<p>In this project a new type of metal oxide semiconductor (MOS) sensor for biosensing was investigated. With the use of a porous gold film as aninternal reference electrode, measurements of pH were performed in liquid. This new approach for liquid measurements demands new methods andstudies to increase the conductivity and adhesion in liquid of the porous gold film. The films have been deposited, either by sputtering orevaporation. Extensive studies included the investigation of depositions parameters on film structure and investigating the film morphology. Thesurface structure was studied with a scanning electron microscope (SEM). pH measurements were preformed with promising results. The adhesionof the electrode was greatly improved by using grains of titanium underneath the gold film. This new approach could lead to new applications anddevices for MOS sensors and its sensor relatives.</p>

In this project a new type of metal oxide semiconductor (MOS) sensor for biosensing was investigated. With the use of a porous gold film as aninternal reference electrode, measurements of pH were performed in liquid. This new approach for liquid measurements demands new methods andstudies to increase the conductivity and adhesion in liquid of the porous gold film. The films have been deposited, either by sputtering orevaporation. Extensive studies included the investigation of depositions parameters on film structure and investigating the film morphology. Thesurface structure was studied with a scanning electron microscope (SEM). pH measurements were preformed with promising results. The adhesionof the electrode was greatly improved by using grains of titanium underneath the gold film. This new approach could lead to new applications anddevices for MOS sensors and its sensor relatives.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23243号 / 農博第2450号 / 新制||農||1084(附属図書館) / 学位論文||R3||N5333(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 白井 理, 教授 三芳 秀人, 教授 森 直樹 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Gold black porous coatings were thermally evaporated in the chamber backfilled with inert gas pressure and their optical properties were studied in near-far-IR wavelengths. The porosities of coatings were found to be extremely high around ~ 99%. Different approaches of effective medium theories such as Maxwell-Garnett, Bruggeman, Landau-Lifshitz-Looyenga and Bergman Formalism were utilized to calculate refractive index (n) and extinction coefficient (k). The aging induced changes on electrical and optical properties were studied in regular laboratory conditions using transmission electron microscopy, Fourier transform infrared spectroscopy, and fore-probe electrical measurements. A significant decrease in electrical resistance in as deposited coating was found to be consistent with changes in the granular structure with aging at room temperature. Electrical relaxation model was applied to calculate structural relaxation time in the coatings prepared with different porosities. Interestingly, with aging, absorptance of the coatings improved, which is explained using conductivity form of Bergman Formulism. Underlying aim of this work was to utilize gold blacks to improve sensitivity in un-cooled IR sensors consist of pixel arrays. To achieve this, fragile gold blacks were patterned on sub-mm length scale areas using both stenciling and conventional photolithography. Infrared spectral imaging with sub-micron spatial resolution revealed the spatial distribution of absorption across the gold black patterns produced with both the methods. Initial experiments on VOx-Au bolometers showed that, gold black improved the responsivity by 42%. This work successfully establishes promising role of gold black coatings in commercial un-cooled infrared detectors.

La première partie du travail présenté ici se concentre sur l’optimisation d’une cathode à oxygène. Tout d’abord, l’utilisation d’une nouvelle enzyme (la BOD de Magnaporthe oryzae) permet de multiplier le courant de réduction de l’oxygène en eau jusqu’à neuf fois. Ensuite la synthèse d’un polymère rédox adapté a permis d’améliorer le coefficient de diffusion des électrons dans l’hydrogel résultant en l’augmentation de la densité de courant générée. Enfin nous sommes passés d’uneélectrode de carbone en 2 dimensions à une fibre d’or poreuse tridimensionnelle. Après modification de cette fibre avec l’hydrogel rédox à base de BOD de M. oryzaenous avons évalué sa biocompatibilité : in vitro les tests ont montré l’absence totale de cytotoxicité et seule une très faible réponse inflammatoire ; in vivo aucune infection ne s’est déclarée pendant les 8 semaines d’implantation dans les souris etla formation d’une capsule fibrotique autour de l’électrode traduit sa bonne intégration dans les tissus de l’animal. La seconde partie concerne la biopile dans son intégralité, construite à partir de la cathode optimisée et d’une anode adaptée à base de GDH. Elle permet de générer jusqu’à 240 μW.cm-2 dans du tampon Pipes/CaCl2 à 5mM de glucose. La biopile a ensuite été testée dans du sang humain total. Un maximum de 129 μW.cm-2 a été obtenu dans un échantillon avec une glycémie de 8,2 mM sous air. De plus nous avons constaté que la densité de puissance délivrée augmente proportionnellement avec la glycémie des différents échantillons de sang testés, faisant de la biopile à la fois une source d’électricité et un biocapteur à glucose ce qui n’avait jamais été démontré auparavant. / The first part of the work presented here focuses on the optimization of an oxygen cathode. First, the use of a new enzyme (BOD from Magnaporthe oryzae) permit to increase the current of reduction of oxygen into water by a factor nine. Then the synthesis of a suitable redox polymer greatly improved the diffusion coefficient of electrons in the hydrogel, resulting in an increase of the current density. Finally we switched from a two-dimensional carbon electrode to a three-dimensional porous gold fiber. After modification of the fiber with the redox hydrogel based on BOD from M. oryzae, we assessed its biocompatibility: in vitro the tests showed the total absence of cytotoxicity and only a very low inflammatory response; in vivo noinfection appeared during the 8 weeks of implantation in mice and the formation of afibrotic capsule around the device reflects its successful integration into the animal tissues.The second part concerns the full biofuel cell, elaborated from the optimized cathode and an adapted GDH-based anode. It could generate up to 240 μW.cm-2 at 5mMglucose in Pipes/CaCl2 buffer. The biofuel cell was then tested in whole human blood. A maximum of 129 μW.cm-2 was obtained in a sample with 8,2 mM glycaemiaunder air. In addition we observed that the delivered power density increased proportionally with the glycaemia of the different blood samples tested, making the biofuel cell both a power source and a glucose biosensor at the same time which had never been shown before.