The sensor is a device that converts a form of energy concerning which the information is sought, called the measurand, to a form (electrical) in which it can be usefully processed or interpreted. Sensors rely on physical or chemical phenomena and materials where those phenomena appear to be useful. Those phenomena may concern the material itself or its geometry. Hence, the major innovations in sensors come from new materials, new fabrication techniques or both. Normally, thin film sensors are realized by depositing a sensing film on a suitable substrate. There could be many combination of metals and insulating materials being deposited depending upon the application or sensing requirements. In general, sensors for various applications are fabricated using a variety of liquid phase technologies (also called as wet methods) and gas phase technologies (also called as dry methods) of deposition. Hence sensor fabrication technology requires various combination of processing technologies and newer materials. In the present work, an attempt is made to design and fabricate a thin film based pressure sensor using a combination of wet and dry deposition techniques. The diaphragm, used for sensing the pressure is coated with a hard anodic coating (Al2O3) using a wet technology, viz. pulse hard anodizing technique, for electrical insulation requirement. The piezo-resistive strain sensing films were deposited onto this coating by dry method, namely, DC Magnetron sputtering technique.. Chapter 01 gives a brief overview of sensors, their classification, principles of sensing,characteristics, materials used in the fabrication of sensors like conductors and insulators, the components of a sensor. Chapter 02 gives brief information about various techniques of depositions viz., liquid phase technologies (wet methods) and vapour phase technologies (dry methods) used to fabricate the sensors. Also, information regarding the coating property evaluation and coating characterization techniques is included. The chapter 03 presents a detailed account of work carried out to obtain an electrically insulating layer by the development of pulse hard anodizing process for aluminum alloy diaphragm, necessary process optimization and testing. The details related to the development, fabrication and testing of thin film based pressure sensors using aluminum alloy diaphragm with hard anodic coating are presented in Chapter 04. The thin film strain gauges were deposited using DC magnetron sputtering technique. The information about mask design, deposition process parameters, calibration etc is also included. Chapter 05 provides summary of the work carried out and conclusions. The scope of carrying out further work is also outlined.

Στην παρούσα εργασία μελετάται πειραματικά η ανάπτυξη μεμβρανών πορώδους αλουμίνας με ελεγχόμενο πάχος, διάμετρο πόρου, σε ηλεκτρολύτη οξαλικού οξέος συγκεντρώσεως 0.3Μ με εφαρμοζόμενη τάση 40V και 50V. Για την κατανόηση του μηχανισμού της δημιουργίας των μεμβρανών πορώδους αλουμίνας γίνεται μια βιβλιογραφική παρουσίαση των μοντέλων ανάπτυξης της. Από τα πειράματα προκύπτει ότι ο ρυθμός ανάπτυξης του πάχους της μεμβράνης ακολουθεί τον νόμο του Faraday με απόδοση που εξαρτάται από την τάση ανοδίωσης. Τέλος υπολογίζεται η ενέργεια ενεργοποίησης για την αντίδραση του σχηματισμού της πορώδους αλουμίνας. Η ενέργεια ενεργοποίησης που αφορά την αντίδραση του αλουμινίου με τον ηλεκτρολύτη. / Ιn the present study, the synthesis of porous alumina membranes with controlled thickness and pore diameter is investigated. More specifically, the experimental condition under study was oxalic acid 0.3M under an applied voltage of 40V and 50V. In order to understand the growth mechanism of the porous alumina membrane formation, a bibliographic view of the growth models is presented. The experiments result in the conclusion that the thickness growth rate of the porous alumina membrane obeys the Faraday law for electrolysis with an efficiency being dependent on the anodization applied voltage. Finally, the activation energy for the porous alumina formation concerning the reaction of aluminum with the electrolyte, is calculated.

In the current study, we give a report when oxalic acid was used as an electrolyte to synthesize an AAO template with hexagonal pore array. Optimum parameters were observed as 0.4 M of oxalic acid, anodizing voltage of 45 V, temperature of approximately 8 °C and the period of 120 minutes. Atomic force microscope (AFM) and High resolution scanning electron microscope (HRSEM) showed that template has an average pore diameter of 103 nm. Co and MnOx (x = 1,2) nanostructures were selectively deposited in the pores of the template using a novel atomic layer deposition (ALD) technique. The diameter sizes and the array of the nanostructures and the template were corresponding. Energy dispersive xrays (EDX) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Co and MnOx (x =1,2) on the samples while x-ray diffraction (XRD) provided an indication of their orientations. Magnetic force microscopy as main characterization tool showed the existence of multi-domains on both Co and MnOx (x =1,2) nanostructures.

Ce travail porte sur le développement d’une technique de structuration de surface pour le silicium. Celle-ci repose sur trois étapes essentielles : la lithographie, l’implantation ionique et le retrait par voie humide. Le motif formé par lithographie est transféré par homothétie dans la couche sous-jacente de silicium grâce à l’implantation ionique. Après le retrait du masque de résine, le substrat est traité par voie humide en vue de retirer des zones localement implantées. Le motif initial défini par la lithographie est ainsi révélé dans le silicium.La compréhension des modifications induites par l’implantation ionique dans le substrat nous a permis de réaliser avec succès un transfert dans le silicium. Nous avons principalement étudié les défauts générés par deux types d’ions : l’argon et l’hydrogène, à travers un certain nombre de techniques de caractérisation. Sur la base de cette étude, les différents traitements humides du silicium ont été investigués : gravure alcaline, gravure acide, dissolution par anodisation. L’optimisation des conditions d’implantation et des paramètres de retrait humide a permis l’obtention de structures 2D puis 3D.La faisabilité de cette technique de structuration a également été démontrée sur d’autres matériaux comme le SiOCH et le nitrure de silicium. / This thesis deals with the development of a patterning process for silicon substrates. Based on ion implantation through a resist pattern to locally modified the underneath layer. Wet etching processes have been developed to reveal the shapes transferred into the silicon substrate. Thanks to morphological, physical and chemical characterizations, modifications induced by ion implantation have been identified and understood.Two ion species (argon and hydrogen) were used in this thesis in order to assess either physical or chemical modifications in silicon substrate. Several wet chemistries: alkaline, acid and dissolution by anodization, were investigated to reveal the final shape. The optimization of the implantation and wet etching processes allowed to obtain 2D and 3D structures with silicon substrate.Moreover, our approach has been successfully implemented to pattern 2D shapes in SiOCH and silicon nitride.

Le Titane (Ti) est un matériau biocompatible largement utilisé dans le domaine biomédical, notamment pour les implants orthopédiques (prothèse de hanche ou du genou par exemple). Il se distingue plus particulièrement par son excellente résistance à la corrosion et sa capacité d’ostéo-intégration. Cependant, une surface plane de Ti n’est pas assez bioactive pour être implantée ; il est nécessaire d’avoir recours à un traitement de surface pour améliorer ses propriétés. La modification de la surface du titane par anodisation permet la synthèse de nanotubes (NTs) de TiO2 ordonnés et verticalement alignés. Cette technique, peu couteuse, rapide et facile à mettre en œuvre permet également de contrôler finement la morphologie des NTs (diamètre, longueur, aspect des parois…). De plus, les NTs étant amorphes après anodisation, la structure cristalline peut être ajustée par un traitement thermique, conduisant à une structure anatase (450°C) ou à une structure mixte d’anatase et de rutile (550°C).Ainsi, des surfaces de différentes morphologies et différentes structures cristallines ont été synthétisées dans ce travail de thèse, afin d’évaluer l’influence des caractéristiques morpho-structurelles sur la résistance à la corrosion en milieu physiologique et sur la bioactivité (formation d’hydroxyapatite et réponse cellulaire).Nous avons démontré dans cette étude que les NTs cristallisés présentent une plus grande résistance à la corrosion et une meilleure bioactivité que les NTs amorphes (ou que les surfaces planes de Ti). Plus précisément, en tenant compte des aspects électrochimiques, thermiques, mécaniques, chimiques et de bioactivité, il semblerait que des NTs mixtes d’environ 720 nm de long et 90 nm de diamètre constituent une surface optimale pour les applications visées.D’autre part, dans le cadre de l’étude des propriétés électrochimiques de l’interface, une attention toute particulière a été accordée dans ce travail de thèse à la modélisation des résultats de mesures par Spectroscopie d’Impédance Electrochimique (SIE). Il s’avère que la réponse en impédance des NTs de TiO2 en milieu physiologique correspond au modèle d’électrode poreuse de De Levie. Toutefois, pour des électrodes poreuses non-idéales, cette théorie peut être généralisée et modélisée par des lignes de transmission. Ainsi, le modèle de ligne de transmission proposé dans cette étude s’ajuste de façon très satisfaisante aux mesures expérimentales. Il permet notamment de mettre en évidence la nature très peu réactive des NTs de TiO2, justifiant ainsi leurs applications dans le domaine biomédical. / Titanium (Ti) is a biocompatible material widely used in the biomedical field, especially for orthopedic implants (for instance hip or knee replacement). It is particularly corrosion resistant and shows remarkable osseointegration properties. However, plane Ti surfaces are not bioactive enough to be implanted; they need to be improved by surface treatments. Surface modification of Ti by anodization enables to synthesize self-organized and vertically aligned TiO2 nanotubes (NTs). This cheap, fast and easily implementable technique also permits a fine tuning of NTs morphology (diameter, length, wall look, etc.). Moreover, since as-anodized NTs are amorphous, crystalline structure may be adjusted by heat treatment, producing anatase structure (450°C) or a mixed structure of anatase and rutile (550°C).Therefore, surfaces of different morphologies and crystalline structures have been synthesized in order to evaluate the influence of these characteristics on corrosion resistance in physiological medium and on bioactivity (hydroxyapatite formation and cell response).We demonstrated that crystallized NTs are more corrosion resistant and more bioactive than amorphous ones or even than flat Ti surfaces. More precisely, considering electrochemical, thermal, mechanical, chemical and bioactive aspects, it seems that mixed NTs of about 720 nm in length and 90 nm in diameter constitute an optimal surface for the present applications.Additionally, in the frame of electrochemical investigations, we focused on modeling experimental results from Electrochemical Impedance Spectroscopy (EIS) measurements. The impedance response of TiO2 NTs in physiological conditions can correspond to porous electrode model as developed by De Levie. However, for non-ideal electrodes, this theory can be generalized and modeled by transmission lines. Thus, the transmission line model developed in this study fits very well with experimental measurements. It suggests that TiO2 NTs are almost non-reactive, justifying their applications in biomedical fields.

Ces travaux de thèse portent sur la fabrication de via traversants conducteurs, brique technologique indispensable pour l’intégration des composants microélectroniques en 3 dimensions. Pour ce faire, une voie « tout-électrochimique » a été explorée en raison de son faible coût de fabrication par rapport aux techniques par voie chimique sèche. Ainsi, la gravure de macropores ordonnés traversants a été réalisée par anodisation du silicium en présence d’acide fluorhydrique puis leur remplissage de cuivre par dépôt électrochimique. L’objectif est de faire du silicium macroporeux une alternative crédible à la gravure sèche (DRIE) pour la structuration du silicium.Les conditions de gravure de matrices de macropores ordonnés traversants ont été étudiées à la fois dans des substrats silicium de type n et p faiblement dopés. La composition de l’électrolyte ainsi que le motif des matrices ont été optimisés afin de garantir la gravure de via traversants de forte densité et à facteur de forme élevé. Une fois gravés, les via traversant ont été remplis de cuivre. En optimisant ces paramètres une résistance minimale égale à 32 mΩ/via (soit 1,06 fois la résistivité théorique du cuivre à 20°C) a été mesurée. / These thesis works deal with the achievement of Through Silicon Via (TSV) essential technological issue for microelectronic device 3D integration. For this purpose, we opted for a “full-electrochemical” way of TSV production because of lower fabrication costs as compared to dry etching and deposition techniques. Indeed, ordered through silicon macropores were carried out by silicon anodization in hydrofluoric acid-containing solution and then filled by copper electrochemical deposition. The main objective is to determine if the macroporous silicon arrays can be a viable alternative as Deep Reactive Ion Etching (DRIE).The etching parameters of through silicon macropore arrays were studied both in low-doped n- and p-type silicon. The electrolyte composition as well as the density of the initiation sites was optimized to enable the growth of high aspect ratio, high density through silicon ordered macropores. After silicon anodization, through via were filled with copper. By optimizing the copper deposition parameters (bath composition and applied potential), the resistance per via was measured equal to 32 mΩ (i.e. 1.06 times higher than the theoretical copper bulk resistivity).

Made available in DSpace on 2014-10-09T12:51:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:36Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:51:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:36Z (GMT). No. of bitstreams: 0 / Investiga-se a influência de diferentes tratamentos sobre o sistema alumínio com cobertura de óxido de alumínio. A anodização do alumínio em meio de ácido sulfúrico e meio misto de sulfúrico e fosfórico foi empregada para alterar a resistência à corrosão, a espessura, o grau de cobertura e a microdureza do óxido anódico; e a eletrodeposição de ferro no interior óxido anódico em meio de sulfato com tratamento químico de selagem com cério, para alterar a sua condutividade elétrica e a sua resistência à corrosão. Para a eletrodeposição de ferro aplicou-se corrente contínua e pulsada e diversificou-se a composição do eletrólito de Fe(SO4)2(NH4)2.6H2O, com a adição dos ácidos bórico e ascórbico e para o tratamento de selagem, variou-se a concentração do CeCl3. A espectroscopia de energia dispersiva de raios X (EDS), a fluorescência de raios X (FRX) e a análise morfológica por microscopia eletrônica de varredura (MEV) permitiram verificar que, a corrente pulsada eleva o teor de ferro na camada anódica e a presença dos aditivos inibe a oxidação do ferro. As curvas cronopotenciométricas obtidas durante a eletrodeposição de ferro indicaram que a mistura dos ácidos bórico e ascórbico aumentaram a eficiência do processo de eletrodeposição. A espectroscopia de impedância eletroquímica (EIE), medidas de microdureza Vickers (H) e análise morfológica evidenciaram que o tratamento de selagem melhora a resistência à corrosão do filme óxido modificado com ferro. As medidas de impedância elétrica por duas pontas permitiram comprovar o aumento da condutividade elétrica do alumínio anodizado com ferro, mesmo após o tratamento com baixas concentrações de cério. Nanofios de ferro foram preparados utilizando os poros do óxido anódico como matriz. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Abstract The aim of this thesis is to study whether nanostructured particles of WO3 could be competitive counterparts of traditional, more bulky materials in resistive gas sensor applications. Pristine and various surface decorated derivatives of three different types of WO3 nanoparticles applied on the surface of lithographically defined Si chips were used in the work to analyse the electrical behaviour of thin films when exposed to different gas atmospheres. Nanosized particles of WO3, obtained by capillary force-induced collapse of porous anodic tungsten oxide in water, were demonstrated as a sensing medium for the detection of H2 and NO analytes. Commercially available nanoparticles of WO3 were also studied. After decorating their surface with metal/metal oxide nanoparticles (Ag, PdOx and PtOx), stable aqueous dispersions were made and used for the inkjet printing of conductive patterns on test chips. Surface decoration was found to affect substantially the gas response behaviour of the materials with the largest differences in response to H2 and NO. The third type of tungsten oxide applied consisted of hydrothermally synthesized nanowires that were also surface decorated with PdO as well as with PtOx. The nanowires were suspended in water and drop cast on test chips for gas sensing measurements. The nanowire based devices allowed ultrasensitive detection of H2 even at room temperature. The results summarized in this thesis indicate that resistive gas sensors based on nanostructured tungsten oxides are excellent alternatives to existing devices utilizing porous thick films or bulky thin films. Their high sensitivity, low operating temperature and low electrical power consumption may enable the construction of portable sensors, for example by inkjet printing, thus having great potential for fast prototyping but also for large scale production at low cost. / Tiivistelmä Väitöstyön tavoitteena on tutkia nanorakenteisten WO3 hiukkasten kilpailukykyä suhteessa perinteisiin suuremman kidekoon materiaaleihin resistiivisissä kaasusensorisovelluksissa. Työssä tutkittiin kolmella eri tekniikalla valmistettujen WO3 nanopartikkeleiden alkuperäisistä ja pintakäsitellyistä versioista muodostettujen ohutkalvojen sähköisiä ominaisuuksia erilaisten kaasukehien funktiona. Veden kapillaarivoimien aikaan saaman huokoisen anodisen volframioksidirakenteen romahduksen kautta saatujen WO3 nanopartikkeleiden osoitettiin toimivan havaintoväliaineena H2 ja NO kaasuille. Myös kaupallisia WO3 nanopartikkeleita tutkittiin. Partikkelien pinta päällystettiin metalli- ja metallioksidinanopartikkeleilla (Ag, PdOx and PtOx), jonka jälkeen niistä muodostettiin vakaita vesipohjaisia seoksia johtavien kuvioiden mustesuihkutulostukseen testisubstraateille. Pintakäsittelyn havaittiin vaikuttavan merkittävästi materiaalien kaasuvasteisiin erityisesti H2:n ja NO:n tapauksessa. Kolmannen tyyppinen väitöskirjassa tutkittu volframioksidimateriaali koostuu hydrotermisesti syntetisoiduista nanojohdoista, jotka ovat pintakäsitelty PdO tai PtOx nanopartikkeleilla. Nanojohdot sekoitettiin veteen ja pipetoitiin testisubstraateille kaasumittauksia varten. Tämän tyyppiset kaasusensorit olivat erityisen herkkiä H2 kaasulle jopa huoneenlämmössä. Väistökirjan tulosten mukaan nanorakenteiset volframioksidimateriaalit ovat erinomainen vaihtoehto perinteisille huokoisille paksukalvoille ja suhteellisen paksuille ohutkalvoille kaasusensorisovelluksissa. Niiden suuri herkkyys, alhainen toimintalämpötila ja matala sähkönkulutus voivat mahdollistaa kannettavien kaasusensorien valmistuksen, esimerkiksi mustesuihkuteknologilla, nopeaan testaukseen ja suuren mittakaavan tuotantoon alhaisin kustannuksin.

Surface roughness exists at many length scales-from atomic dimensions to meters. At sub-micron scale, the distribution of roughness is largely dependent on the process that generates the surface through the mechanisms of material removal/addition involved and the process parameters. The focus of the research is to quantitatively characterize the evolution of sub-micron scale surface roughness in the mechanical, chemical and electrochemical material removal techniques and study the influence of roughness on the mechanical behavior of surfaces. High purity aluminum surfaces are subjected to surface dissolution techniques such as electropolishing, chemical etching and anodization. Owing to the lack of sufficient lateral resolution in conventional roughness measurement techniques and appropriate scale independent roughness characterization techniques, the effect sub-micron scale electrochemical inhomogeneities present on the surfaces have on the roughness evolution at various length scales has not been understood. In this work, the power spectral density method of roughness characterization is used to quantitatively evaluate the roughness length scales affected in the surface generation processes as a function of time. Results indicate that in the case of electropolishing, roughness is not uniformly reduced at all length scales. Further, cut-off frequencies are suggested to optimize the electropolishing process. In chemical etching, the nature of roughness produced is found to be dependent on the nature of the starting surface. The nature of surface and sub-surface structures produced in the initial stage of the anodization process, and the transition from a disordered to an ordered structure are studied. In order to study the mechanical behavior of surfaces as a function of surface roughness, a single asperity indentation is modeled using nanoindentation of micropillar produced by focused ion beam machining of aluminum surfaces. Load-displacement curves are constructed to show the transition from a single asperity deformation to bulk deformation as function of indentation depth. Additionally, indentation responses of polymer coated surfaces with varying degree of roughness that were produced by the aforementioned surface generation processes are studied. it is shown how high interface roughness gives rise to high scatter both in loading and unloading portions of the load-displacement curves. Finally, porous alumina surface generated by the anodization process discussed above is indented to simulate a multi-asperity interaction.