This critical review summarizes recent developments in the fabrication of patterned polymer brushes. As top-down lithography reaches the length scale of a single macromolecule, the combination with the bottom-up synthesis of polymer brushes by surface-initiated polymerization becomes one main avenue to design new materials for nanotechnology. Recent developments in surface-initiated polymerizations are highlighted along with diverse strategies to create patterned polymer brushes on all length scales based on irradiation (photo- and interference lithography, electron-beam lithography), mechanical contact (scanning probe lithography, soft lithography, nanoimprinting lithography) and on surface forces (capillary force lithography, colloidal lithography, Langmuir–Blodgett lithography) (116 references). / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Planar electronic devices represent an attractive approach towards roll-to-roll printed electronics without the need for the sequential, precisely aligned, patterning steps inherent in the fabrication of conventional ‘3D’ electronic devices. Self-switching diodes (SSDs) and in-plane-gate field-effect transistors (IPG-FETs) can be patterned using a single process into a substrate precoated with semiconductor.These devices function in depletion mode, requiring the semiconductor to be doped in order for the devices to function. To achieve this, a reliable and controllable method was developed for doping organic semiconducting polymers by the immersion of optimally deposited films in a solution of dopant. The process was shown to apply both semicrystalline and air-stable, amorphous materials indicating that the approach is broadly applicable to a wide range of organic semiconductors.Simultaneously with the development of the doping protocol specialised hot-embossing equipment was designed and constructed and a high-yielding method of patterning the structures of IPG-FETs and SSDs was arrived at. This method allowed for consistent and reliable patterning of features with a minimum line-width of 200nm.Following the development of these doping and patterning processes these were combined to fabricate controllably doped, functioning planar devices. SSDs showed true zero-threshold rectification behaviour with no observed breakdown in the reverse direction up to 100 V. IPG-FETs showed switching behaviour in response to an applied gate potential and were largely free of detectable gate leakage current, verifying the quality of the patterning process.Furthermore, high-performance semiconducting polymer PAAD was synthesised and characterised in field-effect transistors as steps towards its use in planar electronic devices. It was also shown that this material could be doped using the developed immersion doping protocol and that this protocol was compatible with top-gated device architectures and the use of fluoropolymer CYTOP as a dielectric.

This thesis presents a study of lasing properties and optical amplification in semiconducting conjugated polymers and dendrimers. Configured as surface-emitting distributed feedback lasers, the effect of incorporating wavelength-scale microstructure on the output of the devices is examined along with the ability to create such structures using simplified fabrication processes such as soft lithography. Conjugated materials have received a great deal of interest due to their broad spectral absorption, emission, ability to exhibit gain and ease of processing from solution. As a result, they show great potential for a variety of applications such as photovoltaics, displays, amplifiers and lasers. To date however, there has only been one demonstration of a polymer optical amplifier. A broadband, solution based polymer amplifier is presented where the gain overlaps with the transmission window of polymer optical fibres. The effect of transitions that reduce the availability of gain in conjugated polymers is also examined by studying saturation of absorption in thin films. Producing wavelength scale microstructure is traditionally a slow, expensive technique. Here, solvent assisted micromoulding is used to pattern polymer films in less than two minutes. The effect of the variations in the pattern transfer on the laser characteristics is examined. The micromoulding technique is then applied to fabricating novel device types such as circular gratings and flexible plastic lasers. Encapsulation of the micromoulded laser is then shown to improve the lifetime of the device by over three orders of magnitude. The degradation effects witnessed during this extended operation are characterised quantitatively, an area of study where little data exists in the literature. A novel class of branched dendrimer materials whose properties can be independently tuned due to their modular architecture are configured as blue-emitting distributed feedback lasers. The ability to tune the emission wavelength by varying the film thickness is demonstrated. By changing the chemical groups contained within the molecule, further tuning of the emission can be obtained along with the demonstration of a highly efficient blue-emitting dendrimer laser. Chemosensing using dendrimer lasers is presented by demonstrating the incredibly sensitive response of the laser device to trace vapours of nitro-benzene compounds. The future application of which could be highly beneficial in the detection of explosives.

This dissertation constitutes two major sections. In the first major section, a kinetic analysis was established to investigate the electromigration (EM), enhanced intermetallic compound (IMC) growth and void formation for Sn-based Pb-free solder joints to Cu under bump metallization (UBM). The model takes into account the interfacial intermetallic reaction, Cu-Sn interdiffusion, and current stressing. A new approach was developed to derive atomic diffusivities and effective charge numbers based on Simulated Annealing (SA) in conjunction with the kinetic model. The finite difference (FD) kinetic model based on this approach accurately predicted the intermetallic compound growth when compared to empirical observation. The ultimate electromigration failure of the solder joints was caused by extensive void formation at the intermetallic interface. The void formation mechanism was analyzed by modeling the vacancy transport under electromigration. The effects of current density and Cu diffusivity in Sn solder were also investigated with the kinetic model. The second major section describes the integration of Step and Flash Imprint Lithography (S-FIL®) into an industry standard Cu/low-k dual damascene process. The yield on a Back End Of the Line (BEOL) test vehicle that contains standard test structures such as via chains with 120 nm vias was established by electrical tests. S-FIL shows promise as a cost effective solution to patterning sub 45 nm features and is capable of simultaneously patterning two levels of interconnect structures, which provides a low cost BEOL process. The critical processing step in the integration is the reactive ion etching (RIE) process that transfers the multilevel patterns to the inter-level dielectrics (ILD). An in-situ, multistep etch process was developed that gives excellent pattern structures in two industry standard Chemical Vapor Deposited (CVD) low-k dielectrics. The etch process showed excellent pattern fidelity and a wide process window. Electrical testing was conducted on the test vehicle to show that this process renders high yield and consistent via resistance. Discussions of the failure behaviors that are characteristic to the use of S-FIL are provided. / text

Microelectromechanical systems (MEMS) devices have been increasing in popularity for radio frequency (RF) and microwave communication systems due to the ability of MEMS devices to improve the performance of these circuits and systems. This interdisciplinary field combines the aspects of lithographic fabrication, mechanics, materials science, and RF/microwave circuit technology to produce moving structures with feature dimensions on the micron scale (micro-structures). MEMS technology has been used to improve switches, varactors, and inductors to name a few specific examples. Most MEMS devices have been fabricated using planar micro fabrication techniques that are similar to current integrated circuit (IC) fabrication techniques. These techniques limit the thickness of individual layers to a few microns, and restrict the structures to have planar and not vertical features. One micro fabrication technology that has not seen much application to microwave MEMS devices is LIGA, a German acronym for X-ray lithography, electroforming, and moulding. LIGA uses X-ray lithography to produce very tall structures (hundreds of microns) with excellent structural quality, and with lateral feature sizes smaller than a micron. These unique properties have led to an increased interest in LIGA for the development of high performance microwave devices, particularly as operating frequencies increase and physical device size decreases. Existing work using LIGA for microwave devices has concentrated on statically operating structures such as transmission lines, filters, couplers, and antennas. This research uses these unique fabrication capabilities to develop dynamically operating microwave devices with high frequency performance. This thesis documents the design, fabrication and testing of LIGA-MEMS variable capacitors that exploit the vertical dimension. Also included are methods to improve both the reliable fabrication and operation of these devices as well as material property characterization. Variable capacitors can be found in systems such as voltage-controlled oscillators, filters, impedance matching networks and phase shifters. Important figures-of-merit for these devices include the quality factor (Q), tuning range and tuning voltage. Two different types of variable capacitors are presented, a pull-away design and a design based on the principle of leveraged bending. The pull-away style variable capacitors were found to have high Q-factors, especially the devices fabricated using a thick gold device layer. As an example, the small gold half capacitance electrode design features a Q-factor of 95 at an operating frequency of 5.6 GHz and a tuning ratio of 1.36:1 with a tuning voltage range of 0 to 7.8 V. The design based on leveraged bending significantly improves the tuning ratio to a value of 1.9:1 while still maintaining a high Q-factor similar to those found in the pull-away style designs. A further increase in tuning ratio to a value of approximately 2.7:1 would be possible, based on simulated results, by simply changing the angle of the capacitance electrode in the layout. To improve device performance and fabrication reliability, modifications were made to both the fabrication process and the device layout. In the fabrication process the exposure step, electroplating step, and the etching process were modified to improve the quality of the resulting devices. In the layout, anti-stiction measures were introduced that reduce the contact area during collapse. To improve device characterization as well as the feedback link between simulation and fabrication, a set of test structures called VM-TEST was developed to accurately determine the important mechanical material properties of thick electroplated layers. These structures utilize the measurement of the pull-in voltage in cantilever and fixed-fixed beams, along with measured structure dimensions, to accurately extract the mechanical properties. Both nickel and gold test structures were analyzed with extracted Young’s modulus values of 186.2 and 60.8 GPa respectively. Also presented is a study of the gap shape in cantilever and fixed-fixed beams that significantly reduces the pull-in voltage while still maintaining a required maximum actuator displacement. It was shown that in the case of cantilever beam actuators, an approximately 40% reduction in pull-in voltage is possible, and in the case of fixed-fixed beam actuators, an approximately 30% reduction is possible by simply varying the shape of the gap between the beam and actuator electrode. These results can be used to significantly reduce the pull-in voltage of future designs. These promising results show that the LIGA fabrication process is capable of producing high performance dynamically operating RF MEMS devices, by exploiting the vertical dimension, not typically performed in most existing RF MEMS designs.

Self-assembled microsphere monolayers (SMMs) hold significant promise for micro- and nanopatterning. Here we exploit, for the first time, SMMs as stamps for microcontact printing (μCP) and demonstrate this to fabricate patterned initiator templates that can subsequently be amplified into polymer brushes by surface initiated atom transfer radical polymerization (SI-ATRP). SMM stamps avoid the need for expensive and sophisticated instrumentation in pattern generation, and provide a broad range of accessible surface chemistries and pitch size control.

This thesis is about ‘Dual View’ displays. These are displays that can show different images to different people. For example, the driver of a car could view a GPS map, whilst the passenger who looks at the display from a different angle, could watch a movie. This thesis describes some of the research that took the project from an idea to a refined product. Sharp’s first dual view display is prototyped, and problems such as crosstalk between the two views are seen. These problems are analysed and rectified to bring the device up to a high standard. In July 2005 Sharp used this technology to launch the world’s first dual view product. Since then a new design of dual view display has been investigated. This design is theoretically optimised and experimentally tested. The new design is shown to provide dual view with greater head freedom, greater efficiency, and lower crosstalk than the original parallax barrier design.

This thesis gives, for the first time, a clear exposition of the activities of the Arundel Society (1848-1897). Founded to 'collect diligently and with discrimination the highest and best examples of Art and to bring them before hundreds of English minds' the presence of Aubrey Bezzi, Lord Lindsay, Edmund Oldfield, Samuel Rogers and John Ruskin on the Society's first council meant that the initial publication of engravings after two early Italian artists, Fra Angelico and Giotto, was unsurprising. After 1856, under the guidance of Henry Layard, the archaeologist and politician, the Society became even more firmly committed to copying and publishing frescoes of the early Renaissance. The council's aim in recording and publishing these endangered works of art was to educate the taste of the public and inspire artists to embark on programmes of mural decoration. The water-colours executed for the Society are discussed with particular reference to the reactions of the council, and of members and the press to the problem of their verisimilitude. About two-thirds of these copies were published as chromolithographs and the gains and liabilities of this initially very popular method of reproduction are examined. Other methods employed by the Society to publish fac-similies of classical and medieval ivories and reduced copies of the Elgin marbles are also discussed with general reference to Victorian attitudes towards reproductions. The penultimate chapter attempts to relate the prints and monographs published by the Society to the art historical scholarship of the period. It is shown that the council's publication of decorative quattrocento, provincial cinquecento and early Flemish and German artists was influenced by Henry Layard's preferences. His monographs for the Society are discussed and compared with the more scholarly, if diverse, contributions made by, among others, G. W. Kitchin, John Ruskin, George Scharf and Ralph Wornum. In the final chapter it is argued that the Society's loyalty to the tastes of the mid-century and to the process of chromolithography led to its dissolution.

Conjugated polymers are novel organic electronic materials highly important for organic photovoltaic applications. Charge transport is one of the key properties which defines the performance of conjugated polymers in electronic devices. This work aims to explore the charge transport anisotropy in thin films of P3HT, one of the most common conjugated polymers. Using X-ray diffraction techniques and charge transport measurements, the relation between vertical charge transport through thin P3HT films and structure of the films was established. It was shown that particular orientations of crystalline domains of P3HT, namely face-on and chain-on, are beneficial for vertical charge transport. These orientations provide the efficient pathways for the charges to be transported vertically, either via π-π stacking interaction between the adjacent conjugated chains, or via the conjugated chain backbones. It was also demonstrated that particular orientations of crystallites are favourable for the formation of interconnected percolated pathways providing enhanced vertical charge transport across the film. Deposition of P3HT on most commonly used silicon substrates typically results in the formation of mostly edge-on orientation of crystallites which is unfavourable for vertical charge transport. Nanoimprint lithography was demonstrated as a powerful processing method for reorienting the edge-on crystalline domains of P3HT into chain-on (vertical) orientation. It is also shown that thin P3HT films with preferentially face-on orientations of crystallites can be deposited on graphene surface by spin coating. Using patterning of thin P3HT films by nanoimprint lithography, unprecedentedly high average vertical mobilities in the range of 3.1-10.6 cm2 V-1 s-1 were achieved in undoped P3HT. These results demonstrate that charge transport in thin films of a relatively simple and well-known conjugated polymer P3HT can be significantly improved using optimization of crystallinity,orientation of crystallites, polymer chain orientation and alignment in the films.

Ce travail de thèse concerne la réalisation et l'analyse des propriétés optiques de nanocristaux de silicium. Ces objets de taille nanométrique possèdent des propriétés optiques remarquables, en particulier de photoluminescence. Les propriétés de confinement quantique qui les caractérisent permettent d'obtenir un signal de luminescence intense dans le domaine du visible. Des composants optoélectroniques et photoniques ont été envisagés à base de nanocristaux de silicium. Les raisons physiques du fort signal de luminescence en revanche sont encore mal comprises. Les nanocristaux de silicium sont élaborés par évaporation. L'élaboration et le recuit thermique de multicouches SiO/SiO2 permet d'obtenir des nanocristaux de silicium de diamètre moyen bien contrôlé. Ceux-ci sont issus de la démixtion de la couche de SiO selon la réaction SiOx --> Si + SiO2. Le contrôle du diamètre des nanocristaux de silicium permet de maîtriser la région spectrale de luminescence dans la région du visible.La première partie de ce travail de thèse vise à isoler un ou quelques nanocristaux de silicium. L'objectif est de remonter à la largeur homogène de ces nano-objets. Dans un premier temps, une étude centrée sur le matériau SiOx est réalisée afin de réduire la densité surfacique de nanocristaux de silicium. Dans un deuxième temps, des moyens de lithographie ultime sont mis en oeuvre afin de réaliser des masques percés de trous de diamètres de l'ordre de la centaine de nanomètre. Des expériences de spectroscopie optique sont réalisées sur ces systèmes.La deuxième partie de ce travail vise à contrôler l'émission spontanée de lumière issue des nanocristaux de silicium. Ceci se fait en couplant les modes électroniques aux modes optiques confinés d'une microcavité optique. Le manuscrit détaille les moyens développés afin d'obtenir une microcavité optique dont les modes optiques puissent se coupler efficacement aux nanocristaux de silicium. Les propriétés optiques de ces systèmes sont finalement analysées. / This work concerns the implementation and analysis of optical properties of silicon nanocrystals. These nanoscaled objects have remarkable optical properties, especially in photoluminescence. The properties of quantum confinement that characterize them allow obtaining an intense luminescence signal in the visible range. Optoelectronic and photonic devices have been proposed based on silicon nanocrystals. The physical reasons of the strong luminescence signal, however, are still poorly understood. The silicon nanocrystals are prepared by evaporation. The preparation and thermal annealing of multilayers SiO/SiO2 leads to silicon nanocrystals with a well controlled average diameter. They are created during the demixing of the SiO layer by the reaction SiO ? Si + SiO2. The control the diameter of the silicon nanocrystals influences directly the spectral region of luminescence in the visible region.The aim of first part of this work is to isolate one or a few silicon nanocrystals. The intent is to trace the homogeneous width of these nano-objects. Initially, a study focusing on the SiOx material is conducted to reduce the surface density of silicon nanocrystals. In a second step, lithography is implemented to make masks with holes with diameters of about one hundred nanometers. Optical spectroscopy experiments were performed on these systems.The second part of this work aims controlling the spontaneous emission of light from silicon nanocrystals. This is done by coupling the electronic transmission to optical modes confined in an optical microcavity. The manuscript describes the methods developed to obtain an optical microcavity whose optical modes can be coupled effectively to the silicon nanocrystals. The optical properties of these systems are finally analyzed