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Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have likewise been investigated. Functionalization of acene compounds by placement of groups around the molecule affects the way in which molecules interact in the solid state, in addition to the energetics of the molecule. The use of electron donating or electron withdrawing groups affects the frontier molecular orbitals and thus affects the optical and electronic gaps of the molecules. The use of bulky side groups such as alkylsilylethynyl groups allows for crystal engineering of molecular aggregates, and changing the volume and dimensions of the alkylsilyl groups affects the intermolecular interactions and thus changes the packing motif. In chapter 2, a series of tetracene and pentacene molecules with strongly electron withdrawing groups is described. The investigation focuses on the change in energetics of the frontier molecular orbitals between the base acene and the nitrile and dicyanovinyl derivatives as well as the differences between the pentacene and tetracene molecules. The differences in close packing motifs through use of bulky alkylsilylethynyl groups is also discussed in relation to electron acceptor material design and bulk heterojunction organic photovoltaic characteristics. Chapter 3 focuses on molecular acceptor and donor molecules for bulk heterojunction organic photovoltaics based on anthrathiophene and benzo[1,2-b:4,5-b’]dithiophene central units like literature molecules containing fluorene and dithieno[2,3-b:2’,3’-d]silole cores. The synthetic strategies of developing reduced symmetry benzo[1,2-b:4,5-b’]dithiophene to study the effect of substitution around the central unit is also described. The optical and electronic properties of the donors and acceptors are described along with the performance and characteristics of devices employing these molecules. The final two data chapters focus on new nitrogen containing polycyclic hydrocarbons containing indolizine and (2.2.2) cyclazine units. The optical, electronic and other physical properties of these molecules are explored, in addition to the synthetic strategies for incorporating the indolizine and cyclazine units. By use of alkylsilylethynyl groups, crystal engineering was investigated for the benzo[2,3-b:5,6-b’]diindolizine chromophore described in chapter 4 to target the 2-D “brick-work” packing motif for application in field effect transistor devices. Optical and electronic properties of the cyclazine end-capped acene molecules described in chapter 5 were investigated and described in relation to the base acene molecules. In both cases, density functional theory calculations were conducted to better understand unexpected optical properties of these molecules, which are like the linear acene series despite the non-linear attachment.

This thesis reports a comprehensive study of quaternary BeMgZnO alloy and BeMgZnO/ZnO heterostructures for UV-optoelectronics electronic applications. It was shown that by tuning Be and Mg contents in the heterostructures, high carrier densities of two-dimensional electron gas (2DEG) are achievable and makes its use possible for high power RF applications. Additionally, optical bandgaps as high as 5.1 eV were achieved for single crystal wurtzite material which allows the use of the alloy for solar blind optoelectronics (Eg>4.5eV) or intersubband devices. A systematic experimental and theoretical study of lattice parameters and bandgaps of quaternary BeMgZnO alloy was performed for the whole range of compositions. Composition independent bowing parameters were determined which allows accurate predictions of experimentally measured values. The BeMgZnO thin films were grown by plasma assisted molecular beam epitaxy (P-MBE) in a wide range of compositions. The optimization of the growth conditions and its effects on the material properties were explored. The surface morphology and electrical characteristics of the films grown on (0001) sapphire were found to critically depend on the metal-to-oxygen ratio. Samples grown under slightly oxygen-rich conditions exhibited the lowest RMS surface roughness (as low as 0.5 nm). Additionally, the films grown under oxygen-rich conditions were semi-insulating (>105 Ω∙cm), while the films grown under metal-rich conditions were semiconducting (~102 Ω∙cm). Additionally, with increasing bandgap Stokes shift increases, reaching ~0.5 eV for the films with 4.6 eV absorption edge suggests the presence of band tail states introduced by potential fluctuations and alloying. From spectrally resolved PL transients, BeMgZnO films grown on a GaN/sapphire template having higher Mg/Be content ratio exhibit smaller localization depth and brighter photoluminescence at low temperatures. The optimum content ratio for better room temperature optical performance was found to be ~2.5. The BeMgZnO material system and heterostructures are promising candidates for the device fabrication. 2DEG densities of MgZnO/ZnO heterostructures were shown to improve significantly (above 1013 cm-2) by adding even a small amount of Be (1-5%). As an essential step toward device fabrication, reliable ohmic contacts to ZnO were established with remarkably low specific contact resistivities below 10-6 Ohm-cm2 for films with 1018 cm-3 carrier density.

While the car fleet becomes increasingly larger it is important to lower the amounts of pollutants from each individual diesel or gasoline engine to almost zero levels. The pollutants from these engines predominantly originate from high NOx emissions and particulates, in the case when diesel is utilized, and emissions at cold start from gasoline engines. One way of treating the high NOx levels is to introduce ammonia in the diesel exhausts and let it react with the NOx to form nitrogen gas and water, which is called SCR (Selective Catalytic Reduction). However, in order to make this system reduce NOx efficiently enough for meeting future legislations, closed loop control is required. To realize this type of system an NOx or ammonia sensor is needed. The cold start emissions from gasoline vehicles are primarily due to a high light-off time for the catalytic converter. Another reason is the inability to quickly heat the sensor used for controlling the air-to-fuel ratio in the exhausts, also called the lambda value, which is required to be in a particular range for the catalytic converter to work properly. This problem may be solved utilizing another, more robust sensor for this purpose. This thesis presents the efforts made to test the SiC-based field effect transistor (SiC-FET) sensor technology both as an ammonia sensor for SCR systems and as a cold start lambda sensor. The SiC-FET sensor has been shown to be highly sensitive to ammonia both in laboratory and engine measurements. As a lambda sensor it has proven to be both sensitive and selective, and its properties have been studied in lambda stairs both in engine exhausts and in the laboratory. The influence of metal gate restructuring on the linearity of the sensor has also been investigated. The speed of response for both sensor types has been found to be fast enough for closed loop control in each application. / <p>On the day of the public defence of the doctoral thesis, the status of article III was: in press. Report code: LiU-Tek-Lic-2003:50.</p>

In this dissertation I present results on our efforts to increase the sensitivity and selectivity of silicon nanowire ion-sensitive field-effect transistors for the detection of biomarkers, as well as a novel method for wireless power transfer based on metamaterial rectennas for their potential use as implantable sensors. The sensing scheme is based on changes in the conductance of the semiconducting nanowires upon binding of charged entities to the surface, which induces a field-effect. Monitoring the differential conductance thus provides information of the selective binding of biological molecules of interest to previously covalently linked counterparts on the nanowire surface. In order to improve on the performance of the nanowire sensing, we devised and fabricated a nanowire Wheatstone bridge, which allows canceling out of signal drift due to thermal fluctuations and dynamics of fluid flow. We showed that balancing the bridge significantly improves the signal-to-noise ratio. Further, we demonstrated the sensing of novel melanoma biomarker TROY at clinically relevant concentrations and distinguished it from nonspecific binding by comparing the reaction kinetics. For increased sensitivity, an amplification method was employed using an enzyme which catalyzes a signal-generating reaction by changing the redox potential of a redox pair. In addition, we investigated the electric double layer, which forms around charges in an electrolytic solution. It causes electrostatic screening of the proteins of interest, which puts a fundamental limitation on the biomarker detection in solutions with high salt concentrations, such as blood. We solved the coupled Nernst-Planck and Poisson equations for the electrolyte under influence of an oscillating electric field and discovered oscillations of the counterion concentration at a characteristic frequency. In addition to exploring different methods for improved sensing capabilities, we studied an innovative method to supply power to implantable biosensors wirelessly, eliminating the need for batteries. A metamaterial split ring resonator is integrated with a rectifying circuit for efficient conversion of microwave radiation to direct electrical power. We studied the near-field behavior of this rectenna with respect to distance, polarization, power, and frequency. Using a 100 mW microwave power source, we demonstrated operating a simple silicon nanowire pH sensor with light indicator.

Die markierungsfreie Detektion von molekularen Wechselwirkungen mittels Feldeffekt-basierter Sensoren ist eine vielversprechende Strategie zur Entwicklung einer neuen Generati-on von Biochips mit direkter elektrischer Auslesung und somit geeignet für schnelle, einfache und kostengünstige Analysen. In dieser Arbeit wurde als Transducer eine kapazitive Elektrolyt-Isolator-Silizium- (EIS) Struktur zur markierungsfreien elektrischen Detektion geladener Makromoleküle anhand ihrer intrinsischen Ladung verwendet. Als Modellsystem für die Untersuchung der im EIS-Sensor durch die Ausbildung „planarer“ bzw. „brush“-ähnlicher Molekülschichten induzierten Effekte wurden Polyelektrolyt-Multischichten (PEM) bzw. DNA-Moleküle verwendet. Die Adsorption der positiv und negativ geladenen Polyelektrolyt-Schichten an die Sensor-Oberfläche, sowie der Einfluss der Polyelektrolyt-Konzentration, der Ionenstärke und der Art des Elektrolyten auf das EIS-Signal wurden elektrochemisch untersucht. Zusätzlich wurde die Ausbildung der PEM physikalisch unter Verwendung eines Rasterkraftmikroskopes und der Ellipsometrie charakterisiert. Basierend auf Silizium-Isolator-Silizium-Strukturen wurde zum ersten Mal ein Mikroarray mit „Nanoplate“ EIS-Sensoren entwickelt, die alle auf einem einzigen Chip integriert waren. Dies ermöglicht mittels differenzieller Messanordnungen eine verlässliche Detektion der DNA-Hybridisierung bzw. -Denaturierung. Die Eigenschaften des Biosensors wurden durch Verwendung von Gold-Nanopartikeln für die Immobilisierung der DNA auf der Sensorober-fläche sowie durch eine niedrige Salzkonzentration im Messpuffer entscheidend verbessert. Die Ergebnisse dieser neuen Vorgehensweise wurden mittels Fluoreszenz-Mikroskopie vali-diert. Darüber hinaus wurde ein elektrostatisches Modell für einen EIS-Sensor mit einer „planaren“ und einen weiteren, mit „brush“-ähnlicher Molekularschicht entwickelt. Das Modell prognos-tiziert eine starke Abhängigkeit der Sensorsignalstärke von der Elektrolytkonzentration, der Ladungsdichte auf der Oberfläche und dem Abstand zwischen geladener Schicht und Sensor-oberfläche. Die Prognosen stimmten durchweg gut mit den experimentellen Ergebnissen überein. / Label-free detection of molecular interactions utilizing field-effect devices is one of the most attractive approaches for a new generation of biochips with direct electrical readout for a fast, simple and cost-effective analysis. In this study, a capacitive electrolyte-insulator-semiconductor (EIS) structure was used as transducer for the label-free electrical detection of charged macromolecules via their intrinsic charge. Polyelectrolyte multilayers (PEM) and DNA molecules were utilized as model systems to study the charge effects induced in EIS sensors by the formation of “planar”- and “brush”-like molecular layers, respectively. The layer-by-layer adsorption of positively and negatively charged polyelectrolyte (PE) layers onto the sensor surface as well as the influence of PE concentration, ionic strength and type of the applied electrolyte on the EIS sensor signal was electrochemically studied. In addition, the PEMs build-up was physically characterized using atomic force microscopy, scanning electron microscopy and ellipsometry. An array of on-chip integrated nanoplate EIS sensors based on a silicon-on-insulator structure was developed for the first time, enabling the reliable detection of DNA hybridiza-tion/denaturation in a differential measurement setup. Enhanced DNA biosensor characteris-tics were achieved by the immobilization of DNA molecules on the sensor surface via Au-nanoparticles and used low-concentrated buffer solution for the measurements. The results of this novel approach were validated by means of the fluorescence microscopy method. Furthermore, an electrostatic model for an EIS sensor modified with “planar”- and “brush”-like molecular layers was developed. The model predicts a strong dependence of the sensor signal on the electrolyte concentration, surface charge density and the distance between the charged layer and the sensor surface. This is consistently agreeing with the experimental re-sults.

O transistor de efeito de campo de porta estendida e separada (SEGFET) é um dispositivo alternativo ao tradicional transistor de efeito de campo seletivo a íons (ISFET). A grande vantagem desse dispositivo se refere ao seu fácil processamento, ou seja, se restringe somente a manipulação do eletrodo de porta, evitando processos convencionais de microeletrônica. Neste sentido, sensores iônicos e biossensores podem ser facilmente implementados combinando materiais de reconhecimento químico e/ou biológico. Por sua vez, a técnica de fabricação de filmes finos camada por camada (layer-by-layer, LbL) se mostra versátil para manipulação de diversos tipos de materiais em nível molecular. Materiais orgânicos e inorgânicos podem ser automontados em substratos sólidos por meio da simples adsorção eletrostática formando compósitos com propriedades únicas com o objetivo de serem aplicados em sensores ou biossensores. Neste trabalho, o conceito de dispositivo SEGFET foi combinado com a técnica LbL por meio da manipulação de materiais orgânicos (polieletrólitos, dendrímeros e polianilina) e inorgânicos (TiO2 e V2O5) nanoparticulados a fim de se obter novos sensores de pH e biossensores para a detecção de glicose e uréia, dois importantes analitos de interesse clínico. Numa primeira etapa, diferentes filmes LbL foram produzidos, caracterizados e testados como camada sensível (porta estendida) em dispositivos SEGFETs. Todos os sistemas estudados se mostraram promissores como sensores de pH, ou seja, com uma sensibilidade próxima do valor teórico sugerido pela equação de Nernst (59,15 mV.pH-1). Esses resultados podem ser atribuídos à natureza anfotérica do material da última camada no filme LbL. Numa segunda etapa, as enzima glicose oxidase (GOx) e urease foram convenientemente imobilizadas nos filmes LbL. Pelo fato dessas enzimas gerarem ou consumirem prótons durante a catálise da reação, os filmes LbL modificados enzimaticamente foram utilizados em biossensores de glicose e uréia, apresentando eficiente detecção. Assim, a união de dispositivos SEGFET com a técnica de automontagem se mostrou promissora para construção de sensores e biossensores eficientes e de baixo custo. / Separative extended gate field-effect transistor (SEGFET) device is an alternative to the conventional ion-sensitive field-effect transistor (ISFET). The great advantage of SEGFET refers to its easy processing, i.e., it is limited under only manipulation of the gate electrode, avoiding the conventional microelectronic processes. In this way, ion sensors and biosensors can be easily implemented combining chemical and/or biological recognition materials. In turn, the layer-by-layer (LbL) technique shows be versatile for handling various types of materials at molecular level. In this thesis, the concept of SEGFET device was combined with the LbL technique through the manipulation of organic (polyelectrolytes, dendrimers and poly (aniline)) and inorganic materials (TiO2 and V2O5 nanoparticles) in order to get new pH sensors and biosensors for the detection of glucose and urea, two important analytes of clinical interest. In a first step, different LbL films were produced, characterized and tested as the sensitive layer (extended gate) in SEGFETs devices. All studied systems were promissing as pH sensors, i.e., with a sensitivity close to the theoretical value suggested by Nernst equation (59.15 mV.pH-1). These results can be attributed to the amphoteric nature of the material in the last layer of the LbL films. In a second step, glucose oxidase (GOx) and urease enzymes were conveniently immobilized onto LbL films. Because these enzymes generate or consume protons during catalysis of the reaction, the enzymatically modified LbL films were used in biosensors for glucose and urea, with efficient detection. Thus, the union of SEGFET devices with the LbL technique is promising to building up efficient and low-cost sensors and biosensors.

L'objectif de cette thèse était l’étude de dispositifs électroniques à base de pérovskites hybrides. Dans ce cadre nous avons développé et fabriqué des transistors à effet de champ (FET) ainsi que des cellules solaires à base de perovskite. Dans le cas des transistors, en utilisant des couches minces de pérovskites hybride hautement cristallisées nous avons réalisé des transistors ambipolaires fonctionnant à la température ambiante et présentant une hystérésis faible, une transconductance élevée (pour ce type de matériau), et un rapport Ion / Ioff> 104. Dans le cadre de cette thèse l’utilisation de plusieurs diélectriques nous a permis d’obtenir une forte modulation de la conductance du canal avec des tensions de grille relativement faibles (4-6V). Dans ce cadre l’oxyde d’Hafnium de permittivité relative er=23.5 a montré de très bonnes performances et une très bonne compatibilité pour la croissance de pérovskite hybride. Après plusieurs étapes de polarisation les dispositifs ont présenté un fonctionnement stabilisé et ont été mesurés au cours des cycles consécutifs pendant 14 heures avec peu de changement dans leurs performances. Nous avons mis en évidence que l’augmentation du champ électrique a permis la formation d’un canal de trous à l’interface. La polarisation consécutive des dispositifs à base de HfO2/pérovskite a amené à la création d’un second courant d’électrons et a mis en évidence un fonctionnement ambipolaire final. L’ensemble des dispositifs ont présenté une hystérésis dont l’amplitude était parfois non négligeable. Cela a démontré la présence de charges mobiles ioniques aux interfaces qui influence les courants de sorties du dispositif. Dans la dernière partie de la thèse nous nous sommes intéressés à la croissance de pérovskite hybride pour la production de cellules solaires. Nous avons étudié les deux conditions de croissance suivantes : conditions sous air normal (humidité relative> 60%) et en atmosphère d’azote en boites à gants (humidité relative <0.1 ppm). Par ces deux voies nous avons obtenu respectivement des rendements de conversion photovoltaïque respectivement de 5% et 8%. / The objective of this thesis was the study of electronic devices based on hybrid perovskites. In this context we have developed and produce field effect transistors (FETs) and solar cells based on hybrid perovskite material. In the case of transistors, using thin layers of highly crystallized hybrid perovskites we have made ambipolar transistors operating at room temperature and having low hysteresis, high transconductance (for this type of material) and a ratio of Ion / Ioff > 104. In the context of this thesis, the use of several dielectrics allowed us to obtain a high modulation of the channel conductance with relatively low gate voltages (4-6V). Hafnium oxide with relative permittivity er = 23.5 showed very good performances and a very good compatibility for the hybrid perovskite growth. After several polarization steps the devices exhibited stabilized operation and were measured in consecutive cycles for 14 hours with small change in their performance. We have shown that the increase of the electric field allowed the formation of a hole channel at the interface. The successive polarization of HfO2 / perovskite-based devices led to the creation of a second electron current and demonstrated a final ambipolar device. All the devices presented a hysteresis with amplitude sometimes not negligible. This demonstrated the presence of mobile ion charges at the interfaces that influence the output currents of the device. In the last part of the thesis we focused our work in hybrid perovskite growth for the production of solar cells. We have studied two growth conditions: conditions under normal air (relative humidity> 60%) and nitrogen atmosphere in glove boxes (relative humidity <0.1 ppm). By these two paths we obtained photovoltaic conversion efficiencies of 5% and 8% respectively.

"Circulating tumor cells (CTCs) are cells released into the bloodstream from primary tumors and are suspected to be one of the main causes behind metastatic spreading of cancer. The ability to capture and analyze circulating tumor cells in clinical samples is of great interest in prevailing patient prognosis and clinical management of cancer. Carbon nanotubes, individual rolled-up graphene sheets, have emerged as exciting materials for probing the biomolecular interactions. With diameter of about 1 nm, they can attach themselves to cell surface receptors through specific antibodies and hold a great potential for diagnostic cellular profiling. Carbon nanotubes can be either semiconducting or metallic, and the electronic properties of either type rivals the best known materials. Small size of nanotubes and the ability to functionalize their surface using 1-Pyrenebutanoic Acid, Succinimidyl Ester (PASE), enables a versatile probe for developing a platform for capture and analysis of cancer biomarkers and circulating tumor cells. Although nanotubes have previously been used to electrically detect a variety of molecules and proteins, here for the first time we demonstrate the label free capture of spiked breast cancer cells using ultra-thin carbon nanotube film micro-array devices in a drop of buffy coat and blood. A new statistical approach of using Dynamic Time Warping (DTW) was used to classify the electrical signatures with 90% sensitivity and 90% specificity in blood. These results suggest such label free devices could potentially be useful for clinical capture and further analysis of circulating tumor cells. This thesis will go in-depth the properties of carbon nanotubes, device fabrication and characterization methodologies, functionalization protocols, and experiments in buffy coats and in blood. Combination of nano and biological materials, functionalization protocols and advanced statistical classifiers can potentially enable clinical translation of such devices in the future. "

Thesis (B.S.)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING / Includes bibliographical references. / by David P. Harrahy. / B.S.