the synthesis of inorganic-organic hybrid polymers. With the help of these complexes an approach to the preparation of photochemically patterned, inorganic thin films was developed. Lead zirconate titanate (PZT) was chosen as the inorganic material. The polymerizable moiety was introduced into the precursor sol using methacrylic acid as the polymerizable ligand. Particular attention has been drawn to the investigation of the photochemical reaction of the precursor sol and on the in-situ analysis of the thermally induced conversion into the inorganic PZT thin film, respectively. The process for the preparation of photochemically patterned, inorganic thin films can be divided into two independent steps. These are, on the one hand, the light induced organic polymerization of the synthesized precursor sol and on the other hand, the thermal decomposition of the organic moieties along with the formation of crystalline PZT. Patterned PZT thin films were prepared, for example, using a methacrylated PZT-sol based on n butanol. The solid content of this precursor sol was set to 25 wt. % by diluting with high-boiling point organic solvents. The sol was spin-coated onto steel substrates, followed by the patterning process due to light-induced polymerization. After removal of the unexposed areas using a solvent developer, the pyrolysis reaction was started at 500 °C. The inorganic thin-film was obtained by further heating with a heating rate of 5 K/min to reach a final temperature of 700 °C. Although ferroelectric behavior was verified for these samples, their properties are still inferior compared to commonly prepared ferroelectric thin films. This has been attributed to several different reasons, such as low thickness of the thin film, the formation of undesired side-products and acceptor-doping due to ion diffusion out of the steel substrate, respectively. Firstly, there is an increased risk of electric breakdown within the PZT thin-films due to the low thickness of the films. Secondly, an undesired side-product (Pb2(CrO4)O) forms at the interface of the steel substrate and the PZT thin-film. This leads to a non-ferroelectic layer within the PZT, which drastically reduces the ferroelectric behavior. Finally, Cr3+ ions of the steel substrate can migrate into the PZT thin-film forming an acceptor doped material, which results in a reduced domain wall mobility. The synthesis of the PZT sol was investigated and it was shown that the formation of undesired ester by-products could be avoided, if the volatile products of the ligand exchange reaction of alcohol and methacrylic acid are distilled at reduced pressure, as lower distillation temperatures have to be applied. The coordination of the methacrylic acid ligand in the resulting complexes is bidentate. Although the boiling temperature of n butanol is higher and its vapor pressure is lower, a higher amount of alcohol can be removed during distillation in the case of n butanol based PZT sols compared to sols based on n propanol. This may be attributed to a favored ligand exchange reaction. The size of the PZT precursor cluster is is about 2,0 – 2,5 nm. The methacrylated PZT sol can be prepared with a high degree of reproducibility and is storage-stable over several months. Based on this particle size and the spectroscopic detection of metal oxo groups within the PZT precursor sol, a structure was proposed, which is made up of titan- and zirconium-containing MO6-complexes forming rod-like heterometallic clusters. The polymerizable methacrylic ligands are bound to the outer surface of the clusters and thus are susceptible to the polymerization reaction. The average number of methacrylic ligands per PZT sol cluster was estimated at 5 – 25 depending on the weighting. The UV lithography process was marked by two effects. On the one hand the spin-coated PZT precursor films featured a reversible hazing, which was attributed to a concentration dependent phase separation of the precursor. On the other hand, if the light exposure was performed under a constant stream of nitrogen, the radical polymerization reaction proceeded into the shadow areas of the mask. Usually, this behavior is limited to cationic polymerization and is attributed to long lifetimes of the reactive species. In Photo-DSC experiments, this effect is observed for the methacrylated PZT-sol, as well. However, due to the different sample setup the influence of the atmosphere could not be resolved with this Photo-DSC method. The quality of the pyrolyzed PZT thin films was optimized by variation of the solid content and by variation of the pyrolysis parameters. The methacrylated PZT sols with a solid content of 25 % lead to the formation of homogenous and dense thin-films, whereas the pyrolysis of PZT sols with a solid content of 31 % resulted in xerogel like morphology due to agglomeration of precursor particles. The substrates, used within this work, exerted a major influence on the PZT thin films. Pure silicon wafers were appropriate for the investigations concerning the UV lithography process or the polymerization reaction. However, during the thermal treatment of the PZT precursor thin film, the silicon substrate reacted with the sol forming undesired lead silicate meltings, which inhibited PZT formation. The platinized silicon wafers containing titan and silicon oxide sublayers also showed increased reaction during thermal annealing as the titan adhesion layer migrated into the platinum electrode. As a result, the compressive stress generated in the PZT thin-film due to the combustion of the organic residues could not be compensated by the remaining adhesion layer and, consequently, the platinum electrode delaminated. The resulting samples exhibited a very low mechanical stability. The delamination of the electrode layers was reduced by either intermediate annealing steps at 360 °C or by the application of hotplates instead of a furnace. However, a complete prevention of delamination was not achieved. Hence, due to the ensuing electric breakdown, no ferroelectric properties could be obtained from photochemically patterned PZT thin films on these platinized silicon substrates. Furthermore, the polymerization of the methacrylated PZT sol was investigated in order to obtain a better understanding of the reactions that take place. The light induced polymerization exhibited the Trommsdorf or gel effect, which is typical for radical chain reactions. After curing the resulting films showed very high conversion rates, when diluted in various solvents. This is obtained regardless of the high number of polymerizable C=C bonds per cluster, which can lead to highly branched networks in which the mobility of reactive moieties is usually reduced significantly even at low conversion rates. The increase in the reaction enthalpy depending on the content of UV initiator sufficiently correlates with increasing conversion rates. In literature, this behavior is reported for a number of methacrylate¬-based monomers. The empirical relation of the reaction rates and the concentration of UV initiator was determined as . The overall activation energy for the polymerization of the methacrylated PZT sol was calculated depending on the reaction conversion. Additionally, the copolymerization with difunctional monomers exhibited higher conversion rates than the pure monomers and the onset of the gel effect is delayed. Energy dispersive in-situ x-ray diffraction analyses using synchrotron radiation were performed to examine the influence of the different pyrolysis parameters, such as heating rate and starting temperature of the annealing step. It was observed, that the polymerization of the PZT precursor thin-films, and thus the formation of an organic network, resulted in an increase in the temperature needed for PZT formation. This effect was attributed to the strong covalent organic network, which had accumulated during polymerization, and thus an increased energy was needed for reorganization. By increasing the starting temperature of the annealing step to 500 °C, the reduced formation of undesired pyrochlore was observed, as previously reported in literature. Furthermore, the PZT formation temperature is lower compared to pyrolysis starting at room temperature. This was explained by an increased driving force for PZT crystallization due to a lower amount of pyrochlore phase. In addition, the consecutive phase transformation from pyrochlore into PZT was completed at lower temperatures, if the starting temperature was 500 °C. A comparison of the halfwidth of the PZT reflex at 31° revealed that the polymerized PZT thin films exhibited larger crystallite sizes compared to unexposed thin films. In addition to the higher formation temperature, this was accredited to a lower nucleation rate in the polymerized PZT precursor films. During the interpretation and discussion of the results of this thesis, a number of new and interesting aspects arose, which could not be dealt with within the framework of this study. Therefore, it would be interesting to investigate further substrates for their suitability within the PZT preparation process. The substrates used within this work exhibited a number of significant disadvantages, such as thermal instability and undesired reactions with the PZT precursor. Additionally, alongside the methacrylic ligand which was tested within this work, other polymerizable ligands may be used for the synthesis of photopatternable precursor sols. β diketones, amino alcohols and phosphonates also form stable metal ligand bonds, and thus could be used to introduce the polymerizable moiety. The resulting concept of polymerizable precursors for inorganic thin films might also be transferred to dielectric or magnetic material classes, such as barium titanate. In principle, this process is applicable for all materials that can be synthesized by liquid sol-gel precursors. Additionally, further parameters of the pyrolysis could be investigated with the in-situ x-ray diffraction method, which was used within this thesis. The influence of different annealing atmospheres or different heating rates could also be examined. For the variation of the reaction atmosphere, an adaption of the experimental setup would have to be realized first, which allows the gas supply.

Das Mischkristallsystem PbZrxTi1-xO3 (PZT) gehört durch seine ausgeprägten piezo- und ferroelektrischen Eigenschaften zu den meist verwendeten Funktionskeramiken. In Form von Dünnschichten auf flexiblen Metallsubstraten können sie für unterschiedlichste Anwendungen als Tastschalter, Vibrationsdämpfer, Mikroaktuator oder Ultraschallwandler eingesetzt werden. Ziel der vorliegenden Arbeit ist es, den Gefügeaufbau und den Phasenbestand von PZT-Schichten, die in einem mehrstufigen Sol-Gel-Prozeß auf Blechen der säure- und temperaturbeständigen Chrom-Nickel-Legierung Hastelloy abgeschieden worden sind, zu analysieren und mit ihren ferroelektrischen und die-lektrischen Eigenschaften zu korrelieren. Es wird nachgewiesen, daß das Gefüge gezielt mittels verschiedener Temperaturbehandlungen und unter-schiedlicher Neodymdotierung variiert werden kann. Durch Nd-Dotierung wird das Maximum der Keimbil-dungsrate zu niedrigeren Temperaturen hin verschoben und die Wachstumsgeschwindigkeit gegenüber undotierten Schichten verringert. Die Kristallisation in dotierten und undotierten Schichten ist heterogen und erfolgt bevorzugt an den Grenz- und Oberflächen sowie an den Porenrändern im Innern der Schichten. Die Zusammensetzung der PZT-Sol-Gel-Beschichtungen liegt im Bereich der morphotropen Phasengrenze (x=0,53) zwischen tetragonaler und rhomboedrischer Phase. Erstmals wurde die während der Temperatur-behandlung auftretende Gradientenbildung im Zr/Ti-Verhältnis systematisch mit dem Gefüge und dem Phasenbestand auf Nanometerskala in Verbindung gesetzt. Hierbei konnte aufgezeigt werden, dass langreichweitige Zr:Ti-Fluktuationen vorrangig während der Kri-stallisation der Pyrochlorphase entstehen. Bei der nachfolgenden Perowskitkristallisation wachsen die Kri-stalle über die entmischten Bereiche hinweg, so daß Schwankungen im Zr:Ti-Verhältnis innerhalb der Kristallite erhalten bleiben. Es wird dargelegt, daß die Fluktuationen im Zr:Ti-Verhältnis infolge der starken Spannungen innerhalb der Schicht nur geringe Auswirkungen auf den Verzerrungsgrad der Kristallite und die Zugehörigkeit zur rhomboedrischen oder tetragonalen Perowskitphase haben. Beim Übergang in den ferroelektrischen Zustand ist das Ausmaß der Gitterverzerrung unabhängig von der Kristallitgröße und in Nd-dotierten Schichten generell geringer als in undotierten Schichten. Es wird die Ausbildung einer Zwischenschicht zwischen Metallsubstrat und PZT-Schicht untersucht, die die resultierenden elektrischen Eigenschaften maßgeblich beeinflußt. Sie wird als Oxidschicht identifiziert, be-stehend aus kristallinem NiO und NiCr2O4, verschiedenen Chromoxiden und Pb2(CrO4)O, die als nicht-ferroelektrisches Dielektrikum die resultierende Dielektrizitätskonstante des Substrat-Schichtverbundes stark herabsetzt. Durch Aufbringen einer unterstöchiometrischen La0,75Sr0,2MnO3 (ULSM) - Elektrodierung vor der PZT-Beschichtung gelingt es, die Kontaktierung zu verbessern, die (001)-Orientierung in undotierten Schichten zu steigern und sehr schmale P-E-Hysteresekurven zu erhalten. / Lead zirconate titanate (PbZrxTi1-xO3 , PZT) is one of the most applied ceramic materials because of its dis-tinctive piezo- and ferroelectric properties. Prepared as thin films on flexible, metallic substrates it can be used for various applications as strain gauges, key switches, vibration dampers, microactuators and ultrasonic transducers. The aim of this work is to analyze the microstructure and the phase-content of PZT-thin films deposited on temperature- und acid-resistant hastelloy-sheets, to correlate the results with the ferroelectric and dielectric properties. It is demonstrated, that the specific variation of the microstructure can be achieved by different thermal treatments and the selective addition of Neodymium as dopant. Nd-doping leads to a shift of the maxi-mum nucleation rate towards reduced temperatures and a decrease in the rate of growth compared to undoped films. The PZT-films are prepared by a sol-gel-process in fourfold multilayers with a composition near the mor-photropic phase boundary, where the tetragonal und rhombohedral perovskite-phases coexist. The crystal-lisation in Nd-doped and undoped films takes place heterogeneously, preferentially at the interfaces and on the surface of the multilayered films as well as on the inner surface of pores within the films. For the first time, the Zr:Ti fluctuation phenomena emerging in sol-gel derived PZT films is related to the microstructure and the local phase content on a nanometer scale. In this connection it is proved, that long-distance Zr:Ti gradients arise preferentially before and during the crystallisation of the pyrochlore phase. During the following crystallisation of the perovskite phase, the crystallites grow across these gradients without modifying them. It is pointed out that the fluctuation in the Zr:Ti ratio has only minor influence on the amount of the tetragonal or rhombohedral distortion of the crystallites after the transition from the para- to the ferroelec-tric state due to strong stresses within the films. The magnitude of the lattice distortion is independent of the crystallite size and its extent is generally smaller for crystallites in Nd-doped films than for such in undoped films. After the detailed analysis of the development of the boundary layer between metal subtrate and PZT-film, it is identified as a non-ferroelectric, dielectric buffer-layer containing crystalline NiO und NrCr2O4, different chromiumoxides and Pb2(CrO4)O between the PZT film and the conductive substrate significantly dimini-shing the resulting dielectric properties of the system. By applying a non-stoichiometric La0,75Sr0,2MnO3 (ULSM) – electrode below the PZT-film, a better electrical contact is achieved, the (001)-orientation in undoped films is enhanced and narrow P-E-hysteresis loops can be obtained.