Designs for PnP GaAs/InxGa1-xAs/GaAs heterojunction bipolar transistors (HBTs) are proposed and simulated with the aid of commercial software. Band diagrams, Gummel plots and common emitter characteristics are shown for the specific case of x=1, x=0.7, and x linearly graded from 0.75 to 0.7. Of the three designs, it is found that the linearly graded case has the lowest leakage current and the highest current gain. IV curves for all four possible classes of InAs/GaAs heterojunction (nN, nP, pN, pP) are calculated. A pN heterojunction is fabricated and characterized. In spite of the 7% lattice mismatch between InAs and GaAs, the diode has an ideality factor of 1.26 over three decades in the forward direction. In the reverse direction, the leakage current grows exponentially with the magnitude of the bias, and shows an effective ideality factor of 3.17, in stark disagreement with simulation. IV curves are taken over a temperature range of 105 K to 405 and activation energies are extracted. For benchmarking the device processing and the characterization apparatus, a conventional GaAs homojunction diode was fabricated and characterized, showing current rectification ratio of 109 between plus one volt and minus one volt. Because the PnP material for the optimal HBT design was not available, an Npn GaAs/InAs/InAs HBT structure was processed, characterized, and analyzed. The Npn device fails in both theory and in practice; however, by making a real structure, valuable lessons were learned for crystal growth, mask design, processing, and metal contacts. / Master of Science

Advancements in neural interfacing technologies, such as microelectrode arrays, have significantly contributed to understanding brain function and treating neurological disorders. Decoding the intricacies and functioning of neural circuits is key to further unlocking its potential. Two key approaches, electrical neural recording and optical imaging, have been the basis of stimulating and monitoring neural circuits. Despite the remarkable progress, several key issues such as reliable stimulation of neurons, closed-loop stimulation and monitoring, and undesired background fluorescence during widefield optical imaging remain challenging. After giving a brief background on electrode and microLED arrays, the dissertation delves into the design, microfabrication, and characterization of microelectrode arrays for neural electrical stimulation, recordings, and microLED arrays as a light source for improving optical microscopy. We first discuss a dense conformal electrode array for high spatial resolution stimulation in electrosensory systems. The performance metrics of the integrated system are thoroughly examined through meticulous characterization and optimization processes. Special emphasis is placed on evaluating biocompatibility, electrical properties, and spatial resolution to ensure robust and reliable neural stimulation capability. Next, we discuss a microelectrode device that combines simultaneous electrical recording and 2-photon imaging. We use an Indium Tin Oxide (ITO) material to fabricate a transparent electrode array with a design capable of single neuron recordings. The design, microfabrication, and electrooptical characterization are presented to demonstrate the device’s capability. A system integrating the array with a GRIN lens is also presented to record and image deeper into the brain tissue. Combining both the electrical and optical recordings of neuron ensembles and finding correlations can shed further light on the functioning of neural circuits. To address the problem of unwanted background fluorescence during neural cell imaging, two microLED arrays as light sources are presented. With a microstripe array, we implement optical sectioning structured illumination microscopy (OS-SIM), and with the 2D microLED array, we implemented targeted illumination to reject background fluorescence and improve contrast. We examine the capability of the microLED as a light source with luminance-current-voltage, directivity, and transient measurements. Both implementations highlight the novel non-display application of microLED to address challenges in neural imaging. This research represents a significant contribution to the burgeoning field of neural engineering, offering novel methodologies and technologies that promise to revolutionize our approach to understanding brain functions.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第25482号 / 理博第5063号 / 新制||理||1722(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 有賀 哲也, 教授 堀毛 悟史 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The direct hydrogenation of CO2 to methanol is an attractive approach to employ the greenhouse gas as a chemical feedstock. However, the commercial copper catalyst, used for methanol synthesis from CO-rich syngas, suffers from deactivation at elevated CO2 partial pressure. An emerging alternative is represented by In2O3 as it withstands the hydrothermal conditions induced by the reverse water-gas shift reaction. The active sites for the adsorption of CO2 and the subsequent conversion into methanol were shown to be oxygen vacancies on the surface of In2O3. In this study, N2O was utilized as a probe molecule to quantify the number of vacancies on indium oxide catalysts. The number of inserted oxygen atoms could be correlated to the respective CO2 hydrogenation activity. Furthermore, the atomic efficiency of indium was enhanced by applying atomic layer deposition of indium oxide on ZrO2.

Parmi les nitrures III-V, le matériau InGaN a été intensément étudié depuis les années 2000 pour des applications photovoltaïques, en particulier pour des cellules multi-jonctions, grâce à son large gap modulable pouvant couvrir quasiment tout le spectre solaire. On pourrait alors atteindre de hauts rendements tout en assurant de bas coûts. Cependant, l’un des problèmes de l’InGaN est l’absence de substrat accordé en maille provoquant une grande densité de défauts et limitant ainsi les performances des composants. Nous avons donc étudié la faisabilité de cellules solaires simples jonctions à base d’InGaN sur des substrats alternatifs comme le silicium et le verre afin de baisser les coûts et d’avoir de larges applications. Afin d’adapter l’InGaN sur ces substrats alternatifs, nous avons utilisé une couche tampon en ZnO. Ce travail a été réalisé dans le cadre du projet ANR NewPVonGlass. Plus particulièrement, dans ce projet, mon travail avait pour objectifs de réaliser des caractérisations électriques et optiques des matériaux et des composants. Les deux premières parties de cette thèse introduisent le matériau InGaN et l’effet photovoltaïque. Les techniques de caractérisation utilisées sont expliquées dans le troisième chapitre. Ensuite, les résultats obtenus lors de la caractérisation cristalline du matériau InGaN sont présentés en fonction du substrat, de la concentration d’indium et de l’épaisseur de la couche. Puis, la cinquième partie développe les caractérisations des premières cellules à base d’InGaN sur saphir. Enfin, dans le dernier chapitre, des simulations de cellules solaires à base d’InGaN ont été réalisées. Le modèle développé nous a permis d’optimiser la structure et le dopage du composant et de déterminer les paramètres critiques. Nous montrons donc, dans ce travail, le développement d’une cellule solaire à base d’InGaN : des caractérisations des matériaux de base à celles des cellules solaires, en passant par la modélisation. / Among III-V nitrides, the InGaN material has intensively been studied since the year 2000 for photovoltaic applications, in particular for multi-junction solar cells, thanks to its large tunable band gap covering almost the entire solar spectrum. Then, it will be possible to reach high efficiency and low cost. However, one of the problems of InGaN material is the absence of lattice-matched substrate leading to high defect density which limits device performances. We have thus studied the feasibility of single junction InGaN based solar cells on alternative substrate such as silicon and glass in order to lower the price and to benefit from their wide application fields. To adapt InGaN material on these new substrates, we have utilized ZnO buffer layer. This work has been carried out within the framework of the ANR project NewPVonGlass. More particularly, in this project, I was in charge of the electrical and optical characterizations of the materials and devices. In the two first parts of this manuscript, the InGaN material and the photovoltaic effect are introduced. Then, the characterization techniques are explained in the third chapter. In the fourth part, the results obtained during crystalline characterization of the InGaN materials are presented depending on the substrate, the indium percentage and the InGaN layer thickness. Then, the fifth chapter presents the first InGaN-based solar cell characteristics on sapphire substrate. Finally, in the last part, simulations of InGaN-based solar cell have been performed. The developed model was able to optimize the structure and to determine the critical parameters. Thus, we have shown in this work the development of an InGaN-based solar cell from the base material characterizations to the device tests, through modeling.

Parmi les filières de cellules photovoltaïques, les cellules solaires organiques suscitent un intérêt industriel par leur faible coût financier et de production énergétique et leur application possible sur des substrats flexibles de type plastique. L'ITO (Indium Tin Oxide) est l'électrode transparente conductrice (ETC) la plus utilisée pour ces cellules ainsi que pour d'autres dispositifs optoélectroniques. Cependant, ce matériau n'est pas sans présenter certains inconvénients (rareté de l'indium, structure non adaptée à des substrats flexibles,…), et la recherche d'alternatives à l'ITO est une préoccupation actuelle de la communauté scientifique internationale. Une possibilité est alors offerte par des structures multicouches de type Oxyde|Métal|Oxyde. Le rôle des deux couches d’oxydes est d’accorder, en ajustant les épaisseurs, la position, l’intensité et la largeur de la fenêtre spectrale de transmission. Des travaux numériques et expérimentaux couplés ont été effectués en particulier sur les structures SnOx|Ag|SnOx, TiOx|Ag|TiOx et ZnS|Ag|ZnS. Par microstructuration de telles électrodes ou bien par incorporation d’un bicouche Cu|Ag comme feuillet métallique au coeur de la structure, il est possible d’améliorer leurs performances optiques en amplifiant et en élargissant la fenêtre spectrale de transmission, sans dégrader leur haute conductivité. L’intégration d’électrodes SnOx|Ag|SnOx et TiOx|Ag|TiOx au sein de cellules solaires organiques inverses a été entrepris. Des résultats photoélectriques très prometteurs ont été obtenus avec la structure TiOx|Ag|TiOx qui permet d’atteindre des performances de niveau quasi-équivalent aux cellules de référence à base d’ITO. / Among all variants of photovoltaic thins films, organic solar cells generate a major industrial interest due to low manufacturing costs, reasonable levels of energy production and suitability to flexible substrates like plastic. ITO (Indium Tin Oxide) is the most used Transparent Conductive Electrode (TCE) for organic solar cells as well as other optoelectronic devices. However, this material is not without drawbacks (scarcity of indium, non-suitability to flexible substrates...), and the search for alternatives to ITO is actively pursued by the international scientific community. One possibility is offered by Oxide|Metal|Oxide multilayer structures. By reaching the thin metal layer percolation threshold and by varying its thickness, it is possible to obtain very high conductivity and transparency of this multilayer in the visible spectral range. The role of both oxide layers is to tune the position, intensity and width of the spectral transmission window by adjusting the oxides’ thicknesses. Coupled experimental and numerical works were lead in particularly on SnOx|Ag|SnOx, TiOx|Ag|TiOx and ZnS|Ag|ZnS structures. By microstructuring such electrodes, or by incorporating a Cu|Ag bilayer as metal sheet at the core of the structure, it is possible to increase the optical performances by amplifying and expanding the spectral transmission window without degrading the high conductivity. The integration of SnOx|Ag|SnOx and TiOx|Ag|TiOx electrodes in inversed organic solar cells was undertaken. Very promising photoelectric results were obtained with the TiOx|Ag|TiOx structure which allows to reach performances close to that obtained with ITO-based reference cells.

L’évolution de la microélectronique suit plusieurs axes notamment la miniaturisation des éléments actifs (réduction de taille des transistors), et l’augmentation de la densité d’interconnexion qui se traduisent par la loi de Gordon Moore qui prédit que la densité d'intégration sur silicium doublerait tous les deux ans. Ces évolutions ont pour conséquence la réduction des prix et du poids des composants. L’hybridation ou flip chip est une technologie qui s’inscrit dans cette évolution, elle consiste en l’assemblage de matériaux hétérogènes. Dans cette étude il s‘agit d’un circuit de lecture Silicium et d’un circuit de détection InP ou GaAs assemblés par l’intermédiaire d’une matrice de billes d’indium. La connexion flip chip est basée sur l’utilisation d’une jonction par plots métalliques de faibles dimensions qui permet de diminuer les pertes électriques (faible inductance et faible bruit), une meilleure dissipation thermique, une bonne tenue mécanique. Enfin elle favorise la miniaturisation avec l’augmentation de la compacité et de la densité d’interconnexion.Les travaux de thèse se concentrent sur deux axes principaux. Le premier concerne l’hybridation par brasure avec la technologie des billes d’indium par refusion, et le second concerne l’hybridation par pression à température ambiante (nano-scratch) par l’intermédiaire des nanostructures (Nano-fils d’or, Nano-fils ZnO). Ces travaux ont permis la réalisation d’un détecteur InGaAs avec extension visible de format TV 640*512 pixels au pas de 15 µm. Ces travaux ont également permis la validation mécanique de l’assemblage d’un composant de format double TV 1280*1024 pixels au pas de 10 µm par cette même méthode de reflow. Pour l’axe hybridation à froid, nos travaux ont permis la validation d’une méthode de croissance de nano-fils ZnO par une voix hydrothermique à basse température (<90°C). / Evolution of microelectronics follows several major roads, in particular the size decrease of active elements (reduction of size of transistors), better electrical performances, high I/O density and smaller size. This revolution has been predicted by Gordon Moore who suggested that integrated circuits would double in complexity every 24 months. As a consequence, this evolution induces both the reduction of prices and the weight of components.The term flip chip describes the method of electrically connecting the die to the package substrate. Flip chip microelectronic assembly is the direct electrical connection of face-down (or flipped) integrated circuit (IC) chips onto substrates, circuit boards, or carriers, using conductive bumps on the chip bond pads. Flip chip offers the highest speed electrical performance, reduces the delaying inductance and capacitance of the connection, Smallest Size Greatest I/O Flexibility, Most Rugged, high I/O density and Lowest Cost.This thesis work study concentrates on two main directions. The first one concerns hybridization by means of the technology of Indium bumps associated to a reflow process and the second one is about pressure induced hybridization at low temperature using nanostructures (Nano-scratch). In this work, we have developed a complete process to assemble a focal plane array format of 640 x 512 pixels with a pitch of 15 µm. These studies also allowed the mechanical validation of hybridization of a focal plane arrays 1280*1024 pixels with a pitch of 10 µm. Concerning alternative technologies to flip chip reflow, we introduced and demonstrate the relevance of a method of growth of ZnO nanorods using low temperature wet chemical growth and further hybridization at ambient temperature.

Indium-gallium-zinc oxide (IGZO) and zinc-tin oxide (ZTO) are investigated for thin-film transistor (TFT) applications. Negative bias illumination stress (NBIS) is employed for electrical stability assessment. Unpassivated IGZO and ZTO TFTs suffer from severe NBIS instabilities. Zinc-tin-silicon oxide is found to be an effective passivation layer for IGZO and ZTO TFTs, significantly improving the NBIS stability. NBIS instabilities in unpassivated TFTs are attributed to an NBIS-induced desorption of chemisorbed oxygen from the channel layer top surface, exposing surface oxygen vacancies. A ZTSO layer protects the channel layer top surface from adsorbed gas interactions and also appears to reduce the density of oxygen vacancies. The best device architectures investigated with respect to TFT electrical performance are found to be staggered with aluminum electrodes for unpassivated TFTs and coplanar with ITO electrodes for ZTSO-passivated TFTs. Annealing in wet-O₂ is not found to be effective for improving the performance of IGZO or ZTO TFTs or for reducing the post-deposition annealing temperature. / Graduation date: 2012

Semiconductor quantum dots (QDs) are well established as sub-Poissonian sources of entangled photon pairs. To improve the utility of a QD light source, it would be advantageous to extend their emission further into the near infrared, into the low absorption wavelength windows utilised in long-haul optical telecommunication. Initial experiments succeeded in interfering O-band (1260—1360 nm) photons from an InAs/GaAs QD with dissimilar photons from a laser, an important mechanism for quantum teleportation. Interference visibilities as high as 60 ± 6 % were recorded, surpassing the 50 % threshold imposed by classical electrodynamics. Later, polarisation-entanglement of a similar QD was observed, with pairs of telecom-wavelength photons from the radiative cascade of the biexciton state exhibiting fidelities of 92.0 ± 0.2 % to the Bell state. Subsequently, an O-band telecom-wavelength quantum relay was realised. Again using an InAs/GaAs QD device, this represents the first implementation of a sub-Poissonian telecom-wavelength quantum relay, to the best knowledge of the author. The relay proved capable of implementing the famous four-state BB84 protocol, with a mean teleportation fidelity as high as 94.5 ± 2.2 %, which would contribute 0.385 secure bits per teleported qubit. After characterisation by way of quantum process tomography, the performance of the relay was also evaluated to be capable of implementing a six-state QKD protocol. In an effort to further extend the emitted light from a QD into the telecom C-band (1530—1565 nm), alternative material systems were investigated. InAs QDs on a substrate of InP were shown to emit much more readily in the fibre-telecom O- and C-bands than their InAs/GaAs counterparts, largely due to the reduced lattice mismatch between the QD and substrate for InAs/InP (~3 %) compared to InAs/GaAs (~7 %). Additionally, to minimize the fine structure splitting (FSS) of the exciton level, which deteriorates the observed polarisation-entanglement, a new mode of dot growth was investigated. Known as droplet epitaxy (D-E), QDs grown in this mode showed a fourfold reduction in the FSS compared to dots grown in the Stranski-Krastanow mode. This improvement would allow observation of polarisation-entanglement in the telecom C-band. In subsequent work performed by colleagues at the Toshiba Cambridge Research Labs, these D-E QDs were embedded in a p-i-n doped optical cavity, processed with electrical contacts, and found to emit entangled pairs of photons under electrical excitation. The work of this thesis provides considerable technological advances to the field of entangled-light sources, that in the near future may allow for deterministic quantum repeaters operating at megahertz rates, and in the further future could facilitate the distribution of coherent multipartite states across a distributed quantum network.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This PhD thesis describes our results on the application of indium(I) bromide in carbon-carbon bond forming reactions. Indium enolates, generated in situ from the reaction between indium(I) bromide and α,α-dichloroketones, react with carbonyl compounds and electron-deficient alkenes. Reactions of indium enolate with α,α-dichloroketones, in presence of extra InBr, leads to the formation of 1,4-diketones. The coupling with aldehydes leads alternatively, according as the stoichiometry, to the diastereoselective synthesis of (syn+anti)-2-chloro-3-hydroxy-propan-1-ones (which can be converted to the respective trans-epoxyketones), (E)-α,β-unsaturated ketones and cyclopropanes, upon a sequenced reaction mechanism. We also have developed a methodology for the preparation of cyclopropanes through the reaction of the indium enolate and other organoindium(III) compounds, derived from the reactions between InBr and α,α-dihalo carbonyl compounds and halo-acetonitriles, with electron-deficient alkenes. / Este trabalho descreve os resultados dos estudos realizados sobre aplicações de brometo de índio(I) em reações para formação de ligações carbono-carbono. A reação entre brometo de índio(I) e α,α-diclorocetonas produz, in situ, enolatos de índio que reagem com compostos carbonílicos e alcenos deficientes em elétrons. As reações do enolato de índio com outras moléculas de α,α-diclorocetonas, na presença de InBr em excesso, leva à formação de 1,4-dicetonas. O acoplamento com aldeídos leva alternativamente, conforme a estequiometria, à formação diastereosseletiva de (syn+anti)-α-cloro-β-hidróxi-cetonas (que podem ser convertidas às respectivas trans-epóxi-cetonas), cetonas (E)-α,β-insaturadas e ciclopropanos, segundo um mecanismo de reações sequenciais. Ainda foi desenvolvida uma metodologia para preparação de ciclopropanos através da reação do enolato de índio e de outros compostos organoíndio(III), derivados da reação entre InBr e vários compostos carbonílicos α,α-di-halogenados e halogeno-acetonitrilas, com alcenos deficientes em elétrons.