The microelectronics industry requires continuous advances due to ever-evolving technology and the corresponding need for higher density substrates with smaller features. Specifically, new dielectric materials with enhanced electrical properties are needed. At the same time, adhesion must be maintained in order to preserve package reliability and mechanical performance. As a result, this research investigates the use of thin glass sheets as an alternative substrate material as it offers a number of advantages including coefficient of thermal expansion similar to silicon, good dielectric properties and optical transparency to assist in the alignment of buried features. As part of this project it was necessary to deposit metallic coatings onto the glass sheets to create electrical tracks, pads and microvias. In order to meet these requirements, the metallisation of both smooth as received glass surfaces and surfaces roughened by laser machining using electroless copper and nickel deposition were investigated. This study resulted in a number of important conclusions about the roles of chemical bonding and mechanical anchoring in both the adhesion and catalyst adsorption, that are key factors in the electroless metallisation process.....

Neste trabalho é apresentada a análise de técnicas para a integração de ISFETs (Ion Selective Field Effect Transitors), através do método de montagem por viragem (Flip-chip) usando pasta de solda livre de chumbo e epóxi condutivo de prata, com o objetivo de permitir sua aplicação em Microssistemas de Análise Total (µTAS). Para os testes de integração foram construídas estruturas em dois substratos, o FR-4, pelo método de ligação por fios (wire bonding), e o LTCC, que pode ser aplicado na construção de µTAS. Como os terminais de contato do ISFET tem seu acabamento superficial em alumínio não é possível realizar a montagem por viragem utilizando equipamentos SMT, sendo necessários processos intermediários. Dois processos que permitem o uso de equipamentos SMT foram aplicados: a remetalização, onde camadas de níquel e ouro são depositadas sobre o alumínio do terminal de contato, através do banho químico eletrolítico sem eletrodo (Electroless), e protuberâncias de solda (stud ou ball bumps), que são ligadas ao alumínio do terminal de contato pelo processo conhecido como Stud Ball Bumping (SBB). Na integração do ISFET foi feita a selagem dos terminais de contato e a abertura de uma janela que permite o contato da área ativa (região de porta) do ISFET com as soluções a serem analisadas. A selagem dos terminais de contato foi feita com o fotoresiste SU-8, e a abertura da área ativa foi feita diretamente sobre os substratos de FR-4 e LTCC. Ambos processos apresentaram soldabilidade com a pasta de solda apresentando ponto de refusão em torno de 250°C, indicando que equipamentos SMT podem ser aplicados na montagem por viragem. Verificou-se que o epóxi condutivo de prata foi curado a 100°C por uma hora e também pode ser aplicado na integração do ISFET. Por fim o SU-8 usado na selagem apresentou uma boa adesão aos substratos de FR-4 e LTCC, sendo curado na mesma etapa térmica da pasta de solda e/ou epóxi condutivo de prata ou após estes processos a 150°C por trinta minutos. / In this work is shown the analysis of integration techniques of ISFET (Ion Selective Field Effect Transitor) through the Flip-chip method using lead-free solder paste and silver conductive epoxy, in order to allow its application in Micro Total Analysis System (µTAS). For integration tests two substrates have been made, the FR-4, as already used in the integration of the ISFET, but assembled through wire bonding method, and the LTCC that can be applied in the construction of µTAS. As the ISFET bonding pads has its surface finish in aluminum is not possible assembly through flip-chip method using SMT equipments, requiring intermediate processes. Two process that allow the use of SMT equipment were applied: the remetallization, where nickel and gold layers are deposited on the aluminum bonding pads, through the Electroless chemical baths, and stud or ball bumps, which are connected to bonding pads of aluminum by the process known as Stud Ball Bumping (SBB). In the ISFET integration should be made a seal in the bonding pads and a window that allows the contact of the active area (gate region) of ISFET with the solutions to be analyzed. The sealing of the bonding pads has been made with the photoresist SU-8 and the window of active area were made directly on the FR-4 and LTCC substrates. Both processes presented the solderability with the solder paste reflowed at 250°C, indicating that SMT equipments may be applied to the assembly through flip-chip method, the silver conductive epoxy was cured at 100°C for one hour and can also be applied in ISFET integration. Finally the SU-8 used to sealing have showed a good adherence to the FR-4 and LTCC substrates, being cured in the same thermal step of solder paste and/or silver conductive epoxy or after these processes at 150°C for thirty minutes.

L'enjeu de ce travail est la réalisation de circuits électroniques sur des pièces polymères injectées à forme 3D, appelées MIDs, par microtamponnage (μTP). Le μTP, est une technique de localisation de substances (chimiques ou biologiques) par contact mécanique d'un tampon structuré sur un substrat. Il permet de localiser les pistes conductrices des MIDs en utilisant deux protocoles : le μTP passif et le μTP actif. La première méthode consiste à déposer de manière localisée un thiol par μTP sur la surface de la pièce préalablement métallisée. Le thiol permet de protéger les pistes métalliques qui doivent être conservées après gravure humide. Dans la seconde, un catalyseur (du palladium) est déposé par μTP, suivi de la métallisation electroless des pistes. La problématique du μTP 3D a été étudiée à l'aide d'un tampon épousant la forme de la pièce. Nos résultats expérimentaux couplés à des simulations par éléments finis de la déformation du tampon lors de sa compression au moment du contact avec la pièce, nous ont permis de déterminer les paramètres clefs du procédé : l'alignement du tampon par rapport à la pièce, la gestion du contact et la fabrication du tampon. Il a été mis en évidence que la tolérance de l'alignement est de l'ordre de 100μm pour des motifs structurés de 250μm de hauteur. Un tampon composé d'un support rigide surmonté d'une couche mince structurée permet de limiter ses déformations lors de sa compression. Les enseignements tirés nous ont permis de réaliser nos premiers circuits par μTP à l'aide d'une machine originale développée au laboratoire. La problématique de l'épaississement des couches de cuivre adhérentes sur des pièces en LCP est également abordée, un protocole d'épaississement ayant été validé / The main challenge of this work was the production of electronic circuits on injected 3Dshaped polymer components, called MIDs, by microcontact printing (μCP). μCP is a substance (chemical or biological) localisation technique through mechanical contact between a patterned stamp and a substrate. It enables the MIDs’ conductor tracks to be located using two techniques: passive μCP and active μCP. The first method involves locally depositing a thiol by μCP on the substrate’s surface, which has previously been coated with a thin metallic film. The thiol protects the metallic tracks, which must be preserved after wet chemical etching. Regarding the second method, a catalyst (palladium) is deposited by μCP, followed by the electroless metallization of the tracks. The 3D μCP issue was studied using a stamp, which matched the shape of the substrate. Our experimental results combined with finite element simulations of stamp deformation during compression and whilst in contact with the substrate, revealed the key parameters of the process: stamp/substrate alignment, contact control and stamp manufacturing. We found that the alignment tolerance was around 100μm for a 250μm thickness structured design. A stamp with a rigid support covered in a structured thin film minimises deformation during compression. Thanks to the lessons learned, we carried out our first circuits using μCP with a new machine, which was developed in the laboratory. We also addressed the problem of thickening adhesive copper layers on LCP components, as a thickening procedure had already been validated

Neste trabalho é apresentada a análise de técnicas para a integração de ISFETs (Ion Selective Field Effect Transitors), através do método de montagem por viragem (Flip-chip) usando pasta de solda livre de chumbo e epóxi condutivo de prata, com o objetivo de permitir sua aplicação em Microssistemas de Análise Total (µTAS). Para os testes de integração foram construídas estruturas em dois substratos, o FR-4, pelo método de ligação por fios (wire bonding), e o LTCC, que pode ser aplicado na construção de µTAS. Como os terminais de contato do ISFET tem seu acabamento superficial em alumínio não é possível realizar a montagem por viragem utilizando equipamentos SMT, sendo necessários processos intermediários. Dois processos que permitem o uso de equipamentos SMT foram aplicados: a remetalização, onde camadas de níquel e ouro são depositadas sobre o alumínio do terminal de contato, através do banho químico eletrolítico sem eletrodo (Electroless), e protuberâncias de solda (stud ou ball bumps), que são ligadas ao alumínio do terminal de contato pelo processo conhecido como Stud Ball Bumping (SBB). Na integração do ISFET foi feita a selagem dos terminais de contato e a abertura de uma janela que permite o contato da área ativa (região de porta) do ISFET com as soluções a serem analisadas. A selagem dos terminais de contato foi feita com o fotoresiste SU-8, e a abertura da área ativa foi feita diretamente sobre os substratos de FR-4 e LTCC. Ambos processos apresentaram soldabilidade com a pasta de solda apresentando ponto de refusão em torno de 250°C, indicando que equipamentos SMT podem ser aplicados na montagem por viragem. Verificou-se que o epóxi condutivo de prata foi curado a 100°C por uma hora e também pode ser aplicado na integração do ISFET. Por fim o SU-8 usado na selagem apresentou uma boa adesão aos substratos de FR-4 e LTCC, sendo curado na mesma etapa térmica da pasta de solda e/ou epóxi condutivo de prata ou após estes processos a 150°C por trinta minutos. / In this work is shown the analysis of integration techniques of ISFET (Ion Selective Field Effect Transitor) through the Flip-chip method using lead-free solder paste and silver conductive epoxy, in order to allow its application in Micro Total Analysis System (µTAS). For integration tests two substrates have been made, the FR-4, as already used in the integration of the ISFET, but assembled through wire bonding method, and the LTCC that can be applied in the construction of µTAS. As the ISFET bonding pads has its surface finish in aluminum is not possible assembly through flip-chip method using SMT equipments, requiring intermediate processes. Two process that allow the use of SMT equipment were applied: the remetallization, where nickel and gold layers are deposited on the aluminum bonding pads, through the Electroless chemical baths, and stud or ball bumps, which are connected to bonding pads of aluminum by the process known as Stud Ball Bumping (SBB). In the ISFET integration should be made a seal in the bonding pads and a window that allows the contact of the active area (gate region) of ISFET with the solutions to be analyzed. The sealing of the bonding pads has been made with the photoresist SU-8 and the window of active area were made directly on the FR-4 and LTCC substrates. Both processes presented the solderability with the solder paste reflowed at 250°C, indicating that SMT equipments may be applied to the assembly through flip-chip method, the silver conductive epoxy was cured at 100°C for one hour and can also be applied in ISFET integration. Finally the SU-8 used to sealing have showed a good adherence to the FR-4 and LTCC substrates, being cured in the same thermal step of solder paste and/or silver conductive epoxy or after these processes at 150°C for thirty minutes.

A influência de variáveis do banho na composição, microestrutura e nas propriedades magnéticas de filmes de CoB preparados por deposição química foi estudada. Dois diferentes tipos de agentes complexantes foram utilizados: citrato de sódio e Glicina. Filmes com menor teor de boro foram obtidos com o uso de Glicina como complexante. A deposição de Co é acelerada em presença de Glicina ou de amônia no banho, porque ambos evitam a diminuição do pH na interface solução/filme de CoB em crescimento. A coercividade dos filmes variou em função do teor de boro, sendo que filmes com maior teor de boro apresentaram mais baixa coercividade. Catalisadores de Co/Al2O3 são utilizados na síntese de combustíveis à partir de derivados do Gás Natural (Síntese de Fischer-Tropsch - SFT). O processo usual de preparação destes catalisadores, denominado impregnação úmida, consiste na impregnação do substrato em solução de sal de Co(II), secagem/calcinação e redução com H2 a 300/350 °C. Uma fração considerável do Co não é reduzida à fase metálica na etapa de redução, o que resulta em perdas de área ativa para a catálise da SFT. Normalmente pequenas quantidades de metais preciosos tais como Pt, Ru ou Pd são adicionadas para catalisar a redução dos óxidos de cobalto e aumentar a área superficial ativa do catalisador, o que representa um grande incremento no custo destes catalisadores. Nesta tese, foram investigadas duas propostas alternativas de solução para este problema: a preparação de catalisadores de Co por deposição química sobre Al2O3 e a preparação pelo método usual, mas com adição de pequenas quantidades de Cu,Ag e Au, dos quais Cu e Ag têm custo mais baixo do que os metais preciosos normalmente utilizados. Co foi depositado quimicamente sobre γ-Al2O3, previamente ativada com pequenas quantidades de Pd, utilizando NaBH4 como redutor. Uma amostra de catalisador de CoB/PdAl2O3 (contendo 13,4 % em massa de Co e c.a. 25% at. de boro) foi obtida e caracterizada por RTP, Quimissorção de H2 e XRD, assim como foram efetuados testes de SFT sob diferentes temperaturas de ativação. Para efeito de comparação, foi preparado por impregnação úmida uma amostra de Co/PdAl2O3 contendo 11% em massa de Co, sobre a mesma alumina ativada com Pd utilizada na preparação dos catalisadores de CoB/PdAl2O3. Embora a amostra de catalisador de CoB/PdAl2O3 tenha tido menor área superficial ativa do que a amostra de catalisador de Co/PdAl2O3, sua atividade catalítica foi sensivelmente maior. Essa diferença pode ser explicada supondo-se que o boro é solubilizado durante a reação, deixando uma fase de Co metálico altamente dispersa. Catalisadores de Co/Al2O3 promovidos por metais do grupo 11 foram preparados por impregnação úmida. Além da caracterização por RTP, Quimissorção de H2/titulação de O2 e XRD, a estrutura das amostras de catalisador foi estudada por XANES/EXAFS. Dos resultados de EXAFS e do fato de que altos teores de Cu e Au levaram à desativação do catalisador, é sugerido que durante a redução, o promotor é segregado para a superfície das partículas de Co. Dos três metais testados, Ag e Au apresentaram maior efeito promotor da atividade catalítica, proporcionando maior área superficial ativa para catálise da SFT. Não houve modificações importantes na seletividade dos catalisadores por conta da presença destes metais. / The influence of bath composition on the boron content, microstructure and magnetic properties CoB films deposited by chemical deposition was studied. Two different complexing agents were used in this study: sodium citrate and Glycine. CoB films with lower boron content were obtained with the use of a Glycine containing bath. The Co deposition is accelerated when either Glycine or ammonia is present in the solution because both substances prevent the decrease of the pH in the region near the CoB film/solution interface. The coercivity of the films varied in function of the boron content, as films with larger boron contents showed lower coercivities. Co/Al2O3 is used as a catalyst for the synthesis of liquid fuels from either coal or natural gas derivatives (Fischer Tropsch Synthesis FTS). The usual preparation procedure of such catalysts, known as wet impregnation, consists in the Al2O3 impregnation with a Co(II) aqueous solution, water evaporation/calcination and reduction with H2 at 300/350 °C. A considerable fraction of the cobalt oxides formed during calcination is not reduced to Co0 during reduction and this leads to active area loss. Normally, small quantities of precious metals like Pt, Ru or Pd are added to promote the reduction of cobalt oxides and therefore increase the active area of the Co/Al2O33 catalyst, yet these metals are extremely expansive. In this thesis, two different approaches to solve this problem are presented: the preparation of Co/Al2O3 by chemical deposition of the metallic phase and the use of Cu, Ag or Au (from which, Cu and Ag are cheaper metals) as promoters on wet impregnation prepared Co/Al2O3 catalysts. Cobalt was chemically deposited on γ-Al2O3, activated with a small quantity of Pd, with NaBH4 as a reducing agent. The resulting CoB/PdAl2O3 sample (with 13,4 % wt. Co and approximately 25 % at. of boron) was characterized by TPR, H2 Chemisorption and XRD, as well as SFT tests were made with the catalyst at different pre-reduction temperatures. For the sake of comparison a Co/PdAl2O3 catalyst sample with almost the same Co loading (11 % wt.) was prepared by wet impregnation on the same Pd-activated Al2O3 used to prepare the CoB/PdAl2O3 sample. Although the CoB/PdAl2O3 has a smaller active surface area (measured by H2 Chemisorption) than that of the Co/PdAl2O3 sample, it presented a much higher catalytic activity for the SFT. This difference may be explained assuming that boron impurities (present in the catalyst as boron oxides) is solubilized during the reaction leaving a highly dispersed Co phase. Group 11 promoted Co/Al2O3 catalysts were prepared by wet impregnation and characterized by TPR, H2 Chemisorption/O2 pulse oxidation, XRD and XANES/EXAFS. From the EXAFS results and from the fact that higher loadings of Cu and Au lead to catalyst deactivation, it is proposed that in the reduced catalyst the SFT inactive promoter is segregated to the surface. Silver and Gold were the most active in promoting Co reduction and therefore increasing catalytic activity for the SFT. No important modification in the selectivity of the reaction was observed.

A influência de variáveis do banho na composição, microestrutura e nas propriedades magnéticas de filmes de CoB preparados por deposição química foi estudada. Dois diferentes tipos de agentes complexantes foram utilizados: citrato de sódio e Glicina. Filmes com menor teor de boro foram obtidos com o uso de Glicina como complexante. A deposição de Co é acelerada em presença de Glicina ou de amônia no banho, porque ambos evitam a diminuição do pH na interface solução/filme de CoB em crescimento. A coercividade dos filmes variou em função do teor de boro, sendo que filmes com maior teor de boro apresentaram mais baixa coercividade. Catalisadores de Co/Al2O3 são utilizados na síntese de combustíveis à partir de derivados do Gás Natural (Síntese de Fischer-Tropsch - SFT). O processo usual de preparação destes catalisadores, denominado impregnação úmida, consiste na impregnação do substrato em solução de sal de Co(II), secagem/calcinação e redução com H2 a 300/350 °C. Uma fração considerável do Co não é reduzida à fase metálica na etapa de redução, o que resulta em perdas de área ativa para a catálise da SFT. Normalmente pequenas quantidades de metais preciosos tais como Pt, Ru ou Pd são adicionadas para catalisar a redução dos óxidos de cobalto e aumentar a área superficial ativa do catalisador, o que representa um grande incremento no custo destes catalisadores. Nesta tese, foram investigadas duas propostas alternativas de solução para este problema: a preparação de catalisadores de Co por deposição química sobre Al2O3 e a preparação pelo método usual, mas com adição de pequenas quantidades de Cu,Ag e Au, dos quais Cu e Ag têm custo mais baixo do que os metais preciosos normalmente utilizados. Co foi depositado quimicamente sobre γ-Al2O3, previamente ativada com pequenas quantidades de Pd, utilizando NaBH4 como redutor. Uma amostra de catalisador de CoB/PdAl2O3 (contendo 13,4 % em massa de Co e c.a. 25% at. de boro) foi obtida e caracterizada por RTP, Quimissorção de H2 e XRD, assim como foram efetuados testes de SFT sob diferentes temperaturas de ativação. Para efeito de comparação, foi preparado por impregnação úmida uma amostra de Co/PdAl2O3 contendo 11% em massa de Co, sobre a mesma alumina ativada com Pd utilizada na preparação dos catalisadores de CoB/PdAl2O3. Embora a amostra de catalisador de CoB/PdAl2O3 tenha tido menor área superficial ativa do que a amostra de catalisador de Co/PdAl2O3, sua atividade catalítica foi sensivelmente maior. Essa diferença pode ser explicada supondo-se que o boro é solubilizado durante a reação, deixando uma fase de Co metálico altamente dispersa. Catalisadores de Co/Al2O3 promovidos por metais do grupo 11 foram preparados por impregnação úmida. Além da caracterização por RTP, Quimissorção de H2/titulação de O2 e XRD, a estrutura das amostras de catalisador foi estudada por XANES/EXAFS. Dos resultados de EXAFS e do fato de que altos teores de Cu e Au levaram à desativação do catalisador, é sugerido que durante a redução, o promotor é segregado para a superfície das partículas de Co. Dos três metais testados, Ag e Au apresentaram maior efeito promotor da atividade catalítica, proporcionando maior área superficial ativa para catálise da SFT. Não houve modificações importantes na seletividade dos catalisadores por conta da presença destes metais. / The influence of bath composition on the boron content, microstructure and magnetic properties CoB films deposited by chemical deposition was studied. Two different complexing agents were used in this study: sodium citrate and Glycine. CoB films with lower boron content were obtained with the use of a Glycine containing bath. The Co deposition is accelerated when either Glycine or ammonia is present in the solution because both substances prevent the decrease of the pH in the region near the CoB film/solution interface. The coercivity of the films varied in function of the boron content, as films with larger boron contents showed lower coercivities. Co/Al2O3 is used as a catalyst for the synthesis of liquid fuels from either coal or natural gas derivatives (Fischer Tropsch Synthesis FTS). The usual preparation procedure of such catalysts, known as wet impregnation, consists in the Al2O3 impregnation with a Co(II) aqueous solution, water evaporation/calcination and reduction with H2 at 300/350 °C. A considerable fraction of the cobalt oxides formed during calcination is not reduced to Co0 during reduction and this leads to active area loss. Normally, small quantities of precious metals like Pt, Ru or Pd are added to promote the reduction of cobalt oxides and therefore increase the active area of the Co/Al2O33 catalyst, yet these metals are extremely expansive. In this thesis, two different approaches to solve this problem are presented: the preparation of Co/Al2O3 by chemical deposition of the metallic phase and the use of Cu, Ag or Au (from which, Cu and Ag are cheaper metals) as promoters on wet impregnation prepared Co/Al2O3 catalysts. Cobalt was chemically deposited on γ-Al2O3, activated with a small quantity of Pd, with NaBH4 as a reducing agent. The resulting CoB/PdAl2O3 sample (with 13,4 % wt. Co and approximately 25 % at. of boron) was characterized by TPR, H2 Chemisorption and XRD, as well as SFT tests were made with the catalyst at different pre-reduction temperatures. For the sake of comparison a Co/PdAl2O3 catalyst sample with almost the same Co loading (11 % wt.) was prepared by wet impregnation on the same Pd-activated Al2O3 used to prepare the CoB/PdAl2O3 sample. Although the CoB/PdAl2O3 has a smaller active surface area (measured by H2 Chemisorption) than that of the Co/PdAl2O3 sample, it presented a much higher catalytic activity for the SFT. This difference may be explained assuming that boron impurities (present in the catalyst as boron oxides) is solubilized during the reaction leaving a highly dispersed Co phase. Group 11 promoted Co/Al2O3 catalysts were prepared by wet impregnation and characterized by TPR, H2 Chemisorption/O2 pulse oxidation, XRD and XANES/EXAFS. From the EXAFS results and from the fact that higher loadings of Cu and Au lead to catalyst deactivation, it is proposed that in the reduced catalyst the SFT inactive promoter is segregated to the surface. Silver and Gold were the most active in promoting Co reduction and therefore increasing catalytic activity for the SFT. No important modification in the selectivity of the reaction was observed.

L’électronique souple utilisée dans les technologies RFID et NFC est aujourd’hui en plein essor et la demande croît exponentiellement chaque année. De nombreuses applications sont possibles comme les antennes RFID et les conducteurs transparents. Pour répondre à cette demande, il est nécessaire de proposer une technologie de fabrication à bas coût. Aujourd’hui les antennes sont fabriquées en R2R (Roll to Roll) par des méthodes soustractives à des coûts trop élevé et générant des déchets. Les méthodes d’impressions, qui sont additives, permettent aujourd’hui de réaliser des objets à la demande. L’objectif de cette thèse est de développer une technologie de rupture par rapport à l'existant. Les développements actuels se faisant majoritairement sur des nanoparticules d’argent, la stratégie de la thèse a été de développer un primaire métallisable (encre catalytique) pour la métallisation par voie chimique (electroless Cuivre). Dans cette étude nous avons abordés les différentes étapes qui ont permis de sélectionner le polymère adéquat pour la métallisation par voie chimique, à basse température, d'optimiser son greffage ainsi que son incorporation dans une formulation complète d’encre catalytique. Différentes preuves de concepts ont été obtenues grâce à la technologie développée par voie jet d’encre. La métallisation electroless permet d’obtenir une résistivité de 1.8 µΩ.cm et une excellente adhésion sur des substrats souples peu onéreux de faible point de transition vitreuse comme le PET et le PVC. La température du procédé de métallisation n’excède pas 50 °C. / The flexible electronics used in RFID and RFID and NFC technologies is now a booming market and demand is growing exponentially each year. Many applications are possible, such as RFID antennas and transparent conductors. To meet this demand, it is necessary to offer a low-cost manufacturing technology. Today antennas are manufactured in R2R (Roll to Roll) by subtractive methods and at high cost and generating waste. The methods of printing, which are additive, allow today to realize objects on demand. The aim of this thesis is to develop a breakthrough technology compared to the existing one. The current developments are predominantly done thanks to silver nanoparticles, the strategy of thethesis was to develop a metallizable primer (catalytic ink) for metallization by chemical means (electroless copper). In this study we will see the different steps that allowed us to select the appropriate polymer for chemical metallization, at low temperature and optimize its grafting as well as its incorporation in a complete formulation of catalytic ink. Different proofs of concepts have been obtained thanks to the technology developed by inkjet. The metallization electroless makes it possible to obtain a resistivity of 1.8 μΩ.cm and a very good adhesion on the inexpensive flexible substrates and weak point of glass transition polymer such as PET and PVC. The temperature of the metallization process does not exceed 50 °C.

No description available.

No description available.

Solid oxide fuel cells (SOFCs) have attracted much interest as the most efficient electrochemical device to directly convert chemical energy to usable electrical energy. The porous Ni-YSZ anode known as the state-of-the-art cermet anode material is found to show serious degradation when using hydrocarbon as fuel due to carbon deposition, sulphur poisoning, and nickel sintering. In order to overcome these problems, doped strontium titanate has been investigated as a potential anode material due to its high electronic conductivity and stability in reducing atmosphere. In this work, A-site deficient strontium titanate co-doped with lanthanum and calcium, La₀.₂Sr₀.₂₅Ca₀.₄₅TiO₃ (LSCT[sub](A-)), was examined. Flat multilayer ceramics have been produced using the aqueous tape casting technique by controlling the sintering behaviour of LSCT[sub](A-), resulting in a 450µm thick porous LSCT[sub](A-) scaffold with a well adhered 40µm dense YSZ electrolyte. Impregnation of CeO₂ and Ni results in a maximum power density of 0.96Wcm⁻² at 800°C, higher than those of without impregnation (0.124Wcm⁻²) and with impregnation of Ni alone (0.37Wcm⁻²). The addition of catalysts into LSCT[sub](A-) anode significantly reduces the polarization resistance of the cells, suggesting an insufficient electrocatalytic activity of the LSCT[sub](A-) backbone for hydrogen oxidation, but LSCT[sub](A-) can provide the electronic conductivity required for anode. Later, the cells with the configuration of LSCT[sub](A-)/YSZ/LSCF-YSZ were prepared by the organic tape casting and impregnation techniques with only 300-m thick anode as support. The effects of metallic catalysts in the anode supports on the initial performance and stability in humidified hydrogen were discussed. The nickel and iron impregnated LSCT[sub](A-) cell exhibits a maximum powder density of 272mW/cm² at 700°C, much larger than 43mW/cm² for the cell without impregnation and 112mW/cm² for the cell with nickel impregnation. Simultaneously, the bimetal Ni-Fe impregnates have significantly reduced the degradation rates in humidified hydrogen (3% H₂O) at 700°C. The enhancement from impregnation of the bi-metal can possibly be the result of the presence of ionic conducting Wustite Fe₁₋ₓO that resides underneath the Ni-Fe metallic particles and better microstructure. Third, in order to improve the ionic conductivity of the anode support and increase the effective TPBs, ionic conducting ceria was impregnated into the LSCT[sub](A-) anode, along with the metallic catalysts. The CeO₂-LSCT[sub](A-) cell shows a poor performance upon operation in hydrogen atmosphere containing 3% H₂O; and with addition of metallic catalysts, the cell performance increases drastically by almost three-fold. However, the infiltrated Ni particles on the top of ceria layer cause the deposition of carbon filament leading to cell cracking when exposure to humidified methane (3% H₂O). No such behaviour was observed on the CeO₂-NiFe impregnated anode. The microstructure images of the impregnated anodes at different times during stability testing demonstrate that the grain growth of catalysts, the interaction between the anode backbone and infiltrates, and the spalling of the agglomerated catalysts are the main reasons for the performance degradation. Fourth, the YSZ-LSCT[sub](A-) composites including the YSZ contents of 5-80wt.% were investigated to determine the percolation threshold concentration of YSZ to achieve electronic and ionic conducting pathways when using the composite as SOFC anode backbone. The microstructure and dilatometric curves show that when the YSZ content is below 30%, the milled sample has a lower shrinkage than the unmilled one due to the blocking effect from the well distributed YSZ grains within LSCT[sub](A-) bulk. However, at the YSZ above 30% where two phases start to form the individual and interconnected bulk, the composites without ball milling process show a lower densification. The impact of YSZ concentration and ball milling process on the electrical properties of the composites reveals that the percolation threshold concentration is not only dependant on the actual concentration, but also related to the local arrangement of two phases. In Napier University, the electroless nickel-ceramic co-depositon process was investigated as a manufacturing technique for the anodes of planar SOFCs, which entails reduced costs and reduced high-temperature induced defects, compared with conventional fabrication techniques. The Ni-YSZ anodes prepared by the electroless co-deposition technique without the addition of surfactant adhere well to the YSZ electrolyte before and after testing at 800°C in humidified hydrogen. Ni-YSZ anodes co-deposited with pore-forming starch showed twice the maximum power density compared with those without the starch. It has therefore been demonstrated that a porous Ni-YSZ cermet structure was successfully manufactured by means of an electroless plating technique incorporating pore formers followed by firing at 450°C in air. Although the use of surfactant (CTAB) increases the plating thickness, it induces the formation of a Ni-rich layer on the electrolyte/anode interface, leading to the delamination of anode most likely due to the mismatched TECs with the adjacent YSZ electrolyte.