Magnetism in a solid | dia, para, ferro, or of other forms | originates majorly from its electrons; one could, infact, ignore the nuclear contribution. There are two types of electrons in a solid: bound, and free (also called itinerant). It is interesting to note that although several experimental techniques exist that measure the total magnetization/ susceptibility of a solid, no experiment directly probes the individual magnetic contributions from the bound and the itinerant electrons. In the past couple of decades, owing to the advent of sophisticated fabrication facilities, certain man-made, (ferro)magnetic materials have come into existence whose carrier concentrations can be tuned extrinsically: doped semiconductors like DMS (diluted magnetic semiconductors) and hexaborides are two such examples. However, whether the (ferro) magnetism in these materials originate from their itinerant carriers is still an open question. A conclusive answer to this question is eagerly awaited by the scientific community; the answer is not only supposed to solve debates related to the physics of ferromagnetism, but, also, should lend a helping hand in selecting right materials to build devices for upcoming exotic technologies such as Spintronics. A novel experimental technique is proposed in this work that directly measures the itinerant carrier magnetism of a solid. The technique is practically demonstrated on the bulk semiconductor: n-type GaAs. A Landau-Peierls itinerant (dia)magnetic susceptibility as low as 1 10 8 cm 3/mol | which is 10 3 times smaller than the magnetic background stemming from the bound electrons in the GaAs host lattice, and 10 times lower than the sensitivity limit of the SQUID | was clearly, and reproducibly detected from samples having carrier concentrations as low as 5 10 15 cm 3. The technique relies on measurements with MIS capacitors fabricated out of the given semiconductor. Unfortunately, as an artifact, such MIS fabrication processes unintentionally, but unavoidably, introduce certain energy levels in the semiconductor band-gap that unwantedly communicate with its bands by trapping and releasing carriers. Such traps lie along the interface of the semiconductor and the oxide. Though clear signals, which match with theoretically estimated signals within acceptable accuracy, have been measured from the itinerant electrons in GaAs, this work demonstrates theoretical calculations showing that the signals decrease in magnitude owing to the presence of such interface traps. Quantifying this decrement comes as an added advantage of this work, because such measurements can then directly probe the MIS interface and find the concentration of the interface traps (Dit) more accurately and precisely than what is done at present. Thus, the experimental technique this work proposes can also probe a given MIS interface, using time-varying magnetic fields, and reveal a more accurate and precise measure of Dit. Otherwise, the existing techniques for measuring Dit su er from imprecision caused by several theoretical assumptions. A more general technique which can extract Dit accurately and precisely, without needing to know the particular physical model that the interface traps follow for a given MIS capacitor, is what one requires at present, to give CMOS technology the direction and impetus it needs to cross-over to the non-Silicon territory. Such a technique is theoretically developed in this work. How a magnetic field a effects the MIS Energy Band Diagram is also derived in the process. The technique that is developed and demonstrated in this thesis, capable of directly probing both the itinerant magnetism and the MIS interface of a given semiconductor, depends on successfully measuring a very small voltage drop across a MIS capacitor when the latter is externally subjected to a high, time-varying magnetic field. This voltage signal originates because the semiconductor's electronic density of states depends on the magnetic field, thus rendering the semiconductor's electron chemical potential, i.e. the Fermi level, magnetic field dependent. The idea of detecting such magnetic field dependence of electron chemical potential was theoretically proposed more than five decades back, but an experimental detection of the phenomenon, in any bulk (i.e. three dimensional) solid, had remained elusive despite numerous trials. Virtually, the topic had been `dead' for the past couple of decades with very few reports (of trials) getting published on it. The primary reason behind such a failure is an interesting spurious effect that arises and overshadows the signal otherwise coming from the magnetic shift of the electron chemical potential. This is the spurious Hall voltage caused by the time-varying magnetic field and the eddy current it induces in the semiconductor following Faraday's Law of Electromagnetic Induction. Unless this Hall voltage can be reduced below a threshold, there is no hope of successfully measuring the sample signal. In this work, we have discussed about this spurious effect in details and have given experimental recipes to avoid it from interfering with the data. Infact the data we publish for n-GaAs is free from any such spurious effects. From that viewpoint, this work becomes the first to report the experimental detection of the magnetic field dependence of a Fermi level in any bulk solid. A common pulse magnet capable of producing high magnetic field pulses, lasting for only some tens of milliseconds, was built and used for the purpose of this work. For certain samples other than GaAs, however, the spurious Hall voltage may be larger and the proposed technique may fail as one may not be able to rule out the spurious effect with the simple recipe demonstrated here for GaAs. In such a case, measurements are encouraged, instead, in a special magnet uniquely developed to rule out the Hall voltage. This magnet was constructed in-house, and can sit on a table-top and generate magnetic fields as high as a few Teslas that can, further, be `temporally shaped' by the user. Such a class of pulse magnets whose pulse waveforms can be programmed over time are called controlled waveform magnets (CWMs) and the work presented in this thesis also demonstrates the construction and calibration of such a CWM.

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Esta Tese aborda o estudo de transistores por efeito de campo orgânicos (OFETs do inglês, Organic Feld-Effect Transistors). Entender o comportamento da carga acumulada no canal do OFET, a qual é responsável pelo processo de condução elétrica no dispositivo, é de grande importância para ajudar a melhorar sua eficiência ou a propor um modelo teórico que descreva o comportamento do transistor em todos os seus regimes de operação. Vários trabalhos na literatura investigam o campo elétrico na camada semicondutora do transistor (ao longo do canal) gerado pela acumulação de cargas, porém nenhum investiga o campo na camada dielétrica de OFETs, que é diretamente proporcional à carga acumulada no canal. Investigou-se inicialmente o campo elétrico na camada dielétrica do dispositivo por meio da espectroscopia vibracional por Geração de Soma de Frequências (espectroscopia SFG do inglês, Sum-Frequency Generation). Espectros SFG obtidos nos dispositivos polarizados exibiram uma banda em ~1720 cm-1, devido ao grupo carbonila da camada dielétrica orgânica (PMMA – poli(metil metacrilato)), cuja a amplitude foi proporcional à voltagem de porta aplicada, indicando que esses grupos polares foram orientados sob ação do intenso campo elétrico no dispositivo. Esse sinal SFG induzido pelo campo pode ser devido a duas contribuições, um termo não linear de segunda ordem (devido à reorientação molecular) e outro de terceira ordem (interação entre os campos ópticos e o campo estático no volume do material). Observamos uma redução quase completa do sinal SFG em altas temperaturas (próximas da Tg do polímero dielétrico), indicando que o mecanismo de reorientação molecular é o responsável pelo sinal SFG gerado. Foram realizadas então medidas preliminares de microscopia SFG para mapear esse sinal SFG ao longo do canal de OFETs a base dos polímeros N2200 (semicondutor) e PMMA (dielétrico). Os resultados conseguem demonstrar a variação da densidade de carga acumulada no canal quando o dispositivo está polarizado e próximo à saturação. Usando Microscopia por Modulação de Carga (microscopia CMM do inglês, Charge Modulation Microscopy), que é outro método não invasivo para investigar a acumulação de cargas em um dispositivo operando, mapeamos a distribuição de carga no canal desses OFETs com alta resolução espacial (sub-micrométrica). Além disso, uma simulação da densidade de carga esperada e dos perfis de CMM foi realizada usando um modelo ambipolar para OFETs. Com base nessas simulações, propusemos uma modulação de onda quadrada do OFET, que permite uma comparação mais direta dos perfis de CMM com o perfil de densidade de carga ao longo do canal do transistor. Usando o esquema proposto, esses perfis foram medidos e comparados com o esperado com base no modelo ambipolar. Em geral os perfis de densidade de carga obtidos concordam bem com o modelo, usando apenas um único parâmetro global ajustável, exceto muito próximo do eletrodo de dreno e no regime de saturação profunda, quando os experimentos apresentam um artefato devido à eletro-absorção e não permitem uma comparação precisa com o modelo. Portanto, espera-se que esta Tese tenha contribuído para o avanço de técnicas de caracterização da distribuição de carga em OFETs, e assim melhorar o entendimento de seus mecanismos de funcionamento. / This Thesis deals with the study of Organic Field Effect Transistors (OFETs). Understanding the behavior of the accumulated charge along the OFET channel, which is responsible for the electrical conduction process in the device, is of great importance for improving its efficiency or proposing a theoretical model that describes the behavior of the transistor in all its operating regimes. Several studies in the literature investigate the electric field in the semiconductor layer of the transistor (along the channel) generated by the charge accumulation, but none investigates the field in the OFET dielectric layer, which is directly proportional to the charge accumulated in the channel. The electric field in the dielectric layer of the device was initially investigated by Sum-Frequency Generation (SFG) vibrational spectroscopy. SFG spectra obtained in the polarized devices exhibited a band at ~ 1720 cm-1, due to the carbonyl group of the organic dielectric layer (PMMA - poly (methyl methacrylate)), whose amplitude was proportional to the applied gate voltage, indicating that these polar groups were oriented by the intense electric field in the device. This field-induced SFG signal may be due to two contributions, a second order non-linear term (due to molecular reorientation) and a third order term (interaction between the optical fields and the static field in the material volume). We observed an almost complete reduction of the SFG signal at high temperatures (close to the Tg of the dielectric polymer), indicating that the molecular reorientation mechanism is responsible for the generated SFG signal. Preliminary SFG microscopy measurements were performed to map this SFG signal along the channel of OFET fabricated with N2200 (semiconductor) and PMMA (dielectric) polymers. The results demonstrate the variation of the accumulated charge density along the channel when the device is polarized and close to saturation. Using Charge Modulation Microscopy (CMM), which is another noninvasive method to investigate the accumulation of charges in an operating device, we mapped the charge distribution in the channel of these OFETs with high spatial resolution (sub-micrometer). In addition, a simulation of the expected charge density and CMM profiles was performed using an ambipolar model for OFETs. Based on these simulations, we proposed a square-wave modulation of the OFET, which allows a more direct comparison of the CMM profiles with the charge density profile. Using the proposed scheme, these profiles along the transistor channel were measured and compared with those expected from the ambipolar model. In general, the obtained charge density profiles agree well with the model, using only a single global adjustable parameter, except very close to the drain electrode and in the deep saturation regime, when the experiments have an artifact due to the electro-absorption and do not allow a precise comparison with the model. Therefore, it is expected that this Thesis has contributed to the advancement of techniques to characterize the charge distribution in OFETs, and thus improve the understanding of its operating mechanisms. Keywords: Field-effect transistors. Organic electronics. Nonlinear optics. Sum-frequency generation. Polarization of dielectrics. Charge modulation microscopy. Metal-insulator-semiconductor capacitor.

Printing since many years has been a well-known high throughput technology for producing replications of graphic arts entities (texts, images, aesthetics, gloss and physical impressions) over large varieties of substrates which are dedicated for various needful applications like newspapers, magazines, posters, official documents, packages, braille, textiles, decorative articles and many more. Due to the fact, that printing is a liquid-solution based replication process, where basic ink and substrate are needed, it is now not only limited to printing of graphic arts. Whenever an ink is deposited over a defined substrate and the process can be multiplied, it can be termed as printing and once the final product contains a functionality other than graphic arts application, it can be called as “Printed Functionality”. Some examples for printed functionalities can be found in the following fields: A. Printed electronics (using inks having electronic properties); B. Printed micro-fluidics (using inks having polymeric and elastic properties for directive purposes); C. 3-Dimensional printing (using inks containing binding properties for developing three dimensional structures); D. Printed photonics (using inks having self-assembling properties for building-up symmetric micro-structures); E. Printed pyroelectrics (using inks containing thermally flammable properties); F. Printed ceramics (using inks with ceramic particles) and G. Printed optics and functional surfaces (using inks with transparency, absorbency and reflective properties). All these mentioned applications require functional inks which in turn exhibits some physical-chemical properties e.g. particle size, particle loading, fluid’s rheological properties etc. These properties determine the feasibility of the material’s deposition (in this case the functional inks) with a suitable printing technology. The inkjet printing technology among others has several advantages such as contactless deposition processability, digitalization (batch size one & turn-over time zero), user defined customization and adaptation, industrial relevance, minimal ink demand for R&Ds, freedom of substrate regularity and µm-scale print accuracy etc. Some of the imminent players in the inkjet printing technology market are Canon, Kodak, Hewlett Packard, Fujifilm Dimatix, Konica Minolta and XAAR. They provide print solutions from small to industrial scale printheads, printers, equipments and accessories for the realization of huge variety of application ideas. The inkjet is a versatile, but yet matured technology which finds its use in various application areas e.g. home office documentation, large format posters, variable data printing, security printing, textile printing, wallpapers, household articles, curved surfaces like bottles, printing over edible items, printing of elevated surfaces etc. And, hence there are several literatures published which show the use of the inkjet printing technology in the development of products for printed electronics. Some of the common examples are development of passive and active devices e.g. capacitors, resistors, thin-film-transistors, photovoltaics, sensors, circuits like logic gates for electronic switching, device arrays for detection purposes, point of care health applications, energy harvesting applications etc. But, the exploitation of the inkjet technology has not been intense enough to declare the industrial relevance of the technology to be utilized as a fabrication tool in the market. Meanwhile, all the researchers around the globe aim at a single goal, which is the development of “Proof of Concept” devices and applications. Thus, here in this dissertation the implementation of the inkjet printing technology as a digital fabrication tool is exploited to manufacture and up-scale the printed electronic products, which can show an industrial relevance to the commercial market. The main motivation why printed electronics is in great demand (scientific point of view) and has intensely emerged in the last decades, is because of the primary challenges faced in the fabrication process steps of the µ-electronics society. It is know that the classically fabricated µ-electronic products are in the market since long time due to their high reliability, consistent performance and defined applications in circuitry. But, what cannot be ignored is the involved fabrication steps promote several demerits such as the in-flexibility towards the fabrication process, material wastage, in-ability to up-scale into larger areas and huge quantities, and physical rigidity. Some of these mentioned problems are commonly seen e.g. spin coating, chemical vapor-phase deposition, physical vapor-phase deposition, atomic layer deposition and sputtering fabrication technologies. In this present dissertation, on the contrary, the challenges linked with the manufacturing process of the µ-electronic devices using the inkjet technology are focused and attempts are made to counteract them. Some of the foreseen challenges are: A. process workflow adaptation in device manufacturing; B. validation and evaluation of device performance; C. industrializing the inkjet technology (manufacturing µ-electronics in massive quantities); D. evaluating the fabrication yield of printed devices; D. Generating statistics regarding reliability and scalability; and E. demonstrating tolerances in electronic performances. These are definitely the challenges which must be overcome, and these key research points are addressed in the dissertation.