<p>The discovery of semi-conducting and conducting organic materials has opened new possibilities for electronic devices and systems. Applications, previously unattainable for conventional electronics, have become possible thanks to the development of conjugated polymers. Conjugated polymers that are both ion- and electron conducting, allow for electrochemical doping and de-doping via reversible processes as long as both forms of conduction remain available. Doping causes rearrangement of the -system along the polymer backbone, and creates new states in the optical band gap, resulting in an increased electronic conductivity and also control of the color (electrochromism). Doping can also occur by charge injection at a metal – semiconducting polymer interface. Electrochemical electronic devices and solid state devices based on these two types of doping are now beginning to enter the market.</p><p>This thesis deals with organic based-devices whose working mechanism involves electrolytes. After describing the properties of conjugated polymers, fundamentals on electrolytes (ionic conductivity, types, electric double layer and the electric field distribution) are briefly presented. Thereafter, a short review of the field of organic field effect transistors as well as a description of transistors that are gated via an electrolyte will be reviewed.</p><p>Paper I present a novel technique to visualize the electric field within a two-dimensional electrolyte by applying the electrolyte over an array of electronically isolated islands of electrochromic polymer material on a plastic foil. By observing the color change within each polymer island the direction and the magnitude of the electric field can be measured. This technology has applications in electrolyte evaluation and is also applicable in bio-analytical measurements, including electrophoresis. The focus of paper II lies on gating an organic field effect transistor (OFET) by a polyanionic proton conductor. The large capacitance of the electric double layer (EDL) that is formed at organic semiconductor/polyelectrolyte upon applying a potential to the gate, results in low operation voltages and fast response. This type of transistor that is gated via electric double layer capacitor is called EDLC-OFET. Because an electrolyte is used as a gate insulator, the role of the ionic conductivity of the electrolyte is considered in paper III. The effect on the electronic performance of the transistor is studied as well by varying the humidity level.</p>

The long-term goal of this research project is the development of solution-based inorganic dielectric and semiconductor materials for inkjet printed electronics. The main focus of this thesis involves testing of the materials and devices under development. A new solution-based inorganic dielectric material (HfOSO₄), given the name hafsox, is developed and shows excellent dielectric properties. Hafsox with the addition of lanthanum, to improve film dehydration, has successfully been demonstrated as a gate dielectric. Metal-insulator-metal (MIM) capacitance testing of hafsox with lanthanum, has resulted in a low loss tangent of 0.30% at 1 kHz, a relative permittivity of 11.47 at 1 kHz, a breakdown voltage of 6.30 MV cm⁻¹, and a leakage current density of 4.38 nA cm⁻² at 1 MV cm⁻¹. Progress has also been achieved in the development of solution-based semiconductor materials. To date the most successful of these materials is zinc indium oxide (ZIO), which has been demonstrated as a thin-film-transistor (TFT) channel material. This ZIO TFT is a depletion-mode device with a turn-on-voltage of V[subscript on]~ -19 V, a threshold voltage of V[subscript T] ~-16 V, and a drain current on-to-off ratio of ~10³. Mobilities extracted from this ZIO TFT include an incremental mobility of μ[subscript inc] ~0.05 cm² V⁻' sec⁻', an effective mobility of μ[subscript eff] ~0.02 cm² V⁻' sec⁻', and an average mobility of μ[subscript avg] ~0.02 cm² V⁻' sec⁻' at V[subscript GS]=20 V. The development of metal-semiconductor field-effect transistors (MESFET) TFTs is also investigated as a means of eliminating the need for a dielectric material in order to reduce the complexity of fabricating circuits. MESFETs are attempted with semiconductor materials such as CdS that is deposited by chemical bath deposition (CBD) and SnO₂ that is deposited by RF magnetron sputtering, but with little success. The most successful MESFET-like device fabricated, employing SnO₂ as the channel material, is a strong depletion-mode device with a small amount of gate voltage modulation. / Graduation date: 2006

The neutron and electron radiation effects in Ill-V compound semiconductor heterostructure devices are studied in this thesis. Three types of devices investigated are AlGaAs/GaAs high electron mobility transistors (HEMTs), AlGaAs/InGaAs/GaAs heterostructure insulated gate field effect transistors (HIGFETs), and InP/InCaAs/InGaAs single heterojunction bipolar transistors (SHBTs). HEMTs and HIGFETs are primarily investigated for neutron irradiation effects. Detailed optimized processing of HEMT devices is introduced. Numerical as well as analytical models that incorporate radiation induced degradation effects in HEMTs and HIGFETs are developed. The most prominent radiation effects appearing on both HEMT and HIGFET devices are increase of threshold voltage (V[subscript T]) and decrease of transconductance (g[subscript m]) as radiation dose increases. These effects are responsible for drain current degradation under given bias conditions after irradiation. From our experimental neutron irradiation study and our theoretical models, we concluded that threshold voltage increase is due to the radiation-induced acceptor-like (negatively charged) traps in the GaAs channel region removing carriers. The mobility degradation in the channel is responsible for g[subscript m] decrease. Series resistance increase is also related to carrier removal and mobility degradation. Traps introduced in the GaAs region affect the device performance more than the traps in the AlGaAs doped region. V[subscript T] and g[subscript m] of HIGFET devices are less affected by neutron radiation than they are in HEMTs. This difference is attributed to different shapes of the quantum well in the two devices. The main effects of electron and neutron irradiation of SHBTs are decrease of collector current (I[subscript c]), decrease of common-emitter DC gain, increase of the collector output conductance (��I[subscript c]/��V[subscript CE]), and increase of collector-collector offset voltage. The decrease of breakdown voltage of reverse biased base-emitter junction diode is responsible for increasing the output conductance after irradiation. Base-collector junction degradation also induces collector-emitter offset voltage increase. / Graduation date: 2003

Graduation date: 2001

Detection of biomolecules is important for the diagnosis and treatment of diseases. Low concentration detection, specific biomolecule detection, and point-of-care use are appealing characteristics for biosensors because of the possibility of early detection and quick results of specific biomolecules. Furthermore, inexpensive biosensors are appealing so that they are accessible to the general population. The biosensors in this study have the potential to satisfy these characteristics. In this study graphene field-effect transistors (G-FET) were fabricated. Graphene was grown using chemical vapor deposition (CVD) and transferred to a silicon/silicon oxide substrate. The CVD method is the most scalable and cost-effective method of producing graphene for devices. Standard photolithography was used to pattern and then deposit metal electrodes. Two separate experiments were conducted; one using electrostatic attraction to bind protein to the active area of the G-FET to detect the protein poly-L-lysine (PLL) and one using an aptamer modified G-FET to selectively detect the protein thrombin. Analyte was delivered using a homebuilt, pressure driven, microfluidic, mass flow system. Both experiments showed a detection of the protein. The PLL experiment showed a clear change in the effective gate voltage of the G-FET. The thrombin experiment showed a change in the effective gate voltage that varied with differing concentrations of thrombin present. Furthermore, in the thrombin experiment by changing from a thrombin solution back to buffer the effective gate voltage was brought back to its original value. A competing protein was introduced and gave a signal comparable to the signal of a 10 times smaller concentration of thrombin. All of this shows that CVD grown graphene in a FET biosensor can be used for protein detection. Furthermore, the specific detection of thrombin suggests that aptamer modified G-FETs with CVD grown graphene can be used as a protein specific biosensor. / Graduation date: 2013

Graduation date: 1996

Graduation date: 1996

Originally presented as the author's thesis (Swiss Federal Institute of Technology), Diss. ETH No. 16228. / Summary in German and English, text in English. Includes bibliographical references (p. 123-132).

Notre recherche se base sur la structuration des polymères conjugués qui présentent des propriétés optiques et électroniques intéressantes en raison de leur structure moléculaire intrinsèque. En effet, la structure des polymères conjugués se compose d’une alternance de simples et de doubles liaisons donnant lieu à une délocalisation des électrons le long des chaînes. Cette conjugaison est à l’origine de leurs propriétés de luminescence et de leur caractère semi-conducteur. Ces polymères sont couramment utilisés dans des dispositifs électroniques où ils jouent le rôle de composant actif. Le fonctionnement de ces dispositifs repose sur la capacité des charges à se déplacer le long des chaînes (processus intramoléculaire) et d'une chaîne à l'autre (processus intermoléculaire) et par conséquent, ces propriétés de transport dépendent de l’arrangement des chaînes polymères dans le solide, qui lui-même découle des interactions supramoléculaires. Il est donc impératif de maîtriser ces interactions et d’étudier l’influence qu’elles ont sur les performances de tels dispositifs électroniques. C’est précisément sur ce point que porte notre travail : étudier et contrôler la formation de nanostructures en termes de dimensions, de forme et de localisation, en appliquant une contrainte physique extérieure à un film de polymère conjugué. Le polymère conjugué sur lequel notre étude se base principalement est le poly(3-hexylthiophène), P3HT. Ce polymère est semi-cristallin et possède une mobilité de charge élevée (0.18 cm2/V.s), ce qui en fait un très bon candidat en tant que composant actif dans les transistors à effet de champ. Nous avons, dans le cadre de notre recherche, étudié la structuration de films minces de P3HT, réalisée par l’application de contraintes physiques extérieures. L’utilisation d’une pointe de microscope à force atomique travaillant en mode contact permet de déformer plastiquement la surface polymère en créant des structures périodiques en surface des films mais elle permet, en outre, d’orienter les chaînes polymères dans la direction de passage de la pointe. Différents paramètres expérimentaux ont été étudiées comme par exemple, la résolution choisie pendant l’expérience, le nombre de passage effectués par la pointe ou encore l’angle avec lequel la pointe structure le film polymère. Nous avons également démontré que cette technique, appliquée au canal polymère d’un transistor à effet de champ, permet d’améliorer les propriétés électriques du P3HT et par conséquent, d’augmenter les performances du dispositif électronique. Nous avons utilisé une autre méthode, dite de « lithographie douce », afin de structurer le P3HT. Cette technique présente l’avantage de « façonner » le polymère lorsqu’il se trouve en solution et ne nécessite donc pas la formation préalable d’un film. Elle consiste à déposer une goutte de solution polymère sur un substrat, à l’entrée de canaux micrométriques de PDMS; l’écoulement de la solution polymère, qui se fait par capillarité dans les canaux, est donc confiné. Le solvant va ensuite s’évaporer et il reste alors, sur le substrat, un dépôt polymère qui est la réplique négative des canaux de PDMS. L’analyse du dépôt polymère formé grâce à cette méthode révèle, comme c’était le cas pour la technique précédente, une orientation des chaînes polymères au sein des canaux. Dans la dernière partie de ce travail, nous avons étudié le dopage de films fibrillaires de P3HT. L'étude de la morphologie des films dopés montre que la structure fibrillaire est conservée, avec une légère augmentation de la largeur des fibrilles. Cette augmentation résulte d'un déplacement des chaînes polymères les unes par rapport aux autres dans l'axe du squelette conjugué afin de laisser des espaces vacants pour accueillir les contre-ions dans le réseau polymère. Les mesures électriques des films dopés montrent un accroissement très important de la conductivité du polymère. On observe une augmentation de six ordres de grandeur entre les conductivités d'un film neutre et dopé.

The emergence of organic semiconductors is exciting since it promises to open up for straightforward and low-cost fabrication of a wide range of efficient and novel electronic devices. However, in order for this promise to become reality it is critical that new and functional fabrication techniques are developed. This thesis demonstrates the conceptualization, development, realization and implementation of a particularly straightforward and scalable fabrication process: the photo-induced and resist-free imprint patterning technique.Initial experiments revealed that some members of a group of carbon-cage molecular semiconductors – termed fullerenes – can be photochemically modified into dimeric or polymeric structures during exposure to laser light, and, importantly, that the exposed fullerene material retains its good electron-transport property while its solubility in common organic solvents is drastically lowered. With this information at hand, it was possible to design and create well-defined patterns in a solution-deposited fullerene film by exposing selected film areas to laser light and then developing the entire film in a tuned developer solution. An electronically active fullerene pattern emerges at the locations defined by the incident laser beam, and the patterning technique was successfully utilized for the fabrication of arrays of efficient field-effect transistors.In a later stage, the capacity of the photo-induced and resist-free imprint technique was demonstrated to encompass the fabrication of ubiquitous and useful CMOS circuits. These are based on a combination of p-type and n-type transistors, and a blend between a p-type organic semiconductor and an n-type fullerene compound was designed so that the latter dominated. By solution-depositing the blend film on an array of transistor structures, exposing selected transistors to laser light, and then developing the entire transistor array in a developer solution, it was possible to establish a desired combination of (non-exposed) p-type transistors and (exposed) n-type transistors. We finally utilized this combination of transistors for the fabrication of a CMOS circuit in the form of well a-functional organic inverter stage.