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Properties of polymers in thin films are distinct from those in the bulk due to the significant effects of free or substrate surfaces. The presence of a free surface allows an increased mobility of polymer chains in the near surface region, therefore, a lower glass transition temperature (T_g). With this lower surface T_g, a surface-specific crystallization phenomenon occurring at temperatures much lower than the bulk crystallization temperature (T_c) in polymers including PET, PEN and PVOH has previously been observed. However, whether or not this surface-specific crystallization is a phenomenon observable in all crystallizable polymers is still a question. Similarly, due to this greater mobility, phase separation may also be able to take place in the near-surface region of a polymer blend at a temperature much lower than the bulk phase separation temperature. Yet, no such investigation on polymer blends has been carried out. In addition, it is interesting to study the thin-film behaviours of a block copolymer that undergoes both phase separation and crystallization and compare these with corresponding bulk behaviour. In this thesis, the thin-film crystallization behaviour of polyamide 12 (PA12) in spin-cast films is presented together with some investigation of crystallization of polyamide 6 (PA6) and polystyrene. Polystyrene and poly(methyl methacrylate) (PS/PMMA) systems are used to illustrate the phase behaviours specific to the near-surface region. Finally, the microstructural evolution in high hard block content thermoplastic polyurethane (TPU) thin films on annealing has also been investigated. These TPUs have hard segments (HS) extended by 2 methyl 1,3 propanediol (2M13PD) or 1,5 pentanediol (15PD). With its flexible chains, PA12 crystallizes during spin coating forming as-spin-cast crystals with morphology that varies with solvent evaporation rate and film thickness. Despite the as spin-cast crystals, the free surface allows secondary surface crystallization of PA12 at an annealing temperature (T_a) roughly 20°C below the bulk T_c. The secondary surface crystals were indicated to exist in the most stable crystalline phase of PA12. Similar secondary surface crystallization has also been observed in the PA6 films but at a higher T_a due to the higher T_g of PA6. In addition, surface-specific crystals have been observed in PS (semicrystalline, likely due to some stereoregularity of composition), a polymer with bulky side groups. The PS surface crystals are, however, flat-on oriented showing the important effect of side groups on the morphology or growth shape of surface crystals. The discovery of these surface crystals supports the universality of surface specific crystallization. Using fast solvent quenching, it is possible to "freeze in" a structure containing both PS and PMMA in the near surface region. On annealing, surface-specific phase behaviours (observable as pits, undulations and aggregations) confined to the near-surface region take place first at temperatures around or just below the bulk polymer T_g, while bulk vertical phase separation and dewetting of PS to PMMA, forming holes, network structures and islands, occur at temperatures well above T_g. This surface specific phenomenon, being a result of the free surface, should be applicable to other phase separation systems with a free surface as well. An increase in the crystallinity of PS was found to promote the phase separation process, but the free surface effect is independent of the interplay between the crystallization and phase separation. Rather than having a two-phase morphology, as was previously observed in melt-quenched bulk samples, 2M13PD extended TPU spin-cast films showed a single-phase morphology as-spin-cast. However, the HS ordering, the formation of mesophase, the melting of HS ordered regions, and microphase mixing observed in thin films are consistent with the bulk results but with slightly different transition temperatures due to spatial confinement. With a more flexible chain extender, e.g. 15PD, the hard and soft phase separation is more limited. The thin film investigations have allowed a better understanding of the microstructural evolution in these high hard block content TPUs on annealing by imaging the morphology directly. A thin-film specific phenomenon: formation of large multilayer flat-on crystals, was also observed in these TPU thin films. These crystals are initially developed from preformed aggregations and are believed to be induced by the significant substrate effect in thin films and the free surface effect.

The purpose of this research is to study the effect of the thermal treatment on the devices. We dissolved polymer light emitting materials in different solvents to discuss the influence on polymer thin film and device efficiency at different thermal conditions. We confirmed that the best thermal condition was changed as that of solvent changes. In this study, we dissolved polymer blue light material¡ÐBP105 in Toluene and o-xylene. The glass transition temperature (Tg) of BP105 is 120.7¢J, and the boiling point of Toluene and o-xylene were 110 and 145¢J. That is namely the boiling point of Toluene and o-xylene are lower and higher, respectively, than the Tg of BP105. This makes us to compares the thermal treatment conditions on different influence from different boiling point of solvents. The interrelations between the thermal treatment temperature, the boiling point of solvents and the glass transition temperature of polymer is an interesting topic to study, because it does affect the surface morphology of polymer thin films and the characteristic of devices. The device structure is as follows: ITO/ PEDOT:PSS/ BP105/ LiF/ Ca/ Al. Known from the experimental results that the spectra and the morphologies of polymer thin films will change in the different thermal treatment condition, and the choice of different solvent will also affect the best thermal treatment condition for device processing. We observed the surface roughness of polymer thin film is one of the important factors to affect the device efficiency in this study. We found that if the boiling point of used solvent was higher than the thermal treatment temperature, which was higher than the Tg of polymer, the surface roughness of polymer thin film is more smooth resulting in higher current injecting and higher stability of the device. The best thermal treatment temperature is 130¢J by using o-xylene as solvent. The surface roughness of polymer thin film is 0.393 nm, and the maximum brightness of the device is 8593 cd/m2 at 12.5 V as a configuration of ITO(1500Å)/PEDOT:PSS(800Å)/BP105(650Å)/LiF(10Å)/ Ca(100Å)/ Al(2000Å). The luminous and the power efficiencies are 3.98 cd/A, and 1.43 lm/W, respectively, at the current density 100 mA/cm2.

Title: Plasma polymers in the nanostructured and nanocomposite coatings Author: Artem Shelemin Department / Institute: Department of the Macromolecular Physics Supervisor of the doctoral thesis: Prof. RNDr. Hynek Biederman, DrSc. Abstract: The thesis represents the main results of my research work aimed to study nanostructured and nanocomposite films of plasma polymer. A few alternative experimental approaches were developed and investigated which ranged from low pressure (gas aggregation cluster sources and glancing angle deposition) to atmospheric pressure (dielectric barrier discharge and plasma jet) plasma processing. The metal/metal oxide Ti/TiOx, AlOx and plasma polymer SiOx(CH), Nylon 6,6 nanoparticles were prepared. The analysis of morphology of deposited plasma polymer coatings was performed by AFM and SEM. The chemical composition of films was studied by XPS and FTIR. Keywords: plasma polymer, nanoparticle, thin film, nanostructures

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