L'absence de structure cristalline dans les verres métalliques tendrait à suggérer qu'aucun effet d'échelle sur leur comportement mécanique ne pourrait exister. Cependant, la diminution de la taille des éprouvettes de verre métallique, principalement solliciter en micro-compression sur des micro-pilliers usiné au FIB à partir de BMG révèlent une transition entre des mécanismes de déformation localisés dans des bandes de cisaillement pour des échelles supérieures à 400 nm et des mécanismes qui présentent des déformations homogènes en dessous de 400 nm. Des interrogations demeurent cependant sur l'impact des procédés d'élaboration des échantillons. Dans cette thèse, on s'intéresse à une autre voie de caractérisation des effets d'échelle sur le comportement mécanique des verres métalliques par l'élaboration et la caractérisation d'éprouvettes obtenues par des procédés de microélectronique dans des films minces de verre métallique de différentes épaisseurs, sans recours à de l'usinage FIB. La structure amorphe et la composition des dépôts réalisés par MS-PVD ont été confirmées par des analyses DRX et MET. L'homogénéité des dépôts entre les différentes épaisseurs a été confirmée par l'invariance du module de Young et du module de cisaillement déterminé par diffusion Brillouin sur chaque épaisseur. Des mesures de nano indentation ont cependant révélé une diminution de la dureté, une augmentation du module de compressibilité et du coefficient de Poisson avec l'augmentation de l'épaisseur des films. L'observation des déformations d'éprouvettes de flexion et des empreintes en nano indentation confirme l'existence d'une taille critique d'éprouvette. Les relations entre les différentes propriétés mécaniques et les observations sur les effets d'échelle sont discutées à partir du modèle des STZ et d'une loi de comportement élasto-plastique parfaite pour toutes les épaisseurs. / The lack of cristalline structure in metallic glasses suggests that no mechanical size effect could be expected. However, if the sample size decreases, a transition around 400 nm in size between deformations localized in shear band and homogeneous deformations was observed mainly on micropillars machined by FIB. But there are still a few questions which remained unanswered on elaboration process and their influence on amorphous structure with the size decreasing. This thesis deals with on a new way to characterize the size effect on the mechanical behaviour of metallic glasses. Metallic glasses thin films were elaborated by MS-PVD and mechanical samples were designed thanks to microelectronic process. Homogeneity of the amorphous structure and of the composition were determined by XRD and TEM. Elastic constant such as Young modulus and shear modulus obtained by Brillouin scattering analysis are also steady whatever the thicknesses. Nevertheless, nano indentation measures showed that Poisson ratio and Bulk modulus increase when the thin films thicknesses increase. Deformations observed on nano bending sample and imprints in nano indentation show also a transition between homogeneous deformation and deformations with shear bands. The origins of these transitions between the mechanical properties are discussed from a elastic perfectly plastic model and the Shear Transition Zone model.

L'objectif principal de cette thèse est dirigé vers l'établissement et l'explication des relations entre les conditions de synthèse des couches minces de CZTSSe, ses propriétés physiques et les performances des dispositifs photovoltaïques. Pour faire face à cette tâche la première approche était de comprendre le mécanisme de formation de la matière par rapport aux conditions de croissance du matériau. Le CZTSSe est synthétisé par un processus de sélénisation en deux étapes, où une première étape de dépôt par PVD de précurseurs est nécessaire, suivie d'une seconde étape de recuit sous atmosphère de sélénium. Différents ordres d'empilement de précurseurs ont été étudiés afin de comprendre la séquence de réactions qui, à partir de leur dépôt, conduise à la couche finale de CZTSSe. Cette étude, fait en plusieurs étapes, a nécessité de un effort important sur la caractérisation du matériau à chaque étape de la synthèse. Le résultat a montré que dans le cas du procédé en deux étapes, le matériau final est indépendant du dépôt de précurseurs. Les possibles implications bénéfiques en raison de l'incorporation de sodium dans le CZTSSe sont également décrites. Cette étude est réalisée en synthétisant la couche de CZTSSe sur différents substrats contenant diffèrent taux de sodium: de cette manière, pendant la synthèse, le sodium migre de substrats vers l'absorbeur. Après quantification du Na dans le CZTSSe juste après la croissance, le matériau est caractérise afin d'évaluer sa qualité. Ensuite il est employé dans une cellule solaire complète pour vérifier ses propriétés photovoltaïques. Les résultats ont montré que, comme pour la technologie CIGS, le sodium est bénéfique pour le CZTSSe, permettant l'augmentation de la tension à circuit ouvert et le rendement de cellule. Le molybdène est le contact arrière le plus utilisé pour les cellules solaires à base CZTSSe. Cependant, il a été suggéré récemment que le Mo n'est pas stable à l'interface avec le CZTSSe. En outre, à ma connaissance, aucune étude expérimentale n'a été effectuée à ce jour pour tester si les cellules solaires construites sur un autre contact arrière pourraient présenter de meilleures propriétés photovoltaïques. A cet effet, divers métaux (Au, W, Pd, Pt et Ni) sont déposées sur le dessus de Mo et testés comme contacts arrières dans les cellules solaire à base de CZTSSe. Il est démontré qu'il est possible synthétiser de films minces de CZTSSe de qualité quand le tungstène, l'or et le platine sont employé comme contacts arrière. Il est démontré que les contacts en W et Au permettent d'augmenter le courant photogénéré, mais aussi que le Mo reste le meilleur contact arrière en termes d'efficacité de conversion. Les effets de la variation du rapport [S]/([S]+[Se]) sur les performances des cellules solaires à base CZTSSe ont été étudiés. Cette étude a été faite par simulations des cellules solaires à base de CZTSSe, où le taux de chalcogènes dans l'absorbeur est varié, avec l'objective de trouver la composition optimale de l'absorbeur. Deux types d'approche différente ont été étudiés: la variation linéaire du rapport des chalcogènes, et une variation parabolique. Les simulations conduisent à un rendement de 16,5% (avec une tension en circuit ouvert de 0,56 V, courant de court-circuit de 37,0 mA/cm2 et un facteur de forme de 79,0%) lorsque la teneur en soufre est diminué linéairement à partir du contact arrière en direction de la couche tampon. Sur la base de ces résultats, nous proposons que l'ingénierie de bande interdite sur la base de la variation du taux [S]/([S]+[Se]) dans l'absorbeur est un outil puissant qui permet d'augmenter les performances des cellules solaires à base CZTSSe sans changer la qualité de l'absorbeur en lui-même. / The main objective of this PhD thesis was directed toward establishing and explaining the relationships between synthesis conditions of CZTSSe, its physical properties and performance of photovoltaic devices. To tackle on this task the first approach was to understand the formation mechanism of the material in relation to the growth conditions. CZTSSe is synthesized by two-step selenization process, where a first step of precursor deposition by PVD is required, followed by a second step of annealing. Different precursor stacking orders have been studied in order to understand the sequence of reactions that, starting from their deposition, lead to the final CZTSSe layer. This study made step-by-step has required a strong effort on the material characterization at each step of the synthesis. The result demonstrated that in the case of two-step process, the final material is independent of the precursor deposition. The possible beneficial involvements due to incorporation of sodium in CZTSSe are also disclosed. This study is carried out by synthesizing CZTSSe on different sodium-containing substrates: in this way sodium migrates from the substrates to the absorber. After quantification of Na in CZTSSe right after growth, the latter is characterized to evaluate its quality and employed in a full solar cell to check on its photovoltaic properties. Results demonstrated that, as for CIGS technology, sodium is beneficial for CZTSSe allowing increasing the open circuit voltage and efficiency. Molybdenum is the most used back contact in CZTSSe based solar cells. However, it has been suggested recently that Mo is not stable at the interface with CZTSSe. In addition, to the best of our knowledge, no experimental study has been carried out so far to test whether solar cells built on another back contact could exhibit better photovoltaic properties. For this purpose, various metals (Au, W, Pd, Pt, and Ni) are deposited on top of Mo, and it is demonstrated that it is possible to synthesize device-quality CZTSSe thin films on W, Au, and Pt back contacts. It is shown that that W and Au back contacts allow enhancing the photogenerated current, but that Mo remains the best back contact in terms of power conversion efficiency. The effects of [S]/([S]+[Se]) ratio tuning on CZTSSe based solar cell performances have been studied by solar cell capacitance simulator (SCAPS) to find out the optimum absorber composition. Two different kind of approach have been studied: linear variation of the chalcogens ratio, and a parabolic variation. The simulations lead to an efficiency of 16.5% (with open-circuit voltage of 0.56 V, short-circuit current of 37.0 mA/cm2 and fill factor of 79.0%) when the sulfur content is linearly decreased from the back contact towards the buffer layer. Based on these results, we propose that bandgap engineering based on the control of [S]/([S]+[Se]) ratio in the absorber is a powerful tool which allows increasing the performances of CZTSSe based solar cells without changing the absorber material quality.

Cu(In,Ga)Se2 (CIGS) is a semiconductor material and the basis of the promising thin-film photovoltaic technology with the same name. The CIGS film has a typical thickness of 1-2 mm, and solar cells based on CIGS technology has recently reached efficiencies of 23.3%. Ultra-thin CIGS solar cells use sub-micrometer thick films that require significantly less material and can be manufactured in a shorter amount oftime than films with typical thicknesses. With decreasing thickness, both electrical and optical losses get more significant and lower the overall performance. Electrical losses can be decreased by increasing the overall film quality and by utilising a graded bandgap throughout the CIGS layer. The band gap can be changed by varying the[Ga]/([Ga]+[In]) (GGI) ratio. Higher overall film quality and a higher band-gap towards the back of the absorber are expected to increase the performance. In this work, sputtered CIGS solar cells were made with different CIGS layer thicknesses, that ranged between 550-950 nm. Increased heat during deposition was examined and shown to increase the film quality and performance for all thicknesses. Two different ways of doping CIGS with Na was examined and it was found that higher Na content lead to an increasing predominance of the (112) plane. The bandgap was graded by varying the GGI composition throughout the CIGS layer and depth profiles were made with Glow-Discharge Optical Emission Spectroscopy (GDOES). It was found that a sputtered CuGaSe2 (CGS)layer below the CIGS-layer lead to a steep increase of the GGI near the back contact. When CGS made up 10% of the total CIGS layer thickness, a significant increase in performance was observed for all thicknesses. CIGS-absorbers with a less graded region with low GGI, making up 30% or 60% of the total CIGS layer thickness were made. A decrease in GGI in that region, was shown to increase the current but lower the voltage. No substantial increase in total performance compared to a fully graded CIGS layer was seen regardless of layer thickness. For further work the optical losses needs to be addressed and work on increasing the optical path in the CIGS layer needs to be done.

Os antigos e já bem desenvolvidos dispositivos para tratamentos e/ou análise de amostras têm sido grandemente estudados para novas adaptações, devido à importância de se construir sistemas miniaturizados. A obtenção destes sistemas miniaturizados baseia-se não apenas na construção ou metodologia, mas pode depender de modificação superficial para melhoria de desempenho ou diferenciação de aplicações. A modificação de superfície com filmes finos obtidos por plasma é bem conhecida na Microeletrônica. Assim, este trabalho teve como objetivo avaliar a possibilidade do uso da modificação superficial pela produção de filmes finos a partir da polimerização por plasma de Tetraetilortossilicato, TEOS - para fabricação de estruturas miniaturizadas, principalmente para retenção e/ou pré-concentração, em pré-tratamento de amostras ou mesmo para proteção de sistemas de detecção. A metodologia utilizada correspondeu a testes destes filmes em canais ou membranas seletivas. Quanto aos canais utilizou-se geometria planar e/ou tridimensional; as membranas foram testadas em geometria planar. Microcanais tridimensionais, usados tanto em fase gasosa como líquida, foram testados para determinação de retenção/pré-concentração de compostos orgânicos voláteis. Para testes de retenção de compostos inorgânicos em fase líquida (água como solvente) utilizaram-se não só microcanais, tridimensionais ou planares, como também membranas. Proteção de sistemas de detecção exigiu o uso de geometria plana. Quanto ao filme a base de TEOS, este foi testado imediatamente após a deposição, após envelhecimento por no mínimo seis meses ou após exposição a condições adversas como a que levam à hidrólise de radicais orgânicos presentes no filme, ou mesmo após hidrofobização da superfície, por exposição à Hexametildissilazana, HMDS. A construção de dispositivos, com canal planar ou tridimensional, permitiu o desenvolvimento de diferentes sistemas de tratamento, e respectivos métodos de análise, para separação, retenção e pré-concentração de amostras. Os resultados obtidos demonstraram que um dispositivo com canal tridimensional, tratado pela deposição a base de TEOS e posterior hidrólise do filme, permite a retenção de íons e formação de clusters de cobre, em fase líquida. Do mesmo modo, permite a separação de compostos orgânicos em pequena concentração e retenção de compostos polares, em fase gasosa. Para dispositivo planar foi observada a separação de íons através de estrutura plana, similar às utilizadas em eletrocromatografia. Os estudos processados permitiram propor pequenos dispositivos, de baixo custo e fabricação simples, que podem ser facilmente implantados na área de análises. Assim, o canal tridimensional testado tem comportamento semelhante ao de uma pré-coluna. Como é de simples construção e sua entrada e saída possui similaridades com uma pré-coluna comercial, a instalação desta pré-coluna em um cromatógrafo miniaturizado requererá poucas etapas. Essa nova pré-coluna também apresentaria grandes vantagens se fosse adicionada imediatamente antes de detectores não específicos, tais como os usados no nariz eletrônico. Pela diminuição de compostos presentes na mistura, as dificuldades de análise dos resultados igualmente decresce, pela maior facilidade de criação de padrões. / The long-established and well-known devices for sample pretreatment and/or analysis have been widely studied to new adaptations due to the miniaturization trend. The production of these miniaturized systems requires not only new approach on manufacturing and methodology but also depends on surface modification for performance improvement or new applications development. Surface modification using plasma-produced thin films is well established in Microelectronics. Therefore, the aim was to evaluate the use of Plasma polymerized Tetraethylorthosilicate surface modification on manufacturing of miniaturized structures. The main use of such a modification is on devices for sample pretreatment - retention, pre-concentration, or even for protecting detection system surface. The methodology carried out tested these thin films in channels and selective membranes. Whereas channels used three-dimensional and planar geometries, membranes were tested only with planar geometries. Three-dimensional microchannels, used in gaseous or liquid phase, were tested for retention/preconcentration of volatile organic compounds (VOCs). Retention of inorganic compounds in aqueous liquid phase was tested using not only three-dimensional and planar microchannels but also membranes. Protection of detection systems required planar geometry. TEOS thin film was tested after: deposition, ageing for several months; exposition to severe environmental conditions that leads to hydrolysis of organic radicals present in the film; surface hydrophobization due to hexamethyldisilazane, HMDS, exposure. Manufacturing of miniaturized three-dimensional and planar devices leads to some solutions on sample pretreatment and respective analysis methodology. These devices can be used for separation, retention and pre-concentration. The results pointed out that a threedimensional microchannel with plasma deposited TEOS film previously hydrolyzed allows ion retention and clusters formation in a copper aqueous solution. Furthermore, in gaseous phase, VOCs in small concentration can be separated whereas polar compounds can be retained. Planar device allows separation of inorganic ions in a structure similar to the ones used in electrochromatography. Small and low-cost devices are thus here provided, which can easily be machined and are very useful in the chemical analysis field. The three-dimensional microchannel presented behavior similar to the one of a chromatographic pre-column. This microchannel can also be easily adapted to a miniaturized chromatograph. Other possible use is in sample pretreatment, coupled ahead of non-specific detectors, such as electronic noise arrays, since it can decrease the numbers of compounds to be detected and, consequently, reduce drawbacks concerning results analysis.

Made available in DSpace on 2014-06-11T19:29:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-04-13Bitstream added on 2014-06-13T19:38:01Z : No. of bitstreams: 1 cincotto_fh_me_sjrp.pdf: 789637 bytes, checksum: 23f32cf9d8279cacf5618ee5020c1dc6 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A formação de filmes poliméricos contendo azobenzeno tem recebido atenção especial devido à sua aplicação em dispositivos fotônicos. Neste trabalho estudamos a eletropolimerização de Bismarck Brown R (4-3- (2,4-diamin-5-metilfenil)- 4-metilfenildiazenil]diazenil-6-metilbenzeno-1,3-diamindiclorohidrato), filmes ultra-finos sobre substratos de ITO. Foi realizado o estudo do comportamento do filme polimérico variando-se parâmetros durante a etapa de eletropolimerização para a otimização do poliBBR, visando o desenvolvimento de eletrodos modificados para serem utilizados como sensores químicos. O uso da técnica eletroquímica na preparação de filmes poliméricos tem diversas vantagens, tais como a formação do filme diretamente sobre diferentes substratos, controle de espessura do filme, alta reprodutibilidade, geração de polímeros dopados e possibilidade de imobilização de espécies durante a fase de polimerização. Os filmes ultra-finos depositados nos substratos condutores por eletropolimerização foram caracterizados eletroquimicamente (voltametria cíclica e pulso diferencial), espectroscopia de ultravioleta-visível e microscopia de força atômica (AFM). O trabalho se destaca por possuir pouco ou nenhum relato na literatura sobre os dados obtidos dos estudos eletroquímicos e ópticos do comportamento do polímero de Bismarck Brown R. Foram obtidos dados interessantes no comportamento óptico no estudo da imobilização de íons metálicos na estrutura polimérica do BBR, destacando-se as diferentes geometrias e conformações (cis e trans) investigadas no trabalho / The formation of azobenzeno containing polymeric films have been special attention due to its application in photonic devices. In this work we studied the electropolymerization of Bismarck Brown R (4-3-(2,4-diamin-5-methylphenyl)-4-methylphenyldiazenyl]diazenyl-6-methilbenzene-1,3-diamindiclorohidrato), ultra thin films on substrates of ITO. Was carried out study the behavior of the polymer film varying the parameters during the step for the electropolymerization polyBBR optimization, in order to develop modified electrodes to be used as chemical sensors. The use of electrochemical technique for preparing polymer films have several advantages, such as film formation directly on different substrates, film thickness control, high reproducibility, generating doped polymers and possible immobilization of species during the polymerization. The ultra-thin films deposited in conductive substrates were characterized electrochemically (cyclic voltammetry and differential pulse), UV-Vis spectroscopy and atomic force microscopy (AFM). The work stands out due to little or no reports in the literature on data obtained from studies of the electrochemical and optical behavior of polymer Bismarck Brown R. We obtained interesting data on optical behavior in the study immobilization of metal ion in the polymeric structure of the BBR, highlighting the different geometries and conformations (cis and trans) investigated in the work

Les films minces déposés sur des substrats flexibles ont été intensivement étudiés ces dernières années en raison de leur nombreuses applications en électronique flexible. Depuis peu, l'électronique flexible est étendu aux matériaux magnétiques conduisant ainsi au domaine émergeant de la magnéto-électronique flexible actuellement à l'avant garde des sujets de recherche de la spintronique. Ce travail de thèse est dédié à l'étude des propriétés magnéto-mécaniques de films minces magnétiques (Ni, NiFe, Co2FeAl, CoFeB, FeCuNbSi) sur des substrats flexibles. Les analyses structurales ont montré que les films de Ni et de CFA sont polycristallins non-texturés ; le CFB est amorphe. Par conséquent, les propriétés élastiques et magnéto-élastiques de ces films sont considérées comme étant isotropes. Une technique basée sur une utilisation conjointe d'essai mécanique, la résonance ferromagnétique (FMR) et la corrélation d'images numériques (CIN) a été développée pour étudier les propriétés magnéto-mécaniques de films minces sur substrats flexibles. A l'aide de cette méthode, il est possible de suivre l'évolution de l'anisotropie résiduelle omniprésente dans les films magnétiques sur substrats flexibles. Cette anisotropie est liée aux propriétés mécaniques contrastées lorsqu'on dépose un film mince rigide (grand module d'Young) sur un substrat flexible (petit module d'Young). L'effet du recuit sur les propriétés élastiques et magnéto-élastiques a été soigneusement étudié dans le film CFB validant ainsi l'intérêt porté à ses alliages pour des applications en spintronique. Enfin, la résonance ferromagnétique est employé en balayage en fréquence pour suivre la variation de la direction de l'aimantation en fonction des déformations induites par l'application de tension électrique sur l'actionneur piézoélectrique. Un retournement de 90° de la direction de l'aimantation dans le film Co2FeAl sur substrat flexible de Kapton® est observé. / Thin films deposited on flexible substrates have been widely studied in the last decades due to the numerous applications in flexible electronics. Recently, flexible electronics have been extended to magnetic materials leading to the so-called emerging feld of flexible magnetoelectronics which is actually at the cutting-edge of spintronics research topics.This thesis is devoted to the study magnetomechanical properties of magnetic thin films (Ni, NiFe, Co2FeAl, CoFeB, FeCuNbSi) on flexible substrates. Structural analysis have 130 Abstracts hown that the Ni and CFA films are found to be polycrystalline with no strong preferred orientations ; the CFB film is amorphous. Consequently, the elastic and magnetoelastic properties are isotropic. For the study of the magnetomechanical properties, a set-up based on a jointly use of deformation test (bending or piezoactuation), ferromagnetic resonance (FMR) and digital image correlation (DIC) have been developped. Thanks to this method, it is possible to follow the evolution of the inescapable residual anisotropy encountered in magnetic thin films on flexible substrates under deformation and to determine the effective coefficient of magnetostriction of the films (sometimes unknown).This residual anisotropy is ascribed to contrasted mechanical strength when a sti thin film is deposited on a compliant substrate. The effect of the annealing temperature on the elastic and magnetoelastic have been studied carefully in CFB validating then theinterest on such alloys for spintronics applications. Finally, we have employed FMR inits sweep frequency mode to study the effective evolution of magnetization direction as function of the voltage-induced strains. A 90-degree magnetization rotation in Co2FeAl thin film on Kapton® polyimide substrate is observed.

Orientador: José Arana Varela / Banca: Maria Aparecida Zaghete Bertochi / Banca: Miguel Jafelicci Junior / Banca: Andrea Simone Stucchi de Camargo / Banca: José Antonio Eiras / Resumo: Nesta tese estudou-se a preparação de filmes finos de PZT não dopados e dopados com Nióbio, depositados sobre substratos de Pt/Ti/SiO2/Si para aplicações em memórias não voláteis de acesso randômico (NVRAM) e memórias ferroelétricas de acesso randômico (FeRAM). A dopagem dos filmes de PZT com Nióbio foi realizada visando obter valores ótimos nas propriedades ferroelétricas para a aplicação destes filmes como memórias ferroelétricas. Todavia, problemas como imprint, corrente de fuga e fadiga na polarização, estão presentes nos dispositivos de memórias contendo filmes de PZT sobre substratos platinizados. Para tentar resolver estes problemas, estudamos a produção de eletrodos de LaNiO3 depositados sobre substratos de SiO2/Si, para substituição dos substratos com eletrodos de Pt na preparação de filmes de PZT. Além disso, a dopagem do PZT com Nb levou a uma melhoria na resistência à fadiga em substratos platinizados. Os filmes foram preparados pelo método das soluções precursoras poliméricas. A influência do tratamento térmico, em forno convencional e em forno microondas, nas propriedades microestruturais e ferroelétricas dos filmes também foi avaliada. / Abstract: In this thesis, we have studied the preparation of non-doped and Nb-doped PZT thin films deposited on Pt/Ti/SiO2/Si substrates for applications in NVRAM and FeRAM devices. Nb doping of PZT films produces good values of ferroelectric properties for the application as ferroelectric memories. PZT films on Pt electrodes present imprint, fatigue and leakage current. We have prepared LaNiO3 films on SiO2/Si substrates to substitute Pt electrodes. Moreover, Nb-doped PZT films deposited on Pt electrodes lead to improved fatigue resistance when compared with non doped PZT films. Non-doped and Nb-doped PZT thin films and LaNiO3 thin films were deposited by the polymeric precursor method. The influence of the thermal treatment in conventional and microwaves oven on the microstructural and ferroelectric properties was evaluated. / Doutor

Resumo: Problemas com a resistência de união metal-cerâmica têm sido encontrados quando o titânio é utilizado em Odontologia. A proposta deste estudo foi aumentar a resistência na interface titânio-cerâmica pela aplicação de um filme fino de platina na superfície do titânio, por meio da utilização da técnica de deposição por pulverização catódica. Dez padrões (1.0 x 4.0 x 30 mm) foram obtidos por meio de cortes de placas de resina acrílica e incluídos em um revestimento à base de zircônia. As fundições de titânio para preenchimento dos moldes foram realizadas em uma máquina de fundição centrífuga. As amostras foram lixadas até as dimensões finais (0.50 x 3.0 x 30 mm) para a remoção da camada -case e jateadas com pó de alumina (grupo controle) e de dióxido de titânio (grupo experimental). Uma cerâmica de ultrabaixa temperatura de fusão foi aplicada no centro da superfície (8.0 x 1.0 x 3 mm). A resistência de união foi determinada pelo teste de flexão de três pontos em uma máquina universal de ensaios com uma velocidade de 0,5mm/min. As amostras foram analisadas por meio de microscopia óptica e microscopia eletrônica de varredura antes e após os ensaios mecânicos. Os resultados revelaram valores maiores de união entre o titânio e a cerâmica quando o filme de platina foi aplicado (25,70 l 4,54 MPa), mas não houve diferença estatística significante em relação ao grupo controle (24,32 l 3,11 MPa), o que indica que o primeiro grupo também possui uma resistência de união suficiente para uso clínico. / Abstract: Problems with metal-ceramic bond strength have been encountered when titanium is used in prosthetic dentistry. The purpose of this study was increase the bond strength of titanium-ceramic interface applying a platinum film on the titanium surface using DC-sputtering deposition technique. Ten 1.0 x 4.0 x 30 mm patterns were cut from sheet of acrylic resin and invested in a zirconia-based investment material. Titanium castings were made using a centrifugal casting machine. Specimens were grinded to final dimensions (0.50 x 3.0 x 30 mm) to remove the -case layer and blasted with alumina (control group) and titanium dioxide (experimental group) powders. An ultra low-fusing dental ceramic was applied to the center of the surface (8.0 x 1.0 x 3 mm). The bond strength was determined by three-point bending test. at a universal testing machine with a loading rate of 0,5mm/min.The samples were analyzed using Optical Microscopy and Scanning Electron Microscopy before and after the mechanical testing.The results showed greater values of adherence between titanium and ceramic when the platinum film was applied (25,70 l 4,54 MPa), but there were no statistic differences to those of the controls (24,32 l 3,11 MPa) that indicates that the first one has also sufficient bond strength for clinical use. / Orientador: Aelcio Zangrandi / Coorientador: Ana Paula Rosifini Alves / Banca: Sigmar de Mello Rode / Banca: Cecília Amélia de carvalho Zavaglia / Mestre

Nas últimas décadas, o interesse na eletrônica flexível tem aumentado. Sistemas que apresentam benefícios, tais como: baixo custo, melhor desempenho, transparência, confiabilidade e melhores credenciais ecológicas, estão sendo extensivamente pesquisados por vários grupos. Os transistores de filmes-finos possuem potencial para alcançarem essas características. Dispositivos baseados em óxido de zinco (ZnO) tem atraído pesquisadores devido as suas propriedades elétricas, sensoriais e ópticas. Neste trabalho, nanopartículas de ZnO foram utilizadas como semicondutor ativo e cross-linked PVP (polivinilfenol) e PECVD-SiO2 (plasma enhanced chemical vapor deposition silicon dioxide) como dielétricos de porta para integrar transistores de filmes-finos. Este processo de integração tem por objetivo os pré-requisitos de baixo custo e baixa temperatura (<200°C). Por esta razão, a utilização de técnicas de integração simples, como o spin-coating ou a técnica de sidewall-etchback, foram utilizadas. Infelizmente, existem problemas relacionados à confiabilidade em dispositivos baseados em ZnO, entre eles a degradação no tempo ou a histerese. Após uma investigação experimental da histerese na característica de transferência, um modelo qualitativo para o comportamento observado é proposto. Observou-se que a direção da histerese é afetada pela variação da temperatura quando o dielétrico polimérico é usado. Baseando-se na caracterização dos transistores, a polarização do PVP, as armadilhas na superfície das nanopartículas e na interface com o dielétrico, bem como a liberação de moléculas de oxigênio da superfície das nanopartículas foram atribuídas como as principais causas da histerese. Além disso, uma flutuação discreta da corrente é observada em testes de estresse devido à captura e liberação de portadores em determinados caminhos de corrente no transistor, semelhante a random telegraph signal (RTS), relatado em MOSFET nanométricos. Este resultado suporta o hipotético mecanismo de transporte de elétrons (caminhos de percolação) em filmes compostos por ZnO nanoparticulado. / During the last decades, the interest in flexible electronics has arisen. Systems that present benefits such as low cost, improved performance, transparency, reliability and better environmental credential are being extensively researched by several groups. Thin-film transistors (TFT) have good potential concerning these technologies. Therefore, zinc oxide (ZnO) based devices have been attracting researchers for its electrical, sensory and optical properties. In this work, ZnO nanoparticles were used to integrate thin-film transistors, in which cross-linked PVP (Poly(4-vinylphenol)) and PECVD-SiO2 (plasma enhanced chemical vapor deposition silicon dioxide) were used as gate dielectric layer. The complete integration process targets low cost and low temperature requirements (< 200°C). For this reason, simple process techniques as spin-coating or sidewall-etchback were used. Unfortunately, there are different reliability concerns in ZnO devices, among them aging or hysteresis. An experimental investigation of the hysteresis in the transfer characteristic is performed, and a qualitative model for the observed behavior is proposed. It was observed that the hysteresis direction is affected by temperature variation when the polymeric dielectric is used. The PVP bulk polarization, the traps in nanoparticles and at the polymeric dielectric interface, as well as the desorption of oxygen molecules in the surface of the nanoparticles, were attributed as the main cause of the hysteretic behavior. Moreover, capture and release of charge carriers by traps at determined current paths in the transistor lead to discrete current fluctuations in stress tests, similar to random telegraph signal (RTS) reported in nanoscale MOSFET. This result supports the hypothesis of charge transport mechanism (percolation paths) in nanoparticulate ZnO.

Visando determinar os valores ótimos para o processo de serramento de anéis bobinados de filme metalizado ultrafino de alumínio com dielétrico de poliéster a partir das condições atuais do processo de fabricação de capacitores pela empresa Epcos do Brasil, realizou-se a avaliação de diferentes tipos de serras circulares variando-se a velocidade de rotação (n) e o tempo de corte (tc). Desenvolvido projeto de experimento desses três fatores a fim de obter o resultado das interações entre eles quanto à resistência de isolamento (Riso) das peças cortadas. A serra de 160 dentes de metal-duro com revestimento de filme de carbono tipo diamante (DLC) apresentou os melhores resultados quanto à “Riso” acima de 0,378 G e quanto ao número de peças com valor abaixo deste. Constatou-se que “n” não influencia significativamente para a distribuição de “Riso”; porém, gera menos peças abaixo do especificado. Já “tc” não influencia significativamente o processo. Quanto ao tipo de dente, o perfil reto obteve melhor resultado para lâminas de serra com 80 dentes e perfil curvo para lâminas com 160 dentes. Já a espessura da lâmina não influenciou de forma expressiva o processo. A lâmina de aço-rápido apresentou adesão de alumínio na lateral do corpo da serra e, consequentemente, adesão de material na superfície de corte. As lâminas de metal-duro sem revestimento apresentaram falhas no filme metalizado por causa do atrito gerado entre a superfície de corte e a lateral da lâmina; esse inconveniente é eliminado quando ela é revestida com filme DLC apresentando melhorias quanto à “Riso” das peças para “n” menores. Também houve adesão de alumínio na parte inferior do dente devido a uma delaminação da camada de filme DLC. / In order to determine the optimal values for the sawing process of wound rings of metalized ultra-thin film with dielectric of polyester from current conditions of capacitor manufacturing process by Epcos company in Brazil, it was performed the evaluation of different types of circular saws varying the rotational speed (n) and the cutting time (tc). Developed experiment design methodology for these three factors in order to get the result of the interactions between them regarding to the insulation resistance (Riso) of cut parts. Through the analysis of the main effects, the cemented carbide saw with 160 teeth and diamond-like carbon (DLC) film coating showed the best results in terms of "Riso" above 0,378 G and regarding to the number of parts with value below the specified. It was found that "n" does not influence significantly the distribution of "Riso"; however, generates fewer parts below the specified. Now "tc" does not significantly influence the process. Regarding the tooth type, straight profile obtained better results for saw blades with 80 teeth and curved profile for blades with 160 teeth. However the thickness of the blade did not influence significantly the process. The high speed steel blade presented adhesion of aluminum on the side of the saw body and, consequently, adhesion of material on the cutting surface. The cemented carbide blades uncoated presented failures on metalized film because of the friction generated between the cutting surface and the side of the blade; this drawback is eliminated when it is coated with DLC film presenting improvements to the parts "Riso" for lower "n". There was also aluminum adhesion on the bottom of the tooth due to a delamination of the DLC film layer.