In der vorliegenden Arbeit wurde eine neue Klasse von implantierbaren biochemischen Sensoren bezüglich ihrer Sensitivität im physiologisch relevanten pH- (pH 7,4) sowie Glukose-Konzentrationsbereich (2 - 20 mM) entwickelt und untersucht. Die Glukose-sensitiven Hydrogele basieren auf der Bindung von 5-fach-Zuckern an Boronsäuregruppen, die in einem Acrylamid-basierten Hydrogel mit N,N′-Methylenbisacrylamid (BIS) als Vernetzter (AAm/APB/BIS, 80/20/0,75 mol%) verankert sind. Weiterhin konnten pH-sensitive Hydrogele auf Basis von 2-(Dimethylamino)ethyl Methacrylate (DMAEMA), Hydroxypropyl-methacrylat (HPMA) sowie Tetraethyleneglycol dimethacrylate (TEGDMA) als Vernetzter in unterschiedlichen Zusammensetzungen und Geometrien untersucht werden. Die verwendeten Hydrogele wurden hinsichtlich der Diffusionsprozesse sowie ihrer Quellkinetik charakterisiert, um deren Sensitivität, Selektivität, Reproduzierbarkeit und Ansprechzeit gegenüber den physiologischen Parametern (pH, pCO2, Glukose) zu verbessern. Die aufgebauten pCO2-Sensoren zeigten vielversprechende Ansprechzeiten von wenigen Minuten. Die Glukose und pH-Sensoren wiesen im physiologischen Medium (PBS) deutlich höhere Ansprechzeiten von mehreren Stunden auf. Die Kombination von piezoresistiven Drucksensoren mit Stimuli-sensitiven Hydrogelen bietet nicht nur eine große Vielfalt bezüglich der zu detektierenden Analyten, sondern ermöglicht auch miniaturisierte und implantierbare Sensoren für die kontinuierliche Erfassung von physiologischen Parametern. So war die Verkapselung zum Schutz und zugleich zur Gewährleistung der Biokompatibilität und ohne Beeinträchtigung der Funktionalität und Flexibilität der elektronischen Bauteile das Ziel. Dazu wurden die Sensoren mit dem Polymer Parylene C eingehaust, dass zusätzlich eine Polyethylenglykolschicht enthielt. Hierfür wurden Blockcopolymere mittels Ringöffnungspolymerisation synthetisiert, die Polyaminosäuren als Linkermoleküle und PEG zur gezielten Funktionalisierung enthalten. Nach kovalenter Anbindung an die inerte Parylene C-Oberfläche zeigten sich deutlich veränderte Oberflächeneigenschaften und eine verbesserte Zellkompatibilität und Hämokompatibilität. Zudem wurde der sogenannte Tarnkappeneffekt von PEG-Ketten, die sich in der Schicht nach außen ausrichten, festgestellt. Damit wurde Adsorption von Proteinen (Fibronektin, Fibrinogen), die in Entzündungsreaktionen, der Zelladhäsion sowie der Blutgerinnung maßgebend sind, deutlich verringert. / In this work a new class of implantable biochemical sensors with a high sensitivity at physiological pH (pH 7,4) and glucose (2 – 20 mM) ranges were developed and tested. The glucose sensitive hydrogel was made of acrylamide and N,N′-methylene-bis(acrylamide) as a crosslinker (AAm/APB/BIS, 80/20/0,75 mol%). The swelling mechanism was based on the reversible interaction of sugar molecules and the boronic acid groups in the hydrogel. Also a pH sensitive hydrogel made of 2-(dimethylamino) ethyl methacrylate (DMAEMA), hydroxypropyl-methacrylat (HPMA) and the crosslinker tetraethylene glycol dimethacrylate (TEGDMA) with different molar ratios and geometries was characterized. The swelling kinetics as well as the diffusion processes of different hydrogels were studied to advance sensitivity, selectivity, reproducibility and response time with respect to physiological parameters (pH, pCO2, glucose). pCO2 sensors showed promising short response times of about 4 min whereas glucose and pH sensors displayed longer response times of several hours in phosphate-buffered saline solution. The combination of piezoresistive pressure sensors and stimuli-sensitive hydrogels enables a great diversity of detecting analytes as well as miniaturized and implantable sensors for continuous measuring of physiological parameters. However, to implant the sensors an encapsulation strategy is needed that secures the electronics as well as ensures the biocompatibility without loss of functionality and flexibility. For this, the devices were coated with the polymer parylene C and an additional layer of blockcopolymers composed of polyaminoacid (PAA) and polyethyleneglycol (PEG) blocks synthesized via ring-opening polymerization. The functionalization units are carried out by the PEG blocks whereas the PAA blocks perform as linker molecules onto the activated parylene C surface. After covalent coupling of blockcopolymers to the inert polymer the surface characteristics changed and hence the cell and blood compatibility was improved. Furthermore the stealth effect of the outwards PEG chains was utilized to reduce the adsorption of proteins like fibronectin or fibrinogen. These proteins play a major role in inflammatory processes, cell adhesion and blood coagulation. The results gave proof that the encapsulation leads to decisively reduced physiological reactions.

In this report, a novel smart nanocantilever with self-deflection sensor using embedded piezo-resistor and self-actuation using integrated piezo-electric actuator is proposed, designed and simulated to enable highly sensitive label free biosensor and ultra-short cantilever probe for AFM applications. The smart nanocantilever comprises of a triangular Si3N4 nanocantilever (10µm long, 400nm width and 100nm thickness) connected to a multi-layer support structure (Si3N4 (100nm)/PZT (100nm)) having n-type silicon piezo resistor (7µm long ,2µm width and 20nm thickness) embedded in the Si3N4 layer in both the support structure and nanocantilever. The nanocantilever is designed to maximize the resonance frequency and lower spring constant whereas piezoelectric actuator and piezo resistor is designed to maximize excitation and maximize change in resistance of nanocantilever respectively. The results show that the nanocantilever enhances sensitivity in static mode by factor of 36.5 while in dynamic mode by a factor of 658 for AFM application. For biosensor application, the nanocantilever enhanced the sensitivity in static and dynamic mode by factors of 5.6 and 13.8, respectively. / I denna rapport presenteras en ny, smart nano-kantilever med självdetektion via sensorer som använder inbäddade piezoresistorer, och självpådrivning via integrerade piezoelektriska pådrivare. Dessa är designade och simulerade för att möjliggöra högsensitiva titelfria biosensorer och ultrakorta kantilever-prober för AFM-applikation. Den smarta nano-kantilevern består av en triangulär Si3N4 nano-kantilever (10µm lång, 400nm bred and 100nm djup) kopplad till en stödstruktur med flera lager (Si3N4 (100nm)/PZT (100nm)) och med en n-typ silikon piezoresistor (7µm lång ,2µm bred and 20nm djup) inbäddad i Si3N4 – lagret i både stödstrukturen och i nano-kantilevern. Denna är designad för att maximera resonansfrekvens och sänka fjädringskonstanten, medan den piezo-elektriska pådrivaren och piezo-resistorn är designade för att maximera excitering samt resistansändring för nano-kantilevern. Resultatet i denna rapport visar att nano-kantilevern förstärker känslighet i statiskt läge med en faktor på 36,5, med motsvarande faktor på 658 i dynamiskt läge för AMF- applikation. För biosenor-applikation förstärkte nano-kantilevern känsligheten i statiskt och dynamiskt läge med 5,6 och 13,8 respektive.

O objetivo deste estudo foi o desenvolvimento de compósitos poliméricos flexíveis e altamente condutores elétricos preparados por moldagem por compressão e por fabricação de filamentos fundidos (FFF) para possíveis aplicações como materiais piezoresistivos ou piezoelétricos para sensores de compressão. Compósitos baseados em misturas de poli(fluoreto de vinilideno)/poliuretano termoplástico (PVDF/TPU) como matriz e contendo várias frações de negro de fumo-polipirrol (CB-PPy) como aditivo condutor foram preparados. Diversas técnicas de caracterização foram realizadas para avaliar as propriedades mecânicas, térmicas, químicas e elétricas, morfologia e printabilidade dos materiais investigados. Primeiro, blendas de PVDF/TPU com diferentes composições foram produzidas por mistura por fusão seguida de moldagem por compressão. Os resultados mostraram que a flexibilidade desejada para os materiais foi melhorada com a adição de TPU aos compósitos de PVDF. As imagens SEM evidenciaram a obtenção de uma blenda co-contínua com 50/50 vol% de PVDF/TPU. As blendas compostas de PVDF/TPU 38/62 vol% e a blenda co-contínua de PVDF/TPU 50/50 vol% foram selecionadas como matrizes para a preparação de compósitos moldados por compressão e impressos em 3D a fim de alcançar uma ótima combinação entre condutividade, propriedades mecânicas e printabilidade. Várias quantidades de negro de fumo-polipirrol, de 0 a 15%, foram adicionadas às blendas selecionadas para aumentar a condutividade elétrica dos compósitos e possivelmente atuar como agente nucleante para a fase cristalina do PVDF a fim de aumentar sua resposta piezoelétrica. A adição de CB-PPy aumentou a condutividade elétrica de todos os compósitos. No entanto, a condutividade elétrica dos compósitos baseados em blendas co-contínuas PVDF/TPU 50/50 vol% foi maior do que as encontradas para os compósitos de PVDF/TPU 38/62 vol% com mesma concentração de aditivo. De fato, o limiar de percolação elétrico dos compósitos com blenda co-contínua foi de 2%, enquanto o limiar de percolação elétrico dos compósitos compostos da blenda não contínua foi de 5%. Com relação às propriedades mecânicas, a incorporação do aditivo condutor nas blendas resultou em materiais mais rígidos com maior módulo de elasticidade, menor alongamento na ruptura e maior módulo de armazenamento. O módulo de armazenamento (G') e a viscosidade complexa (η*) dos compósitos aumentaram com a adição de CB-PPy. O limiar de percolação reológico foi de 3% para PVDF/TPU/CB-PPy 38/62 vol% e 1% para PVDF/TPU/CB-PPy 50/50 vol%, indicando que uma quantidade maior de carga poderia comprometer a processabilidade dos compósitos. A adição de CB-PPy também resultou na redução dos valores de Tg e Tm dos compósitos devido à redução da mobilidade das cadeias poliméricas. Com base na condutividade elétrica e no comportamento mecânico dos compósitos, três composições diferentes foram selecionadas para a extrusão de filamentos para serem posteriormente utilizados no processo de impressão 3D. No geral, as peças impressas em 3D apresentaram propriedades mecânicas e elétricas inferiores devido à presença de vazios, defeitos e camadas sobrepostas que podem dificultar o fluxo de elétrons. Os valores de condutividade elétrica dos compósitos impressos em 3D de PVDF/TPU/CB-PPy 38/62 vol% contendo 5% e 6% de CB-PPy são de uma a sete ordens de grandeza menores do que os encontrados para os compósitos com a mesma composição moldados por compressão. Mesmo que o valor da condutividade elétrica para o compósito PVDF/TPU 38/62 vol% com 6% de CB-PPy moldado por compressão foi de 1,94x10-1 S•m-1, o compósito impresso em 3D com a mesma composição mostrou um valor muito baixo de condutividade elétrica de 6,01x10-8 S•m-1. Por outro lado, o compósito co-contínuo de PVDF/TPU 50/50 vol% com 10% de aditivo impresso em 3D apresentou um alto valor de condutividade elétrica de 4,14×100 S•m-1 mesmo após o processo de impressão. Além disso, as respostas piezoresistivas dos compósitos foram investigadas. Para os compósitos PVDF/TPU/CB-PPy 38/62 vol%, as amostras moldadas por compressão e impressas em 3D com 5% e 6% de CB-PPy exibiram boa resposta piezoresistiva. No entanto, apenas os compósitos com 6% de aditivo apresentaram valores elevados de sensibilidade e gauge factor, atuação em ampla faixa de pressão e respostas piezoresistivas reprodutíveis durante a aplicação de 100 ciclos de compressão/descompressão para ambos os métodos de fabricação. Por outro lado, para os compósitos co-contínuos de PVDF/TPU/CB-PPy apenas a amostra moldada por compressão com 5% de CB-PPy apresentou respostas piezorresistivas boas e reprodutíveis. A cristalinidade e o teor de fase β do PVDF foram investigados para os compósitos. Embora o grau de cristalinidade das amostras tenha diminuído com a adição de CB-PPy, a porcentagem de fase β no PVDF aumentou. O coeficiente piezoelétrico d33 das amostras aumentou com a porcentagem de fase β. A adição de 6% ou mais de CB-PPy foi necessária para aumentar significativamente o coeficiente piezoelétrico (d33) dos compósitos. O conteúdo de fase β e as respostas piezoelétricas do PVDF foram menores para as amostras preparadas por FFF. Por fim, como pesquisa colateral, a eficiência de blindagem contra interferência eletromagnética (EMI-SE) foi medida para todos os compósitos. Compósitos com maior condutividade elétrica apresentaram melhor blindagem da radiação eletromagnética. Além disso, os compósitos baseados na blenda co-contínua apresentaram maior eficiência de blindagem contra EMI do que os compósitos de PVDF/TPU 38/62 vol%. O principal mecanismo de blindagem foi a absorção para todos os compósitos. As amostras preparadas por FFF apresentaram respostas de EMI-SE menores quando comparadas às amostras moldadas por compressão. / The aim of this study was the development of flexible and highly electrically conductive polymer composites via compression molding and fused filament fabrication for possible applications as piezoresistive or piezoelectric materials for pressure sensors. Composites based on blends of poly(vinylidene fluoride)/thermoplastic polyurethane (PVDF/TPU) as matrix and containing various fractions of carbon black-polypyrrole (CB-PPy) as conductive filler were prepared. Several characterization techniques were performed in order to evaluate the mechanical, thermal, chemical and electrical properties, morphology and printability of the investigated materials. First, PVDF/TPU blends with different compositions were prepared by melt compounding followed by compression molding. The results showed that the flexibility aimed for the final materials was improved with the addition of TPU to PVDF composites. SEM images evidenced the achievement of a co-continuous blend comprising 50/50 vol% of PVDF/TPU. The blends composed of PVDF/TPU 38/62 vol% and the co-continuous blend of PVDF/TPU 50/50 vol% were selected as matrices for the preparation of compression molded and 3D printed composites in order to achieve an optimal compromise between electrical conductivity, mechanical properties and printability. Various amounts of carbon black-polypyrrole, from 0 up to 15%, were added to the selected blends in order to rise the electrical conductivity of the composites and to possible act as nucleating filler for the β crystalline phase of PVDF in order to increase its piezoelectric response. The addition of CB-PPy increased the electrical conductivity of all composites. However, the electrical conductivity of composites based on PVDF/TPU 50/50 vol% co-continuous blends was higher than those found for PVDF/TPU 38/62 vol% composites at the same filler content. Indeed, the electrical percolation threshold of the conductive co-continuous composite blends was 2%, while the electrical percolation threshold of the composites with the nonco-continuous composite blends was 5%. With respect to the mechanical properties, the incorporation of the filler into the blends leaded to more rigid materials with higher elastic modulus, lower elongation at break and higher storage modulus. The storage modulus (G’) and complex viscosity (η*) of the composites increased with the addition of CB-PPy. The rheological percolation threshold was found to be 3% for PVDF/TPU/CB-PPy 38/62 vol% and 1% for PVDF/TPU/CB-PPy 50/50 vol%, indicating that higher amount of filler could compromise the processability of the composites. The addition of CB-PPy also resulted in a reduction on the Tg and Tm values of the composites due to the reduction of the mobility of the polymeric chains. Based on the electrical conductivity and mechanical behavior of the composites, three different compositions were selected for the extrusion of filaments to be used in a 3D printing process. Overall, the 3D printed parts presented lower mechanical and electrical properties because of the presence of voids, defects and overlapping layers that can hinder the flow of electrons. The electrical conductivity values of PVDF/TPU/CB-PPy 38/62 vol% composites containing 5% and 6 wt% of CB-PPy 3D printed samples are one to seven orders of magnitude lower than those found for compression molded composites with the same composition. Even if the electrical conductivity value for PVDF/TPU 38/62 vol% compression molded composite with 6% of CB-PPy was as high as 1.94x10-1 S•m-1, the 3D printed composite with same composition showed a very low electrical conductivity of 6.01x10-8 S•m-1. On the other hand, the 3D printed co-continuous composite PVDF/TPU 50/50 vol% with 10% of filler displayed a high value of electrical conductivity of 4.14×100 S•m-1 even after the printing process. Moreover, the piezoresistive responses of the composites were investigated. For PVDF/TPU/CB-PPy 38/62 vol% composites, the compression molded and 3D printed samples with 5% and 6% of CB-PPy exhibited good piezoresistive response. However, only the composites with 6% displayed high sensitivity and gauge factor values, large pressure range and reproducible piezoresistive responses under 100 cycles for both methods. On the other hand, for PVDF/TPU/CB-PPy co-continuous composites only the compression molded sample with 5% of CB-PPy presented good and reproducible piezoresistive responses. The crystallinity and β phase content of PVDF were investigated for the composites. Althought the degree of crystallinity of the samples decreased with the addition of CB-PPy, the percentage of β phase in PVDF was increased. The piezoelectric coefficient d33 of the samples increased with the percentage of β phase. The addition of 6% or more of CB-PPy was necessary to increase significatively the piezoelectric coefficient (d33) of the composites. The β phase content and piezoelectric responses of PVDF were lower for samples prepared by FFF. Finally, as a collateral research, the electromagnetic interference shielding effectiveness (EMI-SE) were measured for all composites. Composites with higher electrical conductivity showed better shielding of the electromagnetic radiation. In addition, composites based on the co-continuous blend displayed higher EMI shielding efficiency than 38/62 vol% composites. The main mechanism of shielding was absorption for all composites. Specimens prepared by FFF displayed diminished EMI-SE responses when compared to compression molded samples. / Lo scopo di questo studio è lo sviluppo di compositi polimerici flessibili e ad elevata conducibilità elettrica tramite stampaggio a compressione e manifattura additiva (fused filament fabrication) per possibili applicazioni come materiali piezoresistivi o piezoelettrici in sensori di pressione. In particolare, sono stati preparati compositi a base di miscele di poli(vinilidene fluoruro)/poliuretano termoplastico (PVDF/TPU) come matrice e contenenti varie frazioni di nerofumo-polipirrolo (CB-PPy) come riempitivo conduttivo. Sono state utilizzate diverse tecniche di caratterizzazione al fine di valutare le proprietà meccaniche, termiche, chimiche ed elettriche, la morfologia e la stampabilità dei materiali ottenuti. In primo luogo, miscele PVDF/TPU con diverse composizioni sono state preparate mediante mescolatura allo stato fuso seguita da stampaggio a compressione. I risultati hanno mostrato che la flessibilità del PVDF viene notevolemente migliorata dall’aggiunta di TPU. Le immagini SEM hanno evidenziato il raggiungimento di una miscela co-continua per una composizione 50/50% in volume di PVDF/TPU. Le miscele composte da PVDF/TPU 38/62 vol% e la miscela co-continua di PVDF/TPU 50/50 vol% sono state selezionate come matrici per la preparazione di compositi per stampaggio a compressione e manifattura additiva al fine di ottenere un compromesso ottimale tra conducibilità, proprietà meccaniche e stampabilità. Alle miscele selezionate sono state aggiunte varie quantità di nerofumo-polipirrolo, dallo 0 al 15%, per aumentare la conducibilità elettrica dei compositi ed eventualmente fungere da additivo nucleante per la fase β cristallina del PVDF al fine di aumentarne la risposta piezoelettrica. L'aggiunta di CB-PPy ha aumentato la conduttività elettrica di tutti i compositi. Tuttavia, la conduttività elettrica dei compositi basati su miscele co-continue di PVDF/TPU 50/50% in volume era superiore a quella trovata per compositi PVDF/TPU 38/62% in volume con lo stesso contenuto di riempitivo. Infatti, la soglia di percolazione elettrica delle miscele conduttive era del 2%, mentre la soglia di percolazione elettrica dei compositi con miscele composite non continue era del 5%. Per quanto riguarda le proprietà meccaniche, l'incorporazione del riempitivo nelle mescole ha portato a materiali più rigidi con modulo elastico più elevato, allungamento a rottura inferiore e modulo conservativo più elevato. Il modulo conservativo (G') e la viscosità complessa (η*) dei compositi sono aumentate con l'aggiunta di CB-PPy. La soglia di percolazione reologica è risultata essere del 3% per PVDF/TPU/CB-PPy 38/62 vol% e dell'1% per PVDF/TPU/CB-PPy 50/50 vol%, indicando che una maggiore quantità di riempitivo potrebbe compromettere la processabilità dei compositi. L'aggiunta di CB-PPy ha comportato anche una riduzione dei valori di Tg e Tm dei compositi a causa della riduzione della mobilità delle catene polimeriche. Sulla base della conduttività elettrica e del comportamento meccanico dei compositi, sono state selezionate tre diverse composizioni per l'estrusione di filamenti da utilizzare in un processo di stampa 3D. Nel complesso, le parti stampate in 3D presentavano proprietà meccaniche ed elettriche inferiori a causa della presenza di vuoti, difetti e strati sovrapposti che possono ostacolare il flusso di elettroni. I valori di conducibilità elettrica dei compositi PVDF/TPU/CB-PPy 38/62 vol% contenenti il 5% e il 6% di CB-PPy di campioni stampati in 3D sono da uno a sette ordini di grandezza inferiori a quelli trovati per i compositi stampati a compressione con la stessa composizione. Anche se il valore di conducibilità elettrica per il composito stampato a compressione PVDF/TPU 38/62 vol% con il 6% di CB-PPy era pari a 1,94x10-1 S•m-1, il composito stampato in 3D con la stessa composizione ha mostrato un valore molto basso di conducibilità elettrica, pari a 6,01x10-8 S•m-1. D'altra parte, il composito PVDF/TPU 50/50 vol% stampato in 3D con il 10% di riempitivo ha mostrato un elevato valore di conducibilità elettrica, pari a 4,14 × 100 S•m-1, anche dopo il processo di stampa. Inoltre, sono state studiate le risposte piezoresistive dei compositi. Per i compositi PVDF/TPU/CB-PPy 38/62 vol%, i campioni stampati a compressione e stampati in 3D con il 5% e il 6% di CB-PPy hanno mostrato una buona risposta piezoresistiva. Tuttavia, solo i compositi con il 6% hanno mostrato valori di sensibilità e gauge factor elevati, ampio intervallo di pressione e risposte piezoresistive riproducibili in 100 cicli per entrambi i metodi. D'altra parte, per i compositi co-continui PVDF/TPU/CB-PPy solo il campione stampato a compressione con il 5% di CB-PPy ha presentato risposte piezoresistive adeguate e riproducibili. La cristallinità e il contenuto di fase β del PVDF sono stati studiati per i compositi. Sebbene il grado di cristallinità dei campioni diminuisca con l'aggiunta di CB-PPy, la percentuale di fase β in PVDF risulta aumentata. Il coefficiente piezoelettrico d33 dei campioni aumenta anch’esso con la percentuale di fase β. L'aggiunta del 6% o più di CB-PPy è stata necessaria per aumentare significativamente il coefficiente piezoelettrico (d33) dei compositi. Il contenuto di fase β e le risposte piezoelettriche del PVDF sono inferiori per i campioni ottenuti mediante stampa 3D. Infine, come ricerca collaterale, è stata misurata l'efficacia della schermatura contro le interferenze elettromagnetiche (EMI-SE) per tutti i compositi. I compositi con una maggiore conduttività elettrica hanno mostrato una migliore schermatura della radiazione elettromagnetica. Inoltre, i compositi basati sulla miscela co-continua hanno mostrato un'efficienza di schermatura EMI maggiore rispetto ai compositi a 38/62% in volume. Per tutti i compositi, il principale meccanismo di schermatura è l'assorbimento. I campioni preparati mediante manifattura additiva hanno mostrato risposte EMI-SE inferiori rispetto ai campioni stampati a compressione.

Les microphones à électret dédiés à l'électronique grand public et les applications médicales (les audioprothèses) ont atteint les limites de la miniaturisation. Depuis la sortie du premier microphone basé sur une technologie microsystème sur silicium (MEMS: Micro-Electro-Mechanical Systems), les microphones à électret sont progressivement remplacés par les microphones MEMS. Les MEMS utilisent le silicium car il offre des caractéristiques mécaniques exceptionnelles avec de bonnes propriétés électriques et la technologie de fabrication est maintenant bien maîtrisée. La plupart des microphones MEMS qui sont décrits dans la littérature sont constitués d’une membrane qui vibre en dehors du plan du capteur, et utilisent la transduction capacitive. La miniaturisation de tels microphones est limitée car leur sensibilité est liée à la valeur de la capacité qui dépend de la taille de la membrane. En outre, les capteurs capacitifs sont très sensibles aux capacités parasites et aux non-linéarités. Cette thèse présente une nouvelle architecture de microphone MEMS qui utilise des micro-poutres qui vibrent dans le plan capteur. La transduction du signal est réalisée par des nanojauges piézorésistives intégrées dans le microsystème et attachées aux micro-poutres. Ce système de détection original ne présente pas les inconvénients de la détection capacitive et à la différence des piézorésistors classiques intégrés dans la membrane de silicium, les nanofils suspendus permettent d’éliminer les courants de fuite. De plus, l'amélioration de la détection est possible puisque le coefficient piézo-résistif longitudinal est inversement proportionnel à la section du nanofil. Les fluctuations de pression acoustique entraînent les déviations des micro-poutres qui produisent une concentration de contraintes dans les nanogauges. Le comportement du capteur, que l’on cherche à modéliser, est lié à des phénomènes mécaniques, acoustiques et électriques qui sont couplés. En raison des dimensions micrométriques du MEMS, les effets des dissipations thermique et visqueuse doivent être pris en compte dans le comportement acoustique. Pour prédire de façon fiable le comportement du capteur, deux modèles vibroacoustiques sont utilisés: un modèle éléments finis basé sur l'ensemble des équations de Navier-Stokes linéarisées et un modèle approché basé sur un schéma à constantes localisées (représentation par circuit électrique équivalent). Les deux modèles sont complémentaires dans le processus de conception pour déterminer la réponse en fréquence et le taux de bruit du capteur. Le travail est complété par la description des processus technologiques et les défis liés à la fabrication du prototype. Puis deux approches pour la caractérisation fonctionnelle du microphone MEMS sont présentées, la première en tube d’impédance, la seconde en champ libre. / Electret microphones dedicated to consumer electronics and medical applications (hearing aids) have reached the miniaturization limits. Since the release of the first microphone based on Silicon micromachining, electret microphones are constantly replaced by MEMS microphones. MEMS (Micro-Electro-Mechanical Systems) microphones use Silicon that provides exceptional mechanical characteristics along with good electric properties and mature fabrication technology. Regardless of the transduction principle (capacitive, piezoresistive, piezoelectric, optical), all of the MEMS microphones reported in the state of the art literature are based on a membrane deflecting out of the plane of the base wafer. Most of the reported microphones and all of the commercially available MEMS use capacitive transduction. Downscaling of capacitive microphones is problematic, since the sensitivity depends on capacitance value. Moreover capacitive sensors suffer of high sensitivity to parasitic capacitance and nonlinearity. The drawbacks of capacitive detection may be overcome with use of piezoresistive properties of Silicon nanowires. Unlike the classical piezoresistors integrated into silicon membrane, suspended nanowires do not suffer of leakage current. Further improvement of piezoresistive detection is possible since the longitudinal piezoresistive coefficient rises inversely proportional to nanowire section. This thesis presents the considerations of novel MEMS microphone architecture that uses microbeams which deflect in the plane of the base wafer. Signal transduction is achieved by piezoresistive nanogauges integrated in the microsystem and attached to the microbeams. Acoustic pressure fluctuations lead to the deflection of the microbeams which produces a stress concentration in the nanogauges. Accurate simulations of the discussed transducer couple acoustic, mechanical and electric behavior of the system. Due to micrometric dimensions of the MEMS acoustic system, thermal and viscous dissipative effects have to be taken into account. To reliably predict the sensor behavior two acoustic models are prepared: the complete Finite Element Model based on the full set of linearized Navier-Stokes equations and the approximative model based on the Lumped Elements (Equivalent Cirtuit Representation). Both models are complementary in the design process to finally retrieve the frequency response and the noise budget of the sensor. The work is completed by the description of the technological process and the challenges related to the prototype microfabrication. Then the approach to the MEMS microphone characterization in pressure-field and free-field is presented.

Este projeto de pesquisa apresenta o desenvolvimento de protótipos de transmissores industriais de pressão do tipo diferencial piezoresistivo com saída analógica a dois fios 4-20 mA. Os dispositivos usam um DSSP (processador digital de sinal do sensor) para realizar compensação térmica nas temperaturas de 0°C até 80°C e a calibração de pressão diferencial na faixa de 0-25 bard e de pressão de linha de 0-7 barg. Os transmissores permitem a leitura de diversas variáveis industriais: pressão diferencial, pressão relativa e pressão absoluta em fluidos. Os transmissores têm um TEB (total error band) menor que 0,15 de porcentagem de escala plena. A saída analógica dos transmissores diferenciais de pressão é caracterizada utilizando como base normas internacionais BS (British Standards). Os parâmetros avaliados nos transmissores de pressão são: a exatidão, o coeficiente térmico do offset, o coeficiente térmico do span, o total error band, e os desvios no tempo a curto e longo prazo. Esse trabalho é resultado da parceria dada entre o Laboratório de Sistemas Integráveis da Escola Politécnica da Universidade de São Paulo (LSI/EPUSP) e a empresa MEMS Microssistemas Integrados Híbridos de Pressão. / This research project presents the prototypes development of piezoresistive differential pressure transmitters with analog two-wire output of 4-20 mA. The devices use a DSSP (Digital Signal Processor Sensor) to achieve temperature compensation at temperatures from 0°C to 80°C and differential pressure calibration range from 0 bard to 25 bard and line pressure range from 0 barg to 7 barg. The transmitters measure several industrial variables: differential pressure, relative pressure and absolute pressure at fluids. The transmitters have a TEB (total error band) less than 0.15 percent of full scale. The analog output of the differential pressure transmitters is characterized using British Standards-BS. The parameters evaluated in the pressure transmitters are: the accuracy, the thermal coefficient of the offset, the thermal coefficient of the span, the total error band, the start-up drift and long-term drift. This work is the result of the academic and technological partnership between the Laboratory of Integrated Systems of the Polytechnic School of the University of São Paulo (LSI / EPUSP) and the MEMS company - Microssistemas Integrados Híbridos de Pressão Ltda.

Este projeto de pesquisa apresenta o desenvolvimento de protótipos de transmissores industriais de pressão do tipo diferencial piezoresistivo com saída analógica a dois fios 4-20 mA. Os dispositivos usam um DSSP (processador digital de sinal do sensor) para realizar compensação térmica nas temperaturas de 0°C até 80°C e a calibração de pressão diferencial na faixa de 0-25 bard e de pressão de linha de 0-7 barg. Os transmissores permitem a leitura de diversas variáveis industriais: pressão diferencial, pressão relativa e pressão absoluta em fluidos. Os transmissores têm um TEB (total error band) menor que 0,15 de porcentagem de escala plena. A saída analógica dos transmissores diferenciais de pressão é caracterizada utilizando como base normas internacionais BS (British Standards). Os parâmetros avaliados nos transmissores de pressão são: a exatidão, o coeficiente térmico do offset, o coeficiente térmico do span, o total error band, e os desvios no tempo a curto e longo prazo. Esse trabalho é resultado da parceria dada entre o Laboratório de Sistemas Integráveis da Escola Politécnica da Universidade de São Paulo (LSI/EPUSP) e a empresa MEMS Microssistemas Integrados Híbridos de Pressão. / This research project presents the prototypes development of piezoresistive differential pressure transmitters with analog two-wire output of 4-20 mA. The devices use a DSSP (Digital Signal Processor Sensor) to achieve temperature compensation at temperatures from 0°C to 80°C and differential pressure calibration range from 0 bard to 25 bard and line pressure range from 0 barg to 7 barg. The transmitters measure several industrial variables: differential pressure, relative pressure and absolute pressure at fluids. The transmitters have a TEB (total error band) less than 0.15 percent of full scale. The analog output of the differential pressure transmitters is characterized using British Standards-BS. The parameters evaluated in the pressure transmitters are: the accuracy, the thermal coefficient of the offset, the thermal coefficient of the span, the total error band, the start-up drift and long-term drift. This work is the result of the academic and technological partnership between the Laboratory of Integrated Systems of the Polytechnic School of the University of São Paulo (LSI / EPUSP) and the MEMS company - Microssistemas Integrados Híbridos de Pressão Ltda.

Ziel dieser Arbeit ist die Entwicklung selektiver Si1-xCx-Prozesse, die eine mechanische Zugspannung im Kanal von NMOS-Transistoren erzeugen, und so durch eine gezielte Änderung der Bandstruktur die Elektronenbeweglichkeit und damit auch die Leistungsfähigkeit der Bauteile erhöhen soll. In der vorliegenden Arbeit werden die wichtigsten Fragestellungen zum Wachstum der Si1-xCx-Schichten näher beleuchtet. Dabei werden zwei Methoden zum Wachstum der Schichten charakterisiert. Neben einem disilanbasierten UHV-CVD-Verfahren wird ein LP-CVD-Verfahren unter der Verwendung von Trisilan herangezogen. Für beide Prozessvarianten konnten mithilfe einer zyklischen Prozessführung selektive, undotierte und in-situ phosphordotierte Abscheidungen realisiert werden. Es wird gezeigt, dass die Disilanprozesse aufgrund ihrer geringen Wachstumsraten einen hohen Anteil interstitiellen Kohlenstoffs bedingen. Durch FT-IR-Analyse konnte belegt werden, dass sich während des Wachstums Siliziumkarbid-präzipitate bilden, die das epitaktische Wachstum nachhaltig schädigen können. Erweiterte man das Wachstum infolge der Zugabe von German zum ternären System Si1-x-yCxGey (y=0,05…0,07) wurde ein starker Anstieg der Wachstumsraten festgestellt. Die Aktivierungsenergie für das epitaktische Wachstum sinkt durch die Zugabe von German und der substitutionelle Kohlenstoffgehalt kann erhöht werden. Es wird gezeigt, dass German nicht nur für die Unterstützung des Ätzprozesses hilfreich ist, sondern im LP-CVD-Verfahren zur Unterstützung des HCl-basierten Ätzprozesses dienen kann. Ein weiterer Schwerpunkt der Arbeit liegt in der Abscheidung und Charakterisierung in-situ phosphor-dotierter Schichten. Es wird nachgewiesen, dass Phosphor die Wachstumsrate erhöht und dass Phosphor und Kohlenstoff in Konkurrenz um substitutionelle Gitterplätze stehen. Phosphor ist außerdem auch die Spezies, für die die größte Anisotropie hinsichtlich des Einbaus auf Si(110) im Vergleich zu Si(001) beobachtet wurde: Je nach Prozessführung wird auf Si(110)-Ebenen nahezu doppelt so viel Phosphor eingebaut wie auf Si(001). Dieser Effekt ist insofern von großer Relevanz, als dass ein steigender Phosphoranteil auch die thermische Stabilität der Schichten herabsetzt. Die Relaxationsvorgänge basieren bei Si1-xCx-Schichten auf Platzwechselvorgängen substitutioneller Kohlenstoffatome zu interstitiellen Silizium-Kohlenstoff-Hanteldefekten unter der Bildung einer Leerstelle. Es wurde ein Modell vorgeschlagen, nach dem Phosphor durch die Entstehung von PV-Komplexen diese Reaktion begünstigt, wodurch die Relaxationsvorgänge beschleunigt werden. Infolge einer dreidimensionalen Atomsondenanalyse kann der Endzustand der Relaxation – die Bildung stöchiometrischen Siliziumkarbids – belegt werden. In-situ phosphordotierte Si1-xCx-Schichten mit ca. 4*1020 at/cm³ Phosphorgehalt und 1,8 at.% Kohlenstoff wurden erfolgreich in NMOS-Transistoren der 45 nm Generation integriert und mit ebenfalls im Rahmen der Dissertation entwickelten Si:P-Rezepten verglichen. Die höchste Leistungssteigerung von 10 % konnte durch die Kombination aus beiden Prozessen erzielt werden, bei dem auf die spannungserzeugende Si1-xCx-Schicht zur Senkung des Silizidwiderstandes eine Si:P-Kappe aufgebracht wird. Die Einprägung einer Zugspannung in den Transistorkanal wurde mittels Nano beam diffraction nachgewiesen und wurde auf Basis des piezoresistiven Modells mit SiGe-PMOS-Transistoren verglichen.

Silicon magnetic sensors based on the Hall effect have proven to be an excellent sensor choice for many applications, such as position sensing, gear-tooth sensing, contact-less switching and linear sensing. Although a sensor can be trimmed over temperature before it is shipped to the customer, little can be done about the sensitivity's stability once the sensor has been installed in its final application. The goal of this project is to propose and implement mechanisms to stabilize the Hall sensor's sensitivity through the use of mechanical stress feedback and magnetic feedback.

Dans le cadre de ce travail de thèse nous nous sommes intéressés à deux pathologies fémoro-acétabulaires dont la pathogénie semble liée aux « conditions biomécaniques » locales. La première partie de cette thèse était consacrée à l’analyse de l’influence de l’anatomie osseuse sur l’apparition de l’ostéonécrose aseptique de la tête fémorale. Nous avons réalisé des analyses analytique de l’anatomie des patients souffrant d’ONA (notre hypothèse était que nous retrouverions un profil anatomique particulier chez les patients souffrant d’ONA par rapport à la population générale.Nos résultats démontrent que les patients souffrant d’ONA présentent fréquemment une anatomie particulière. Notre modèle en éléments finis de la hanche de dix patients souffrant d’ONAi, a permis de valider notre hypothèse puisqu’il existe un recouvrement quasi-parfait, entre la zone de nécrose osseuse et celle supportant les contraintes fémoro-acétabulaires. L’hypothèse selon laquelle une pathogénie mécanique puisse être responsable du développement l’ostéonécrose aseptique de la tête fémorale est vérifiée par nos travaux.Dans la seconde partie de cette thèse nous avons décrit le rôle mécanique du LA par une évaluation multimodale combinant analyse cinématique,de contraintes fémoro-labrales et enfin analyse en éléments finis. Les résultats de ces études ont permis de constater que le LA se déforme lors du mouvement reflétant une transmission de contraintes fémoro-labrales lors du mouvement d’abduction. Ces contraintes ont pu être enregistrées à l’aide de capteurs piezo-resistifs, elles augmentent lors du mouvement d’abduction. Ces éléments ont été confirmés par notre modèle en éléments finis. / As parts of this thesis we focused on two femoro-acetabular diseases whose pathogenesis appears to be related to "biomechanical local conditions". The first part of this thesis was devoted to analyze the influence of bony anatomy on the development of aseptic osteonecrosis of the femoral head. We thus aimed to analyze ONA patients’ anatomy in a matched-controlled fashioned study. Our results demonstrate that patients with ONA often present a particular anatomy. A finite element model of ten iONA hips validated our hypothesis since we found an overlap between bone necrosis area and femoro-acetabular strains bearing area. The assumption that a mechanical pathogenesis may be responsible for ONA development has been confirmed by our results.If the relationship between bony anatomy and bone disease is quite intuitive, acetabular labrum involvement (AL) in the regulation of femoro-acetabular mechanical conditions is unclear. The mechanical role of the AL is widely controversial, though some authors attributed, AL, a key role in hip joint’s mechanics, others advocated its complete resection in case of painful traumatic tears. We tried to demonstrate AL’s mechanical role in a multimodal analysis combining kinematic, strains and finite element analysis. The AL deforms during abduction movement reflecting femoro-labral strains’ transmission. Those strains have been recorded using piezo-resistive sensors, they increase during adduction to abduction movement. These elements were confirmed by our finite element model: labral resection changed the Femoro-acetabular strains to the detriment of cartilage surfaces.

Cette thèse porte sur l'étude de la durée de vie de composants et modules de puissance dans des environnements thermiques sévères, lorsque les modules de puissance sont amenés à travailler à haute température ou sous des cycles de température de forte amplitude. Les domaines visés par cette étude concernent plus particulièrement des applications extrêmement contraignantes telles que les applications aéronautiques. Un module de puissance est un assemblage de plusieurs matériaux (semi-conducteurs, brasures, céramiques, conducteurs) présentant des propriétés mécaniques, notamment de coefficient de dilatation thermiques (CTE) différentes. Les pertes dans les puces actives et les variations de température ambiante (profils de mission) sont responsables de contraintes mécaniques liées aux différences de CTE entre les différents matériaux. Les modes de défaillance étant principalement d'origine mécanique, ces travaux ont été effectués entre le SATIE et le LMT (Institut Farman). L'étude mécanique a complété des travaux expérimentaux de caractérisation et de vieillissement accéléré de modules de puissance à semi-conducteur. Ces études ont nécessité la mise en place d'essais de vieillissement spécifiques, passifs (utilisation d'une étuve permettant de contraindre les assemblages de puissance sous des cycles thermiques de grande amplitude) et actifs (utilisation de régimes extrêmes de fonctionnement tels que le court-circuit pour accélérer le vieillissement de certaines parties de l'assemblage).La première partie de ce manuscrit présente les principes physiques mis en jeu. Nous présenterons succinctement les concepts de mécanique de la rupture ainsi que les couplages physiques.La deuxième partie porte sur la rupture de la céramique des substrats DCB. Cette rupture peut provenir de défauts répartis aléatoirement dans le matériau. Nous aborderons le problème par une approche statistique où nous introduirons la "Théorie du maillon faible". L'autre cause de rupture est la présence de défauts géométriques que l'on appelle singularité où il existe une concentration des contraintes nécessitant une approche déterministe. A cette occasion nous introduirons le facteur d'intensité des contraintes qui permet d'étudier les problèmes de rupture liés à des zones singulières.La dernière partie portera sur la dégradation de la métallisation du transistor. La recherche d'indicateurs de vieillissement a demandé la mise au point de différents bancs de caractérisation électrique pour la mesure fine de différentes grandeurs électriques (courants de fuite, tensions de seuil, chute de tension à l'état passant...) dans un environnement thermique contrôlé. De plus ces caractérisations électriques sont corrélées à des observations de la métallisation effectuées par un microscope électronique à balayage de manière régulière. Nous chercherons à montrer comment la modification de la morphologie de la métallisation peut modifier les caractéristiques électriques des transistors de puissance testés. / This PhD focuses on the study of the lifetime of components and power semiconductor modules under thermal constraints, when power devices are used at high temperature or under high temperature cycles. The areas covered by this study relate more particularly to extremely harsh applications such as aerospace constraints. A power device is an assembly of different materials (semiconductors, solders, ceramics, conductors) with mechanical properties, including coefficient of thermal expansion (CTE). Losses in the die and ambient temperature variations (mission pro les) are responsible for strain constraints at material interfaces due to CTE mismatch between the different materials. Failure modes result for mechanical constraints so study was done in collaboration between LMT and SATIE laboratories (Farman Institute). The mechanical study completed experimental characterizations and accelerated aging of power semiconductor modules. These studies involved the development of specific aging tests allowing thermal cycles (thermal air streamer to force the power assemblies under thermal cycles of high amplitude) and active power cycles (use of hard working conditions such as short circuit for accelerating the aging of parts of the assembly).The first part of this manuscript presents the physical principles set in. We briefly introduce the concepts of fracture mechanics and the physical couplings.The second part focuses on the fractured DCB ceramic substrates. This failure can arise from defects randomly distributed in the material. We consider the problem using a statistical approach where we introduce the "weak link theory". The other cause of failure is the presence of geometrical defects called singularity where there is stress concentration requiring a deterministic approach. On this occasion we introduce the stress intensity factor which allows to study the failure problems associated with singular zone.The last part will focus on the aging of the transistor metallization. The search for indicators of aging has requested the development of several electrical characterization test benches for the precise measurement of different electrical parameters (leakage currents, threshold voltages, voltage drop in the on state ...) in a controlled thermal environment. Moreover, these electrical characterizations are correlated with observations at different aging states of the metallization degradation using a scanning electron microscope. We seek to show how the change in the morphology of the metallization can change the electrical characteristics of tested power transistors.