We report on a new class of nonionic, photosensitive surfactants consisting of a polar di(ethylene oxide) head group attached to an alkyl spacer of between two and eight methylene groups, coupled through an ether linkage to an azobenzene moiety. Structural changes associated with the interconversion of the azobenzene group between its cis and trans forms as mediated by the wavelength of an irradiating light source cause changes in the surface tension and self-assembly properties. Differences in saturated surface tensions (surface tension at concentrations above the CMC) were as high as 14.4 mN/m under radiation of different wavelengths. The qualitative behavior of the surfactants changed as the spacer length changed, attributed to the different orientations adopted by the different surfactants depending on their isomerization states, as revealed by neutron reflection studies. The self-assembly of these photosensitive surfactants has been investigated by light scattering, small angle neutron scattering, and cryo-TEM under different illuminations. The significant change in the self-assembly in response to different illumination conditions was attributed to the sign change in Gaussian rigidity, which originated from the azobenzene photoisomerization. / Singapore-MIT Alliance (SMA)

The motivation for the current work stems from a unique application, i.e. the photopatterning of optical functionality in a photosensitive material immediately prior to use. In this case, optical devices such as diffraction gratings and optical interconnects are produced in thin films using integrated photonic sources under relatively uncontrolled environmental conditions. The compatibility of the material photoexcitation mechanism with wavelength and fluence levels available from compact solid-state optical sources and the need to understand the impact of local atmospheric composition and temperature on the photosensitive material response are therefore of primary concern. The primary goal of the current study was to investigate photoexcitation mechanisms and photoinduced optical and structural changes in promising candidate material systems for this application: polysilane and polygermane-based molecular hybrid polymers. The work pursued the development of a fundamental understanding of the key photophysical and photostructural responses of thin films composed of both pure, linear-chain polysilanes and of a Ge-Si copolymer. The effects of molecular modifications to the polymers, including polymer backbone catenate structure and side-group identity, on the optical and photosensitive behavior observed in these systems are examined. Through such effort, an understanding of how such structural characteristics influence key photosensitive properties, i.e. the excitation wavelength and the resulting photoinduced optical property changes, was attained. A related objective in the present work was to characterize the thermal stability of these hybrid polymers, specifically in terms of the effect of thermal treatment on as-deposited and photomodified materials. In this case, an evaluation of the similarities and differences in structural modification in response to both thermal and optical fields was pursued. The primary mechanism associated with the photoinduced phenomena observed in both polysilane and polygermane involves backbone chain scissioning and the formation of silane-radicals upon absorption of near-UV (λ ≈ 300 to 400 nm) photons, resonant with the lowest energy, σ - σ* (HOMO-LUMO) transition of the Group IVA backbone. The final photoproducts obtained result from a mixture of different competing processes which occur subsequent to this initial photoscissioning. In aerobic atmospheric environments, the radicals formed capture oxygen and form oxide linkages forming the dominant photoproducts. On the other hand, under anaerobic conditions, photooxidation is suppressed while hydride passivation of the radical dominates the response. The oxidized product, resulting from irradiation under the aerobic environment, exhibited higher refractive index changes than irradiation under anaerobic conditions. Photoexcitation using higher energy photons (typically λ ≈ 230 to 300 nm) are resonant with side-group transitions associated with π-conjugated states of the cyclic moieties. Under these conditions, the excitation accesses both these organic side-groups as well as the Group IVA backbone structure. Such excitation conditions resulted in a larger photoinduced structural modification in the irradiated polymer, as observed both in terms of its electronic structure as well as the resulting refractive index change. Thermally induced structural modification to the backbone and side-group moieties were found to be qualitatively similar those produced under optical irradiation. For example, the primary structural changes were again associated with backbone chain scissioning. Photoinduced structural modifications through resonant optical excitation of the material, however, tended to be more focused on the specific structural moieties accessed.

The primary objective of the research is to investigate photosensitive semiconducting materials, mainly organic, and utilise them in antenna front-end systems and dynamic lenses for sub-THz applications. Mechanisms such as phase-shifting and photo-conductive switching are introduced in EM-devices to alter the antenna performance and behaviour. Using such mechanisms the devices are able to attain frequency, radiation pattern and polarisation reconfigurability. The common inorganic semiconductor, Si, and organic semiconductors such as poly 3-hexylthiophene (P3HT), [6,6]-Phenyl C61 butyric acid methyl ester (PCBM) have been extensively studied and used in the exemplar EM-devices developed for this thesis. In this research, novelty is deployed with the use of photosensitive semiconductors as a means of 'tuning' dielectrics to control the propagation of the emerging beam-field of an antenna. Both organic and inorganic photosensitive semiconductors have been implemented in this work. The research begins by exploring the physical properties of such photosensitive semiconductors at microwave frequencies. Medium-resistivity Si was characterised using a conventional microstrip transmission line and the conductivity of the Si piece in dark and active states were estimated by matching its transmission characteristics with the modelled Si in CST Studio Suite. Thereafter the modelled Si was used in an antenna design to estimate the reconfigurability of the device. However, inorganic semiconductors are being replaced with organic semiconductors because of their inflexibility in device fabrication. Organic polymers, on the other hand, are light in weight, can be cast onto any surface, when blended with an organic solvent, and also photo-excited using white light. Organic polymer heterojunction 95% P3HT: 5% PCBM was characterised and changes in the real and imaginary parts of the complex dielectric constant of the organic blend are measured in the range of -0.05 to -0.55 and +0.01 to +0.52 respectively, over the sub-THz frequency-domain. In order to demonstrate EM-control of a wave using a photo-sensitive material, a two-element patch antenna array using organic polymer P3HT-PCBM is fabricated and the functionality for antenna beam steering examined. Non-optimum illumination of the organic layer on the antenna patches, led to an asymmetric and perturbed beam steer. Hence, a novel optically triggered antenna has been proposed at S-Band (2 - 4 GHz), where sodalime glass is being used as lower substrate, ITO (Indium Tin Oxide), transparent to white-light, as the ground plane and transmission lines along with patches are modelled onto the upper substrate layer (P3HT:PCBM). The estimates of the dielectric changes in the organic polymer blend due to optical excitation were used as inputs in the modelled device to show the proof-of-concept for beam steering with such a phase-shifting device. In addition, the antenna design also demonstrated that with a small change in the real part of the permittivity of the substrate it is possible to generate a maximum beam steer of 5°, using an effective phase-shifting design in CST Studio Suite. At millimetre-wave or sub-terahertz frequencies, small changes in the dielectric with excitation-region depth comparable to the wavelength are plenty to manipulate the emerging wave of an antenna or lens. Hence, an optically-activated dynamic lens is proposed and designed to dynamically control millimetre-wave transmission using optical illumination. The lens acts as a graduated gateway for phase transmission by adjusting the spatial permittivity across the lens. A nearfield measurement system is used to analyse the performance of the lens over the WR-10 (75 - 110 GHz) waveband. The phase distribution of the electric field across the face of the plane organic lens shows a similar pattern in the spatial phase-distribution of the lens plane in the active state as that projected by the illuminating source, allowing for projection-angle-induced cosine errors. Hence the dynamic operation of the lens can be beneficial for beam controlling applications in imaging, surveillance and remote sensing in the mm-wave frequency-domain.

No description available.

Advanced Methods, Materials, and Devices for Microfluidics Celesta E. White 217 Pages Directed by Dr. Clifford L. Henderson Microfluidics is a rapidly growing research area that has the potential to influence a variety of industries from clinical diagnostics to drug discovery. Unlike the microelectronics industry, where the current emphasis is on reducing the size of transistors, the field of microfluidics is focusing on making more complex systems of channels with more sophisticated fluid-handling capabilities, rather than reducing the size of the channels. While lab-on-a-chip devices have shown commercial success in a variety of biological applications such as electrophoretic separations and DNA sequencing, there has not been a significant amount of progress made in other potential impact areas for microfluidics such as clinical diagnostics, portable sensors, and microchemical reactors. These applications can benefit greatly from miniaturization, but advancement in these and many other areas has been limited by the inability or extreme difficulty in fabricating devices with complex fluidic networks interfaced with a variety of active and passive electrical and mechanical components. Several techniques exist for the fabrication of microfluidic devices, but these methods have significant limitations, and alternative fabrication approaches are currently desperately needed. One such method that shows promise for its ability to integrate the desired high levels of functionality utilizes thermally sacrificial materials as place holders. An encapsulating overcoat material provides structural stability and becomes the microchannel walls when the sacrificial material is removed from the channel through thermal decomposition. Disadvantages of this method, however, include numerous processing steps required for sacrificial layer patterning and elevated temperatures needed for the decomposition of initial sacrificial materials. These limitations keep this method from becoming an economical alternative for microfluidic device fabrication. The materials needed for this method to reach its full potential as a valid fabrication technology for m-TAS are not currently available, and it was a major focus of this work to develop and characterize new sacrificial materials, particularly photosensitive polycarbonate systems. In addition to the development of new sacrificial polymers, the framework for a working microfluidic device was developed to show that this concept will indeed provide significant advancements in the development of future generations of microfluidic systems. Finally, novel fabrication methods for microfluidics through combined imprinting and photopatterning of photosensitive sacrificial materials was demonstrated.

Polymers play an integral part in the semiconductor electronic industry. Due to the expanding diversity of a polymer s structural design and the resulting properties, different polymers serve as different components in the makeup and fabrication of the electronic package. The limiting factor in computer processing speed shifts from the transistors gate delay to the interconnect delay below a circuit line width of 1.8 μm for interlayer dielectrics. Silicon dioxide has been used as the insulating layer between metal lines for many computer chip generations. Low dielectric constant polymers will need to supplant silicon dioxide as interlayer dielectrics in order to develop reliable circuits for future generations. Along with serving as interlayer dielectrics, low dielectric constant polymers are also incorporated in first and second level electronic packaging. Deposition and patterning of these polymers can be significantly reduced by using photodefinable polymers. Most photodefinable polymers are in a precursor form for exposure and development in order to dissolve in industrial developers. Once developed, the polymer precursors are cured to produce the final polymer structure. This temperature is as high as 350 oC for many polymers. Thermal curing sets limitations on the use of the polymer in the electronics industry because of either the unwanted stress produced or the incompatibility of other electronic components that do not survive the thermal cure. In addition to a low dielectric constant and photodefinability, many other properties are needed for successful implementation. Polymers must be soluble in organic solvents in order to spin coat films. Water absorption increases the dielectric constant of the patterned films and can lead to various adhesion problems and cause delamination of the film. Mismatches between the coefficients of thermal expansion in adjacent layers can produce residual film stresses which leads to warping of the substrate or interfacial delamination. The glass transition temperature must be high because the thermal expansion is greatly increased when the glass transition temperature is exceeded. A high Young s modulus is also required to withstand external forces from thermal, electrical, and packaging stresses. The goal of this research was to develop novel, low dielectric, photodefinable polymers that can be processed at low temperatures. All polymers discussed will contain one of two monomers with hexafluoroalcohol (HFA) functional groups. Fluorine provides many properties that are advantageous for low dielectric applications whereas alcohols absorb water and increase the dielectric constant. Characterization of the polymers show the effect the fluorine has on the alcohol s high water absorption. All polymers will be synthesized by condensation polymerization of a diamine with a dianhydride or diacid chloride. All other polymers will contain a novel HFA diamine. A new thermoplastic polymer structure based on the cyclization of an HFA situated ortho to an amide linkage produces a benzoxazine ring in the polymer backbone. Cyclization to form polybenzoxazines occurs at temperatures considerably lower than that needed to form polyimides. The lowest processing temperatures are achieved with protection of the HFA that can be cleaved with a photoacid generator.

Dans le cadre de cette thèse un verre phosphate de zinc dopé avec des cations d’argent a été irradié par laser femtoseconde. Cette irradiation induit l’apparition dans le voxel de focalisation, d’une émission de fluorescence et une génération de second harmonique au sein du verre. La fluorescence a été attribuée à la création d’agrégats fluorescents composé d’une dizaine d’atomes d’argent. Une étude spectrale a été réalisée permettant de distinguer les différents types d’agrégats générés. Par ailleurs, la génération de seconde harmonique est attribuée à la présence d’un champs électrique enterré dans la zone irradié par effet EFISH (electric field induced second harmonic). La direction et la répartition de ce champ électrique, ont été étudié optiquement et conduisent à sa représentation spatiale.Les effets des paramètres expérimentaux, tels que le nombre d’impulsions laser, l’énergie par impulsion, la température du verre et le recuit sur les caractéristiques de la GSH et de la fluorescence, ont été étudiés. Enfin un processus global est proposé, expliquant les différentes étapes de la structuration, de la création du champ enterré par migration d’électrons à la réduction des cations d’argent et la croissance des agrégats. / In this work, a phosphate-zinc glass doped with silver ions was irradiated with a femtosecond laser. This irradiation causes the appearance of sub-micron features in the glass. Those features exhibit fluorescence and second harmonic generation. Fluorescence is linked to the aggregations of silver clusters in the glass. Second Harmonic Generation is linked to the creation of a buried electric field inducing an EFISHG effect.Polarization and spectroscopic studies were performed on these features. Those studies allowed us to produce a three-dimensional representation of the features. A phenomenological model, from the interaction of the laser pulses with the glass, to the movement of charges enabling the buried field, is developed to explain the overall process, therefore linking the migration of the electrons to the reduction of silver ion and the cluster growth.

This study investigated the decomposition efficiency of acetone using unmodified (pure TiO2) and modified TiO2 (TiO2/ITO¡BTiO2/N) prepared by sputtering technology. The influence of operating parameters including wavelength and relative humidity on the decomposition efficiency of acetone was further discussed. Operating parameters investigated included light wavelength (350~400, 435~500, and 506~600 nm), photocatalysts (TiO2/ITO, TiO2/N, and TiO2), and relative humidity (RH) (0%, 50%, and 100%). In the experiments, acetone was degraded by photocatalysts in a self-designed batch photocatalytical reactor. Samples coated with TiO2 were placed in the batch reactor. The incident light with different wavelength was irradiated by a 20-watt lamp. Moreover, a low-pressure mercury lamp for UV light or LED lamps for blue and green lights were placed on the top of reactor. Acetone was injected into reactor by using a gasket syringe. Reactants and products were analyzed quantitatively by a gas chromatography with a flame ionization detector followed by a methaneizer (GC/FID-Methaneizer). The structure of the photocatalyst film surface showed taper and the width of column ranged from 100 to 200 nm. The film structure showed crystallization cylindrical surface and the thickness of the photocatalyst film was in the range of 4.0-4.3 £gm. The highest decomposition efficiency of acetone was observed by using TiO2/ITO under visible-light with 50% RH. The synthesis of TiO2 was mainly anatase for the tested photocatalysts. AFM images showed that the photocatalyst surface appeared rugged and the shape showed a mountain ridge distribution . Keywords: sputtering technology, modified photocatalysts, photosensitive, acetone, photocatalytic oxidation, acetone decomposition

Permanent dielectric materials are integral to the fabrication of microelectronic devices and packaging. Dielectrics are used throughout devices to electrically and mechanically isolate conductive components. As such, they are required to have low electrical permittivity and robust mechanical properties. For packaging applications, dielectrics can be directly photo-definable. Dielectrics need to have excellent lithographic properties. These properties are pivotal for enabling high yield and low cost fabrication of reliable, energy efficient devices. The aim of this work was to develop new positive tone dielectrics which have improved or application-specific lithographic, mechanical, and electrical properties. To this end, several new dielectric polymers and chemistries were evaluated and characterized. Initially, it was desired to develop a positive tone, polynorbornene (PNB) dielectric that utilizes diazonaphthoquinone (DNQ) photochemistry. Cross-linking was achieved with epoxy cross-linkers during a thermal cure. Several DNQ-containing compounds were evaluated, but only one had good miscibility with PNB. The dissolution characteristics of PNB were measured with respect to polymer composition, DNQ loading, and cross-linker loading. PNB films exhibited unique dissolution properties, and these measurements allowed for an optimum formulation to be developed. A formulation with 20 pphr DNQ and 10 pphr epoxy cross-linker had sufficient inhibition in unexposed regions and fast dissolution in exposed regions. The resulting dielectric was the first positive tone, DNQ-based PNB dielectric. After achieving photo-definability, the cross-linking of the cured dielectric was evaluated by characterizing the mechanical properties. It was discovered that DNQ acted as a cross-linker in these films, and this insight was key to achieving good curing of the dielectric. Several experiments were performed to support this conclusions, and the reaction kinetics of this cross-linking reaction were evaluated. This effort produced a functional, positive tone dielectric with a sensitivity of 408 mJ cm-2 and contrast of 2.3. The modulus was 2.0 to 2.6 GPa and the dielectric constant of 3.7 to 3.9, depending on the curing conditions. The DNQ cross-linking results led to the investigation of other cross-linking chemistries for positive tone dielectrics. A chemically amplified (CA) photochemistry was utilized along with a Fischer esterification cross-linking reaction. Patterning and cross-linking were demonstrated with a methacrylate polymer. Successful positive tone lithography was demonstrated at a high sensitivity of 32.4 mJ cm-2 and contrast of 5.2. Cross-linking was achieved at 120°C as shown by residual stress and solubility measurements. The CA photochemistry and Fischer esterification cross-linking were also demonstrated using a PNB dielectric, which was shown to have improved lithographic properties: a sensitivity of 8.09 mJ cm-2 and contrast of ≥ 14.2. Work was performed to evaluate the effect of the polymer composition on the mechanical and electrical properties. A polymer with 60 mol% hexafluoroisopropanol norbornene and 40 mol% tert-butyl ester norbornene exhibited a dielectric constant of 2.78, which is lower than existing positive tone dielectrics. It also outperformed existing dielectrics in several other categories, including dark erosion, volume change, cure temperature, and in-plane coefficient of thermal expansion. However, a limitation of this dielectric was cracking in thick films. The final study was to improve the mechanical properties of this CA PNB dielectric specifically to enable 5 µm thick films. First, a terpolymer was tested that included a non-functional third monomer. The dielectric constant increased to 3.48 with 24 mol% of the third monomer. Second, low molecular weight additives were used to lower the modulus. Only one of the five tested additives enabled high quality, thick films. This additive did not significantly affect the dielectric constant at low loadings. An optimized formulation was made, and processing parameters were studied. The additive decreased the lithographic properties, lowering the sensitivity to 175 mJ cm-2 and lowering the contrast to 4.36. In all, this work produced three functional dielectrics with positive tone photo-definability and good lithographic properties. Each dielectric can serve a variety of purposes in microelectronics packaging.

Thesis (Ph.D.)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Henderson, Cliff; Committee Member: Beckham, Haskell; Committee Member: Hess, Dennis; Committee Member: Koros, William; Committee Member: Tolbert, Laren.