Cette étude porte sur l’intégration hybride de transistors à un électron (single-electron transistor, SET) dans un noeud technologique CMOS. Les SETs présentent de forts potentiels, en particulier en termes d’économies d’énergies, mais ne peuvent complètement remplacer le CMOS dans les circuits électriques. Cependant, la combinaison des composants SETs et MOS permet de pallier à ce problème, ouvrant la voie à des circuits à très faible puissance dissipée, et à haute densité d’intégration. Cette thèse se propose d’employer pour la réalisation de SETs dans le back-end-of-line (BEOL), c'est-à-dire dans l’oxyde encapsulant les CMOS, le procédé de fabrication nanodamascène, mis au point par C. Dubuc. / This study deals with the hybrid integration of Single Electron Transistors (SET) on a CMOS technology node. SET devices present high potentiels, particularly in terms of energy efficiency, but can't completely replace CMOS in electrical circuits. However, SETs and CMOS devices combination can solve this issue, opening the way toward very low operating power circuits, and high integration density. This thesis proposes itself to use for Back-End-Of-Line (BEOL) SETs realization, meaning in the oxide encapsulating CMOS, the nanodamascene fabrication process devised by C. Dubuc.

En la presente tesis se muestra una nueva metodología de extracción "inteligente" de modelos circuitales lineales y no lineales para dispositivos MESFET y HEMT, además de efectuar numerosas aportaciones en el campo de las medidas radioeléctricas de dichos dispositivos mediante diseño del hardware y del software necesario para la automatización de las mismas. Por otro lado se presenta un novedoso modelo de Gran Señal para dispositivos HEMT de potencia que da cuenta del fenómeno de la compresión de la transconductancia y es fácilmente implementable en simuladores no lineales comerciales del tipo de MDS, LIBRA, HARMONICA, etc. Además se ha aumentado el rango de validez frecuencial de los modelos de pequeña señal mediante la obtención de las expresiones "exactas" de los modelos usuales de pequeña señal Vendelin-Dambrine, Vickes, Berroth & Bosch, etc. Otra novedad aportada por este trabajo de tesis ha sido aplicar estos modelos lineales a los transistores HEMT, evitando la obtención valores carentes de significado físico como ocurría hasta ahora. Como validación del modelo no lineal de HEMT se han llevado a cabo numerosas simulaciones del mismo en MDS que han sido comparadas con las medidas experimentales realizadas en nuestro laboratorio (Scattering, DC, Pulsadas y Pin/Pout) poniendo de manifiesto la exactitud del modelo. Para validar los modelos de pequeña señal se han efectuado simulaciones con el simulador lineal MMICAD utilizando transistores de diferentes tamaños procedentes de distintas foundries con objeto de visualizar el comportamiento del dispositivo independientemente del origen del mismo. / In this thesis a new methodology for the "intelligent" parameter extraction of linear and non-linear model for GaAs MESFET and HEMT devices is shown, besides numerous contributions in the field of Scattering and DC measurements of this kind of devices by means of hardware design and necessary software for the automation of the same have been done. On the other hand a novel Great Signal model for HEMT devices is presented. This model is capable to model the transconductance compression phenomenon and it is easily to built in commercial non-linear simulators like MDS, LIBRA, Microwave HARMONICA, etc. This work has also increased the frequency range for the usual small-signal models by means of calculate "exact" expressions of them. Another novelty contribution of this thesis is to apply for first time these linear models to HEMT transistors, avoiding the lacking of physical meaning values like it occurred up to now. To make possible the validation of non-linear HEMT model, simulations with MDS software and comparisons with experimental measurements made in our laboratory (Scattering, DC, Pulsed and Pin/ Pout) have been carried out and there was very good agreement between measured and simulated data. To validate small-signal models referred before, simulations with MMICAD software and comparisons between simulated and experimental scattering measurements using transistors of different sizes from several foundries and technological processes have been made.

In dieser Arbeit wurden unterschiedliche Moleküle aus der Klasse der Phthalocyanine (Pc) und Pentacen-Materialien als aktive Schichten in organischen Feldeffekttransistoren (OFETs) mittels organischer Molekularstrahldeposition (OMBD) unter Hochvakuumbedingungen aufgedampft. Die elektrische Charakterisierung von Top-Kontakt (TC) und Bottom-Kontakt (BC) OFET-Konfigurationen, die Auskunft über die Ladungsträgermobilität, die Schwellspannung und das Ein/Aus-Verhältnis gibt, wurde sowohl unter Hochvakuum- als auch unter Umgebungsbedingungen an Luft durchgeführt. Für beide OFET-Konfigurationen wurde Gold für die Source- und Drain-Elektroden genutzt. Aussagen über die Morphologie der untersuchten organischen Schichten, die auf Siliziumsubstraten mit einem 100 nm dicken Siliziumdioxyd (SiO2) Gate-Dielektrikum abgeschieden wurden, wurden mittels Rasterelektronenmikroskopie (SEM) und Rasterkraftmikroskopie (AFM) erhalten. Im Vergleich mit den TC OFETs wurde im Bereich des aktiven Kanals in den BC OFETs die Bildung einer höheren Anzahl von Körnern und Korngrenzen gefunden, welche zur Degradation dieser Bauelemente speziell bei Atmosphärenexposition beiträgt. Es wurden die nachfolgenden fünf Moleküle aus der Klasse der Pc untersucht: Kupferphthalocyanin (CuPc), Fluoriertes Kupferphthalocyanin (F16CuPc), Kobaltphthalocyanin (CoPc), Titanylphthalocyanin (TiOPc), und Lutetium-bis-Phthalocyanin (LuPc2). Diese Moleküle wurden mit dem Ziel ausgewählt, die Performance der OFETs unter vergleichbaren Präparationsbedingungen zu testen, wenn das zentrale Metallatom, die Halbleitereigenschaften oder die molekulare Geometrie geändert werden. Durch die Fluorierung (F16CuPc) wurde eine Änderung im Leitungsverhalten von CuPc von p-Typ zum n-Typ erreicht und in der elektrischen Charakteristik der OFETs nachgewiesen. Diese Resultate wurden ebenfalls mittels Kelvin-Sonden-Kraftmikroskopie (KPFM) erhalten. Der Einfluss der Molekülgeometrie auf die Performance der Bauelemente wurde durch die Änderung der Gestalt der Moleküle von planar (CuPc, F16CuPc, CoPc) zu nicht planaren Einfach- (TiOPc) und nicht planaren Doppeldeckermolekülen (LuPc2) untersucht. Eine höhere OFET-Performance wurde erreicht, wenn planare Pc-Materialien für die Bildung der aktiven Schicht verwendet wurden. Das kann teilweise auf die Morphologie der Pc-Schichten zurückgeführt werden. AFM-Aufnahmen zeigen, dass im Vergleich mit nicht planaren Molekülen größere Körner und deshalb eine geringere Anzahl von Korngrenzen gebildet werden, wenn planare Pc-Moleküle verwendet werden. Für den Fall von TC CuPc OFETs wurde gezeigt, dass die Performance der Bauelemente verbessert werden kann, wenn das Gate-Dielektrikum mit einer selbstorganisierten Monoschicht von n-Octadecyltrichlorosilan modifiziert wird oder wenn das Substrat während der Aufdampfung der CuPc-Schicht auf einer höheren Temperatur gehalten wird. Für die Klasse der Pentacen-Materialien wurde ein Vergleich zwischen der Performance von BC OFETs, die die kürzlich synthetisierten fluorierten n-Typ Pentacenquinon-Moleküle nutzen, und denen, die die p-Typ Pentacen-Moleküle nutzen, präsentiert. Das große Erfordernis hochreine Materialien zu verwenden, um eine Degradation der OFETs zu vermeiden, wurde durch Durchführung von Mehrfachmessungen an den OFET-Bauelementen bestätigt. Aus diesen Experimenten lassen sich Informationen bzgl. der Störstellen an der Grenzfläche organische Schicht/SiO2 ableiten. Weiterhin wurde für einige der untersuchten Moleküle die Performance von BC OFETs unter dem Einfluss von unterschiedlichen Gasen gezeigt.

Die vorliegende Arbeit befasst sich mit der Simulation und Modellierung organischer Feldeffekt-Transistoren (OFETs). Mittels numerischer Simulationen wurden detaillierte Untersuchungen zu mehreren Problemstellungen durchgeführt. So wurde der Einfluss einer exponentiellen Verteilung von Trapzuständen, entsprechend dem sogenannten a-Si- oder TFT-Modell, auf die Transistorkennlinien untersucht. Dieses Modell dient der Beschreibung von Dünnschicht-Transistoren mit amorphen Silizium als aktiver Schicht und wird teils auch für organische Transistoren als zutreffend angesehen. Dieser Sachverhalt wird jedoch erstmals in dieser Arbeit detailliert untersucht und simulierte Kennlinien mit gemessenen Kennlinien von OFETs verglichen. Insbesondere aufgrund der Dominanz von Hysterese-Effekten in experimentellen Kennlinien ist jedoch eine endgültige Aussage über die Gültigkeit des a-Si-Modells schwierig. Neben dem a-Si-Modell werden auch noch andere Modelle diskutiert, z.B. Hopping-Transport zwischen exponentiell verteilten lokalisierten Zuständen (Vissenberg, Matters). Diese Modelle liefern, abhängig von den zu wählenden Modellparametern, zum Teil ähnliche Abhängigkeiten. Möglicherweise müssen die zu wählenden Modellparameter selbst separat gemessen werden, um eindeutige Schlussfolgerungen über den zugrundeliegenden Transportmechanismus ziehen zu können. Unerwünschte Hysterese-Effekte treten dabei sowohl in Transistorkennlinien als auch in Kapazitäts-Spannungs- (CV-) Kennlinien organischer MOS-Kondensatoren auf. Diese Effekte sind bisher weder hinreichend experimentell charakterisiert noch von ihren Ursachen her verstanden. In der Literatur findet man Annahmen, dass die Umladung von Trapzuständen oder bewegliche Ionen ursächlich sein könnten. In einer umfangreichen Studie wurde daher der Einfluß von Trapzuständen auf quasistatische CV-Kennlinien organischer MOS-Kondensatoren untersucht und daraus resultierende Hysterese-Formen vorgestellt. Aus den Ergebnissen läßt sich schlussfolgern, dass allein die Umladung von Trapzuständen nicht Ursache für die experimentell beobachteten Hysteresen in organischen Bauelementen sein kann. Eine mögliche Erklärung für diese Hysterese-Effekte wird vorgeschlagen und diskutiert. In einem weiteren Teil der Arbeit wird im Detail die Arbeitsweise des source-gated Dünnschicht-Transistors (SGT) aufgezeigt, ein Transistortyp, welcher erst kürzlich in der Literatur eingeführt wurde. Dies geschieht am Beispiel eines Transistors auf der Basis von a-Si als aktiver Schicht, die Ergebnisse lassen sich jedoch analog auch auf organische Transistoren übertragen. Es wird geschlussfolgert, dass der SGT ein gewöhnlich betriebener Dünnschicht-Transistor ist, limitiert durch das Sourcegebiet mit großem Widerstand. Die detaillierte Untersuchung des SGT führt somit auf eine Beschreibung, die im Gegensatz zur ursprünglich verbal diskutierten Arbeitsweise steht. Ambipolare organische Feldeffekt-Transistoren sind ein weiterer Gegenstand der Arbeit. Bei der Beschreibung ambipolarer Transistoren vernachlässigen bisherige Modelle sowohl die Kontakteigenschaften als auch die Rekombination von Ladungsträgern. Beides wird hingegen in den vorgestellten numerischen Simulationen erstmalig berücksichtigt. Anhand eines Einschicht-Modellsystems wurde die grundlegende Arbeitsweise von ambipolaren (double-injection) OFETs untersucht. Es wird der entscheidende Einfluß der Kontakte sowie die Abhängigkeit gegenüber Variationen von Materialparametern geklärt. Sowohl der Kontakteinfluß als auch Rekombination sind entscheidend für die Arbeitsweise. Zusätzlich werden Möglichkeiten und Einschränkungen für die Datenanalyse mittels einfacher analytischer Ausdrücke aufgezeigt. Es zeigte sich, dass diese nicht immer zur Auswertung von Kennlinien herangezogen werden dürfen. Weiterhin werden erste Simulationsergebnisse eines ambipolaren organischen Heterostruktur-TFTs mit experimentellen Daten verglichen.

Ce manuscrit expose des travaux effectués entre 1994 et 2004 sur la fiabilité des composants à base de structures MOS et la fiabilité des oxydes ultra-minces de SiO2 (<10nm) utilisés comme isolant de grille dans ces composants. Nous avons établi un lien entre courants de fuite dans l'oxyde (SILC) et injection de porteurs chauds, principalement les trous chauds, dans les oxydes de 3.8 et 4.7nm. La dépendance en champ et en température du SILC soutient un modèle d'effet tunnel assisté par des défauts neutres barycentriques dans l'oxyde, même si une composante partielle de type Schottky est identifiable. Pour les claquages de type Soft-breakdown relevés, nous avons proposé un modèle simple, fondé sur un rétrécissement local de l'épaisseur d'oxyde. Le phénomène LVSILC, typique de la structure MOS en déplétion, est mis en évidence suite à des stress à tension constante pour des oxydes entre 2.5 et 1.2 nm. Nous proposons de l'interpréter comme un effet tunnel assisté par des niveaux proches des bandes de conduction ou de valence de la densité d'états d'interface. Les mécanismes de génération sont principalement déterminés par l'énergie des porteurs injectés (y compris dans le cas d'injections de porteurs chauds), et génèrent une loi d'accélération en VG pour le vieillissement en mode tunnel direct. On établit une loi générale, donnant la probabilité de création de défauts en fonction des paramètres qui déterminent l'énergie des porteurs injectés. <br />Nos études sur les porteurs chauds nous ont aussi amené à étudier la fiabilité de transistor MOSFET lors de contraintes dynamiques (AC), caractéristiques des séquences de polarisation en mode normal de fonctionnement. Le résultat pratique de ce travail est la mise en oeuvre d'une méthodologie s'inspirant de l'hypothèse quasi-statique pour la prévision des durées de vie AC. Cette méthodologie, éprouvée et comparée aux résultats de mesure dans un certains nombre de cas où sa validité est reconnue, est appliquée au cas plus complexe du transistor de passage NMOS. L'accord reste satisfaisant, mais nous avons également mis en évidence les limitations de cette technique lors de séquences faisant intervenir des relaxations, des périodes de dépiégegage ou des dégradations bi-directionnelles.<br />Concernant le lien entre les étapes du procédé et la fiabilité, nous avons étudié l'influence d'une étape d'implantation ionique à haute énergie, qui induit un dégât dans le volume du semi-conducteur détecté électriquement par C(V), mais aussi des courants de fuite similaires au SILC (IILC Implantation Induced Leakage Current). Nous avons mis au point une méthodologie optimisée de détection du Wafer Charging, utilisant des injections très courtes de porteurs chauds (au pic de courant électronique) dans le transistor PMOS. Cette méthode s'est révélée plus sensible et plus révélatrice que les injections pratiquées en régime Fowler-Nordheim ou la simple étude paramétrique pour détecter les défauts latents issus du charging dans les oxydes minces. Enfin, nous avons identifié par DLTS les défauts issus d'une contamination au Fer dans le Silicium (paire Fe-B et Fer interstitiel Fei) et avons observé la re-transformation spontanée du Fei en paire Fe-B en quelques heures.

Ferroelectric field effect transistor (FeFET) memories based on a new type of ferroelectric material (silicon doped hafnium oxide) were studied within the scope of the present work. Utilisation of silicon doped hafnium oxide (Si:HfO2) thin films instead of conventional perovskite ferroelectrics as a functional layer in FeFETs provides compatibility to the CMOS process as well as improved device scalability. The influence of different process parameters on the properties of Si:HfO2 thin films was analysed in order to gain better insight into the occurrence of ferroelectricity in this system. A subsequent examination of the potential of this material as well as its possible limitations with the respect to the application in non-volatile memories followed. The Si:HfO2-based ferroelectric transistors that were fully integrated into the state-of-the-art high-k metal gate CMOS technology were studied in this work for the first time. The memory performance of these devices scaled down to 28 nm gate length was investigated. Special attention was paid to the charge trapping phenomenon shown to significantly affect the device behaviour.

Spintronics (spin based electronics) is a relatively new topic of research which is important both from the fundamental and technological point of view. In conventional electronics charge of the electron is manipulated and controlled to realize electronic devices. Spintronics uses charge as well as the spin degree of freedom of electrons, which is completely ignored in the charge based devices. This new device concept brings in a whole new set of device possibilities with potential advantages like higher speed, greater efficiency, non-volatility, reduced power consumption etc. The first realization of the spintronic device happened in 1989, owing to the discovery of the Giant Magneto-resistive (GMR) structure showing a large resistance change by the application of an external magnetic field. Nobel Prize in Physics is awarded for this discovery in 2007. In less than ten years, such devices moved from the lab to commercial devices, as read head sensors in hard disc drives. This new sensor led to an unprecedented yearly growth in the area l density of bits in a magnetic disc drive. Since 2005, another spintronic device known as Magnetic Tunnel Junction (MTJ) which shows a better performance replaced the existing GMR structures in the read heads. Another device which can potentially replace Si based Dynamic Random Access Memory (DRAM) is Magneto-resistive Random Access Memory (MRAM). Being magnetic it is non-volatile, which means not only it retains its memory with the power turned off but also there is no constant power required for frequent refreshing. This can save a lot of power(~ 10-15 Watts in a DRAM), which is quite significant amount for any portable device which runs under battery. Prototype of a commercial MRAM is also made during 2004-2005 by Infineon and Freescale Semiconductors. Recent development has shown switching of magnetic moment by spin-polarised currents (known as spin transfer torque), electric fields, and photonic fields. Instead of Oersted field switching in the conventional MRAM devices, spin torque effect can also be used to switch a magnetic element more efficiently. Recently Spin-Torque MRAM has gained lot of interest due to it’s less power consumption during the writing process. A continuous research effort is going on in realizing other proposed spintronic devices, such as Spin Torque Oscillator, Spin Field Effect Transistor , Race Track Memory etc. which are yet to get realized or yet to make their entry in the commercial devices. Spintronics can be divided in to two broad subfields viz.(1) Semiconductor Spintronics and (2) Metallic Spintronics. Most of the devices belong to the second class whereas the former one is rich in fundamental science and not yet cleared its path towards the world of application. Any spintronic device requires ferromagnetic material which is generally the source of spin polarized electrons. For semiconductor spintronic devices, the main obstacle is the non-existence of the ferromagnetic semiconductor above room temperature (RT). So the development in this direction is very much dependent on the material science research and discovery of novel material systems. Almost a decade back, Dilute Magnetic Semiconductors (DMS) are proposed to behaving RT ferromagnetism. As a result an intense theoretical and experimental research is being carried out since then on these materials. Still a general consensus is lacking both in terms of theory as well as experiment. There are many methodologies and thin film deposition protocols have been followed by different research groups to realize spintronic device concepts. The deposition techniques such as magnetron sputtering, molecular beam epitaxy have been found very efficient for growing metallic spintronic devices. For semiconductor spintronics especially in the area of Dilute Magnetic Semiconductors (DMS) pulsed laser ablation is also considered to be a viable technique. Even though pulsed laser ablation is a very powerful technique to prepare stoichiometric multi-component oxide films, it’s viability for the growth of metallic films and multilayer is considered to be limited. In this regard, we have used pulsed laser ablation to prepare pure and Co doped ZnO films, to examine the magnetic and magneto-transport behavior of these oxides. In addition extensive work has been carried out to optimize and reproducibly prepare metallic multilayer by Pulsed Laser Deposition to realize Spin Valve (SV) effect, which proves the viability of this technique for making metallic multilayer. This thesis deals with the study of Pulsed Laser Deposition(PLD) deposited DMSs and metallic SVs. The thesis is organized into seven chapters as described below: • Chapter:1 This chapter gives an introduction to Spintronics and the different device structures. It is followed by a brief description of the motivation of the present work. Since magnetism is at the heart of the spintronics, next we attempt to introduce some of the basic concepts in magnetism, which are related to the topics discussed in the following chapters. We discuss about various exchange interactions responsible for the long range ferromagnetic ordering below Curie temperature in different compounds. Other magnetic properties are also discussed. Then another important phenomenon called magnetic anisotropy is brought in. We discuss the origin of different types of anisotropy in materials. These anisotropies are also responsible for magnetic domain formation. Then a description of the different types of domain walls are introduced. Unlike conventional electronics, spintronics deals with spin polarized current. A short description of spin polarization from the band picture and concept of half-metal is introduced. The next part (Section-I) of this chapter gives an overview of the challenges in semiconductor spintronics. The spin injection efficiency from a ferromagnetic metal to a semiconductor is found to be poor. This problem is attributed to the conductivity mismatch at the interface. DMS materials can be potential candidates in order to solve this problem. Ferromagnetism in these proposed materials cannot be explained in terms of the standard exchange mechanisms. A model was first proposed for the hole doped system based on Zener model. A more apt model for the n-doped high dielectric materials is then proposed based on Bound Magnetic Polarons (BMP). These models for the unusual ferromagnetism are briefly discussed. Although ferromagnetism is observed by different groups, often questions are raised about the intrinsic origin of this behavior and the topic is still under debate. In this study we have tried to correlate the magnetic property with the transport property as the transport properties are generally not affected much by the presence of external impurities and probes the intrinsic property of the material. Transport and the magneto-transport in disordered materials in general are discussed. A specific model proposed for degenerate semiconductors, which is used for fitting our experimental data is explained. As the ferromagnetism in these materials are generally found to be related to the defects, different types of possible defects are described. Section-II deals with the metallic SV devices. In the history of spintronics, this is one of the most basic and most studied structures, but still having a lot of interest both fundamentally and technologically. A brief history of this discovery and a chronological progress in the device structure is discussed. Our work focuses on the metallic spin valve (SV) structures. Different types of SVs and their properties are explained. In a SV structure one of the ferromagnets (FM) is pinned using an adjuscent antiferromagnetic layer by an effect called exchange bias. A brief description of exchange bias and the effects of different parameters is given. This is followed by a discussion about the theory of GMR which deals with the spin dependent scattering at the bulk and at the interfaces, their relative contributions, effect of the band matching etc. A simple resistor model is used to explain the qualitative behavior of these SVs. The chapter is concluded with a brief summery and applications. • Chapter:2 This chapter provides a brief description of some of the experimental apparatus that are used to perform various experiments. The chapter is organized according to the general functionality of the techniques. This includes different thin film deposition techniques which are used depending on the requirements and also for comparing the properties of the samples, grown by different techniques. Structural, spectroscopic, magnetic and different microscopy techniques which are extensively used throughout, are discussed and their working principles are explained. This work also involves nano/microstructuring of devices. Mainly two structuring techniques are used viz. e-beam lithography and optical lithography by laser writer. In this section we will be discussing about these two techniques and other associated techniques like lift-off, etching etc. Effect of different parameters on the device structures are highlighted. • Chapter:3 Chapter-3 deals with the synthesis and characterization of the pure and 5% Co doped ZnO bulk samples. First a brief introduction about the ZnO crystal structure, band structure and other properties are given followed by the synthesis technique followed in our study. Synthesis is done by low temeperature in organic co-precipitation method. This liquid phase synthesis gives better homogeniety. As-grown sample is also sintered at a higher temperature. Structural study confirms the proper synthesis of the intended compound. Spectroscopic as well as magnetic study of the bulk doped sample indicates the presence of Co nano clusters in the low temperature synthesized sample, whereas after sintering indication of Co2+ is observed which reflects in the magnetic property as well. These samples are used as target material for laser ablation. • Chapter:4 Chapter-4 presents the results of the pure and Co doped ZnO thin film samples. Thin films are grown by PLD method on r-plane Sapphire substrates. Details of the growth technique and the deposition parameters are explained. Our result shows that 5% Co doped ZnO thin film is ferromagnetic in nature as expected in a DMS material, although the film is grown using a paramagnetic target. We also report that pure ZnO grown in an oxygen deficient condition giving ferromagnetic behavior. Not only that, the obtained saturation moment is much higher compared to the Co doped sample. We have demonstrated that the FM can be tuned by tuning the oxygen content and FM disappears when the film is annealed in an oxygen environment .But for the Co doped sample magnetic property could not be tuned much as Co doping stabilizes the surface states. To exclude the possibilities of the extrinsic origin we have done a detailed magneto-transport study for both doped and undoped films. For ZnO, we have shown a one to one correlation of the magnetic and magneto-transport data which further supports the fact that the obtained magnetic behavior is intrinsic. Fitting of the magnetorsistance (MR) data for the pure and Co doped ZnO samples is done using a semi-empirical formula, consisting of both positive and negative MR terms originally proposed for degenerate semiconductors .Excellent agreement of the experimental data is found with the formula. For pure ZnO sample we have extracted the mobility, carrier concentration etc .by Hall measurement. The fabrication steps of Hall bar sample which involves optical lithography and ion beam etching are discussed. 3D e-e interaction induced transport mechanism is found to be dominant in case of oxygen deficient pure ZnO. • Chapter:5 Chapter-5 demonstrates the tuning of band gap of ZnO by alloying with MgO. By changing the ZnO:MgO ratio in PLD grown films, we could tune the band gap over a wide range. Composition alanalysis is done by Rutherford Back-Scattering. Structural and spectroscopic studies are carried out, which shows tuning of band gap upon alloying with MgO. We could tune ZnO band gap from 3.3eV to 3.92eV by30% MgO alloying, while retaining the Wurtzite crystal structure. • Chapter:6 Chapter-6 demonstrates the metallic Pseudo Spin Valve (PSV) structures grown by sputtering and by PLD. Main focus of this chapter is to show that, PLD can be aviable technique for making metallic PSV and Spin Valve (SV) structures. This is almost an unexplored technique for growing metallic thin film SVs, as it is evident in the literature. NiFe and Co are used as the soft and hard FM layers respectively, Au and Cu are used as the spacer layer. FeMn is used for pinning the Co layer in case of the SV structures. The first section describes the properties of these materials and then substrate preparation, deposition parameters etc. are explained in details. Properties of sputter deposited PSV structures are also described. Thickness variation of different layers, double PSV structure and angular variation of the MR properties are presented. Generally two measurement geometries are followed for the SV measurements viz.(1) Current In Plane (CIP) and (2) Current Perpendicular to Plane(CPP). We have carried out MR studies in both the measurement geometries. Measurement in CPP geometry is much more involved than CIP and need structuring with multiple lithography steps. CPP measurement geometry scheme and the process steps are discussed. For this measurement a special ac bridge technique is followed which is also discussed. In the next part we have demonstrated PSV and SV structures, grown, using PLD in an Ultra High Vacuum (UHV) system. Not only that, we have obtained a CIPMR as high as 3.3%. PLD is generally thought to be a technique for oxide deposition and metallic multilayers are not deposited due to particulate formation, high enegy of the adatom species which can lead to inter-mixing at the interface etc. But in this study we have shown that by properly tuning the deposition parameters, it is possible to grow SVs using PLD. We have found the roughness of the PLD grown films are much lower compared to the sputtered films. For top SV structures we have obtained exchange bias even in the absence of applied field during deposition. This effect is observed by performing magnetic and magneto-resistance measurements. Effect of different layer thicknesses, field annealing etc. are discussed. Two different spacer layers are used and their properties are compared. We have found that the interface engineered structures are giving highest MR among the different samples. Then a conclusion of our study is presented followed by a discussion on the difficulties and challenges faced for optimizing the PLD grown SVs. • Chapter:7 Finally, in Chapter-7, various results are summarized and a broad outlook is given. Perspectives for the continuation of the present work is also given.

Process variability is a major challenge for the design of nano scale MOSFETs due to fundamental physical limits as well as process control limitations. As the size of the devices is scales down to improve performance, the circuit becomes more sensitive to the process variations. Thus, it is necessary to have a device model that can predict the variations of device characteristics. Statistical modeling method is a potential solution for this problem. The novelty of the work is that we connect BSIM parameters directly to the underlying process parameters. This is very useful for fabs to optimize and control the specific processes to achieve certain circuit metric. This methodology and framework is extendable to any future technologies, because we used a device independent, but process depended frame work In the first part of this thesis, presents the design of nominal MOS devices with 28 nm physical gate length. The device is optimized to meet the specification of low standby power technology specification of International Technology Roadmap for Semiconductors ITRS(2012). Design of experiments are conducted and the following parameters gate length, oxide thickness, halo concentration, anneal temperature and title angle of halo doping are identified as the critical process parameters. The device performance factors saturation current, sub threshold current, output impendence and transconductance are examined under process variabilty. In the subsequent sections of the thesis, BSIM parameter extraction of MOS devices using the software ICCAP is presented. The variability of the spice parameters due to process variation is extracted. Using the extracted data a new BSIM interpolated model for a variability aware circuit design is proposed assume a single process parameter is varying. The model validation is done and error in ICCAP extraction method for process variability is less than 10% for all process variation condition in 3σ range. In the next section, proposes LUT model and interpolated method for a variability aware circuit design for single parameter variation. The error in LUT method for process variability reports less than 3% for all process variation condition in 3σ range. The error in perdition of drain current and intrinsic gain for LUT model files are very close to the result of device simulation. The focus of the work was to established effective method to interlink process and SPICE parameters under variability. This required generating a large number of BSIM parameter ducks. Since there could be some inaccuracy in large set of BSIM parameters, we used LUT as a golden standard. We used LUT modeling as a benchmark for validation of our BSIM3 model In the final section of thesis, impact of multi parameter variation of the processes in device performance is modelled using RSM method; the model is verified using ANOVA method. Models are found to be sufficient and stable. The reported error is less than 1% in all cases. Monte Carlo simulation confirms stability and repeatability of the model. The model for random variabilty of process parameters are formulated using BSIM and compared with the LUT model. The model was tested using a benchmark circuit. The maximum error in Monte Carlo simulation is found to be less than 3% for output current and less than 8% for output impedance.

The Thesis reports charge transport studies on conducting polymers, polymer carbon nanotube composites and organic semiconductor devices. Conducting and semiconducting polymers consisting of π-conjugated chains have attracted considerable attention as they combine the optoelectronic properties of semiconductors with mechanical properties and processing advantages of plastics. The chemical/electrochemical/photodoping of these semiconducting polymers can tune the Fermi levels and conductivity in a controlled way, and hence the properties of devices can be easily tailored to suit in several applications. Carbon nanotube (CNT) is another another novel promising material for electronic/optoelectronic applications. Lately there has been a great interest in developing composites of polymer and CNTs to utilize the advantages of both CNTs and polymers. The inclusion of CNTs in polymers improves the mechanical, electrical and thermal properties since the aspect ratio (ratio of length to diameter) is very large, as well its density is rather low. The Thesis consists of 6 chapters. First chapter is a brief introduction of general and transport properties of conducting polymers and polymer-carbon nanotube composites. In Chapter 2, the sample preparation and experimental techniques used in this work are discussed. The charge transport in poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) is presented in Chapter 3. Chapter 4 focuses on the transport measurements in the polymer-CNT composite samples. Chapter 5 elaborates the ac and dc characterization of organic field-effect transistors (OFETs). And chapter 6 presents the conclusion and future directions of the work that has been presented in the Thesis. Chapter 1: In the scientific and technological revolution of the last few years, the study of high performance materials has been steadily increasing including the study of carbon-based materials. Conducting polymers have special properties that are interesting for this new technology. The charge transport in conjugated polymers is important to optimize the performance of devices. The discovery of CNTs with exceptional thermal, mechanical, optical, electrical and structural properties has facilitated the synthesis of new type of nanocomposites with very interesting properties. Nanocomposites represent a guest-host matrix consisting of easily processible functionalized conjugated polymer as host, incorporating CNTs as fillers with versatile electronic and magnetic properties, which provide a wide range of technological applications. To optimize their electrical properties it is essential to understand the charge transport mechanism in detail. Chapter 2: The multi-wall carbon nanotubes (MWNTs) grown by thermal chemical vapor deposition (CVD) are mixed with a 1:1 mixture of 98% H2SO4 and 70% HNO3 to produce sulfonic acid functionalized multi-wall carbon nanotubes (s-MWNTs). The s-MWNTs are dispersed in a solution of Nafion by ultrasonication and then cast on a glass substrate and slowly dried by moderate heating to obtain the composite films. Polyaniline (PANI)-MWNT composites were obtained by carrying out the chemical synthesis of nanofibrilar PANI in the presence of CNTs. This water dispersible PANIMWNT composite contains well segregated MWNTs partially coated by nanofibrilar PANI. The ac and dc charge transport measurements suggest hopping transport in these materials. OFETs are fabricated with pentacene, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT) and poly(3-hexylthiophene) (P3HT) as active materials. A novel technique is used to characterize the acphotoresponse of these OFETs. Chapter 3: Charge transport studies on PEDOT-PSS have been carried out and found that it correlates with the morphology. The dc conductivity of PEDOT–PSS shows enhanced delocalization of the carriers upon the addition of dimethyl sulfoxide (DMSO) and this is attributed to the extended chain conformation. PEDOT-PSS is known to form a phase-segregated material comprising highly conducting PEDOT grains that are surrounded by a sea of weakly ionic-conducting PSS and a wide variation in the charge transport properties of PEDOT-PSS films is attributed to the degree of phasesegregation of the excess insulating polyanion. The magnetotransport and temperature dependent ac transport parameters across different conducting grades of PEDOT-PSS processed with DMSO were compared. Depending on the subtle alterations in morphology, the transport at low temperatures is shown to vary from the hopping regime (Baytron P) to critical regime of the metal-insulator transition (Baytron PH510) There is a significant positive magnetoresistance (MR) for P–films, but this is considerably less in case of PH510-film. From the low temperature ac conductance it is found that the onset frequency for PH510 is nearly temperature independent, whereas in P type it is strongly temperature dependent, again showing the superior transport in PH510. The presence of ‘shorter network connections’ together with a very weak temperature dependence down to ~ 5 K, suggest that the limitation on transport in PH510 arises from the connectivity within the PEDOT-rich grain rather than transport via the PSS barriers. Chapter 4: DC and AC charge transport properties of Nafion s-MWNT and PANI-MWNT composites are studied. Such a detailed investigation is required to optimize the correlation among morphology and transport properties in these composites towards applications in field-effect transistors, antistatic coating, electromagnetic shielding, etc. The conductivity in Nafion s-MWNT shows a percolative transport with percolation threshold pc = 0.42 whereas such a sharp percolation is absent in PANI-MWNT composite since the conduction via PANI matrix smears out the onset of rapid increase in conductivity. Three-dimensional variable range hopping (VRH) transport is observed in Nafion s-MWNT composites. The positive and negative MR data on 10 wt. % sample are analyzed by taking into account forward interference mechanism (negative MR) and wave-function shrinkage (positive MR), and the carrier scattering is observed to be in the weak limit. The electric-field dependence, measured to high fields, follows the predictions of hopping transport in high electric-field regime. The ac conductivity in 1 wt. % sample follows a power law: ( )  A s , and s decreases with increasing temperature as expected in the correlated barrier hopping (CBH) model. In general, Mott’s VRH transport is observed in PANI-MWNT samples. It is found that the MWNTs are sparingly adhered with PANI coatings, and this facilitates inter-tube hopping at low temperatures. The negative MR of MWNT-PANI composites suggest that the electronic transport at low temperatures is dominated by MWNT network. AC impedance measurements at low temperatures with different MWNT loading show that ac conductivity become temperature independent as the MWNT content increases. The onset frequency for the increase in conductivity is observed to be strongly dependent on the MWNT weight percentage, and the ac conductivity can be scaled onto a master curve given by  ( )  0[1 k( 0 )s ]. Chapter 5: Organic field-effect transistors (OFETs) based on small molecules and polymers have attracted considerable attention due to their unique advantages, such as low cost of fabrication, ease of processing and mechanical flexibility. Impedance characterization of these devices can identify the circuit elements present in addition to the source-drain (SD) channel, and the bottlenecks in charge transport can be identified. The charge carrier trapping at various interfaces and in the semiconductor can be estimated from the dc and ac impedance measurements under illumination. The equivalent circuit parameters for a pentacene OFET are determined from low frequency impedance measurements in the dark as well as under light illumination. The charge accumulation at organic semiconductor–metal interface and dielectric semiconductor interface is monitored from the response to light as an additional parameter to find out the contributions arising from photovoltaic and photoconductive effects. The shift in threshold voltage is due to the accumulation of photogenerated carriers under SD electrodes and at dielectric–semiconductor interface, and also this dominates the carrier transport. Similar charge trapping is observed in an OFET with PBTTT as the active material. This novel method can be used to differentiate the photophysical phenomena occurring in the bulk from that at the metal-semiconductor interface for the polymer. Chapter 6: The conclusions from the various works presented in the thesis are coherently summarized in this chapter. Thoughts for future directions are also summed up.

Aujourd'hui, avec l'augmentation de la population, la consommation de médicaments et de produits phytosanitaires dans l'agriculture a considérablement augmenté. Cela devient inquiétant car une grande partie de ces molécules, rejetée dans l'environnement, ne sont pas bien éliminées par les stations d'épuration (lorsqu'elles existent). En trop grande quantité, ces produits deviennent des poisons pour tous les organismes vivants, y compris l’Homme.Des méthodes analytiques classiques pour la mesure de ces produits chimiques existent déjà (méthodes séparatives classiques telles que la chromatographie en phase gazeuse, la chromatographie liquide à haute performance, éventuellement couplée à la spectrométrie de masse, etc.). Cependant, même si elles sont extrêmement précises et fiables, ces techniques sont difficiles à appliquer pour la surveillance sur site et sont généralement coûteuses. Pour cette raison, ma thèse se concentre sur de nouvelles approches analytiques pour détecter de petites molécules en milieu aqueux, telles que ces polluants. Dans une première partie de mon travail, j’ai développé un immunocapteur basé sur une complexation compétitive originale et sur une transduction électrochimique (ampérométrique), pour la détection du diclofénac, un anti - inflammatoire non stéroïdien généralement utilisé pour réduire l’inflammation et soulager la douleur. L'électrode de travail a été fonctionnalisée par deux sels de diazonium, l'un utilisé comme sonde moléculaire (un dérivé du diclofénac couplé à une arylamine) et l'autre comme sonde redox (une quinone) également couplée à une arylamine, capable de transduire l'association haptène-anticorps par une variation de son électroactivité ; en particulier, la transduction a été conçue pour délivrer une augmentation de courant lors de la détection du diclofénac (soit une détection « signal-on »). J’ai montré une limite de détection d’environ 20 fM dans l'eau du robinet, ce qui rend ce type de capteur très compétitif. Dans la suite de mon travail, j'ai conservé la même approche de transduction originale (immunoreconnaissance compétitive) mais appliquée à un transistor à effet de champ organique à grille électrolytique (EGOFET) dont le semiconducteur est le poly (N-alkyldiketopyrrolo-pyrrole dithiénylthiéno [3,2-b ] thiophène) (DPP-DTT) et dont l'électrode de grille a été fonctionnalisée par électrogreffage d'un sel de diazonium fonctionnel capable de lier un anticorps spécifique de l'acide 2,4-dichlorophénoxyacétique (2,4-D), un herbicide courant. Le design de la sonde moléculaire a été rationalisée par modélisation moléculaire afin d’optimiser la capture de l’anticorps en surface de grille. Dans la dernière partie de mon travail, je propose une approche qui met à profit à la fois le couplage capacitif de l'EGOFET mais aussi sa sensibilité aux charges électrostatiques accumulées en surface de grille. J'ai immobilisé en surface de grille un peptide court (Gly-Gly-His) connu pur avoir une forte affinité envers les ions cuivre Cu2+. Le peptide a été immobilisé par électro-oxydation directe de l'amine primaire du premier fragment glycine. J’ai démontré que les dispositifs EGOFET, modifiés par GGH, peuvent transduire la complexation de Cu2+ par des variations significatives de leurs caractéristiques de sortie et de transfert, en particulier par un décalage de la tension de seuil (VTh). / Today, with the increase of population, the consumption of drugs and of chemicals in agriculture has dramatically increased. It becomes a worrisome issue because a large amount of these molecules, excreted to the environment, are not well eliminated by water-treatment plants (when they exist) and are therefore released without control into the ecosystem. In too large quantities, these drugs are poisons for living organisms, including humans. Classical analytical methods for the measurement of these chemicals already exist (classical separative methods such as gas chromatography, high-performance liquid chromatography, possibly coupled with mass spectrometry, etc). However, even if extremely precise and reliable, these techniques are difficult to apply for on-site monitoring and are usually costly. For this reason, my thesis focuses on novel analytical approaches to detect small organic molecules such as these pollutants. In a first part of my work, I developped an original immunosensor based on a competitive complexation and on an electrochemical (amperometric) transduction, for detection of diclofenac, which is a non – steroidal anti – inflammatory drug generally employed to protect patients from inflammation and relieve pain. The working electrode was electrografted with two functional diazonium salts, one as molecular probe (a diclofenac derivative coupled with an arylamine) and the other as redox probe (a quinone) also coupled with an arylamine, able to transduce the hapten-antibody association into a change in electroactivity. The transduction was designed to deliver a current increase upon detection of diclofenac (“signal-on” detection). The detection limit is ca. 20 fM in tap water, which is competitive compared to other label-free immunosensors. In the following part of my thesis, I kept the same original transduction approach (competitive immunoassay) but applied to an Electrolyte-Gated Organic Field-Effect Transistor (EGOFET) based on poly(N-alkyldiketopyrrolo-pyrrole dithienylthieno[3,2-b]thiophene) as organic semiconductor whose gate electrode was functionalized by electrografting a functional diazonium salt capable to bind an antibody specific to 2,4-dichlorophenoxyacetic acid (2,4-D), an herbicide well-known to be a soil and water pollutant. Molecular docking computations were performed to design the functional diazonium salt to rationalize the antibody capture on the gate surface. In the last part of my work, I propose an approach which takes profit not only of the capacitive coupling of the EGOFET but also on its sensitivity to electrostatic charges accumulated on the gate surface. To illustrate this in the field of sensors, I used a short peptide (Gly-Gly-His), known to selectively bind copper ions Cu2+. The peptide was immobilized by direct electrooxidation of the primary amine of the first glycine moiety. I demonstrated that GGH-modified EGOFETs can transduce Cu2+ complexation through significant changes of their output and transfer characteristics, in particular their threshold voltage (VTh).