Highly fluorescent conjugated polymers (CPs) are an important class of biomaterials used for various biological applications including labelling, sensing, and delivery of biological substances. Synthetic versatility and tunable emission make CPs a superior class of biomaterials. Understanding the structure-function relationship of CPs plays a vital role in designing high performing biomaterials. The cationic CPs are self-assembled to conjugated polymer nanoparticles (CPNs) in an aqueous environment due to their amphiphilicity. The physical and biophysical properties of CPNs are highly dependent on the chemical functionality and backbone structure of CPs. Modulation of the surface property and backbone structure of CPNs play an important role for efficient internalization of CPNs into cells. The goal of this dissertation is to understand the structure function relationship of CPNs in an aqueous environment and the change in their photo physical properties upon the self-assembly of CPNs with different backbone structure upon complexation with biologically significant polysaccharides and cell membrane. This work presents the self-assembly of a set of four cationic CPs with different connectivity and backbone structure upon complexation with a linear polyanion hyaluronic acid (HA). The study of photo physical properties changes upon the complexation with series of Glycosaminoglycans (GAGs) provides more insight about how the self-assembly behavior of cationic CPs changes upon the exposure to negatively charged polysaccharides. The understanding of the self-assembly of CPNs with negatively charged biologically important macromolecules under in vitro conditions can give us an idea of photophysical property changes of CPNs during the treatment of CPNs in the cellular environment. The study of the interaction of CPNs with cell membranes using scanning ion conductance microscopy (SICM)-based topography, potential mapping, and confocal microscopy imaging is presented. CPNs are able to induce transient pore like feature formation on the cell membrane during the cellular internalization process. A comparative study of cellular labelling and delivery of siRNA of five CPNs with guanidine motif is presented. The subcellular localization and delivery of siRNA were dependent on the side chain hydrophilicity. The CPNs fabricated with hydrophilic aminoethoxyethanol possesses excellent cellular imaging with higher siRNA delivery.

<p>Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells.</p><p>Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm², and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm.</p><p>Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells.</p><p>A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.</p><p> </p>

<p>In this thesis, the microstructure of organic photovoltaic APFO-3:PC₆₁BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, T_g, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC₆₁BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above T_g. The temperature stability of APFO-3:PC₆₁BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.</p><p> </p><p>The crystallization of PC₆₁BM was also investigated. Above T_g, PC₆₁BM crystallization was found to commence, albeit slowly at temperatures close to T_g. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC₆₁BM thin films above T_g affected PC₆₁BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.</p>

Recent developments in the synthesis and structure-property investigation studies of conjugated polymers have led to the design of novel polymeric materials with tailored properties for advanced technological applications. A promising development in this direction involves the fabrication of conducting polymer based sensors for the detection of metal ions and small organic molecules. Herein, we designed, synthesized and studied a series of amphiphilic copolymers containing alternate phenylene and 2,5- or 2,6- or 3,5-substituted pyridine rings. The basic N-atom of the pyridine ring and the adjacent –OH group from the phenyl ring provide binding sites for metal ions. Thermal properties, and optical properties of polymers in presence of acid, base and metal ions are investigated. A few target polymers showed high sensitivities for metal ions in solution. / Singapore-MIT Alliance (SMA)

In this thesis, the microstructure of organic photovoltaic APFO-3:PC61BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, Tg, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC61BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above Tg. The temperature stability of APFO-3:PC61BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.   The crystallization of PC61BM was also investigated. Above Tg, PC61BM crystallization was found to commence, albeit slowly at temperatures close to Tg. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC61BM thin films above Tg affected PC61BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.

Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells. Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm2, and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm. Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells. A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.

In this study, a novel series of conjugated monomers containing furan and fluorene units / 2,7-di(furan-2-yl)-9H-fluoren-9-one (FOF), 2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (FFF), and 2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan (FHF) were synthesized and their electrochemical polymerization were achieved via potential cycling. Optical and electrochemical properties of the polymers, poly(2,7-di(furan-2-yl)-9H-fluoren-9-one) (PFOF), poly(2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (PFFF) and poly(2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan) (PFHF) were investigated and it was found that polymer films exhibit reversible redox behavior (Epox = 1.083 V for PFOF, Epox= 0.915 V for PFFF and Epox= 0.985 V for PFHF) accompanied with a reversible electrochromic behavior, orange to green for PFOF, yellow to dark blue for PFFF and orange to green for PFHF during oxidation. Their band gap values (Eg) were found to be 2.32, 2.49 and 2.61 eV for PFOF, PFFF and PFHF, respectively.

Conjugated polymers are currently being used for a wide range of electronic applications. In this thesis, we studied two different synthetic approaches that lead to novel monomers and polymers that can be potentially used in electrochromic, or photovoltaic devices. The first approach described in this thesis is the utilization of olefin cross metathesis to create a family of dithienogermole (DTG) monomer derivatives in which synthetic control of the solubilizing side chains is achieved through an alkenyl building block. This alkenyl intermediate allows one to functionalize the DTG moiety though olefin cross metathesis to obtain a wide range of alkyl chain lengths and pendant functionalities on the polymer backbone. This work lead to the first example in the literature in which the synthesis of DTG moieties was not limited by the chain length of the solubilizing alkyl units. It provides a route that avoids the use of distillation for the purification the DTG monomer, allowing for the synthesis of a wide range of DTG derivatives that were previously unobtainable though the conventional synthetic methods. Finally, in this thesis we also describe the work of the use of direct (hetero)arylation polymerizations (DHAP) as a means of obtaining 3,4-propylenedioxythiophene-based conjugated polymers for use in electrochromic applications. This synthetic method offers a rapid route to achieving polymers in high yields with simplified purification procedures and low residual metal content, as determined by inductive coupled plasma-mass spectrometry (ICP-MS). The studied polymers possess comparable electrochromic properties to those previously reported by the Reynolds group, implying that their switching ability from a colored to a transmissive state is independent of the residual metallic impurities.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第19007号 / 工博第4049号 / 新制||工||1623 / 31958 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 伊藤 紳三郎, 教授 赤木 和夫, 教授 辻井 敬亘 / 学位規則第4条第1項該当

Polymer solar cells are promising in that they are inexpensive to produce, and due to their mechanical flexibility have the potential for use in applications not possible for more traditional types of solar cells. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime of polymer solar cells has become at least as important as improving the efficiency.   In this thesis, the relation between morphology and solar cell performance is studied, and the material stability for blend films of the thiophene-quinoxaline copolymer TQ1 and the fullerene derivatives PCBM and PC70BM. Atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) are used to investigate the lateral morphology, secondary ion mass spectrometry (SIMS) to measure the vertical morphology and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to determine the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed TQ1 surface enrichment does not affect the performance. Changes to the unoccupied molecular orbitals as a result of illumination in ambient air are observed by NEXAFS spectroscopy for PCBM, but not for TQ1. The NEXAFS spectrum of PCBM in a blend with TQ1 changes more than that of pristine PCBM. Solar cells in which the active layer has been illuminated in air prior to the deposition of the top electrode exhibit greatly reduced electrical performance. The valence band and absorption spectrum of TQ1 is affected by illumination in air, but the effects are not large enough to account for losses in solar cell performance, which are mainly attributed to PCBM degradation at the active layer surface. / The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime has become at least as important as improving the efficiency for polymer solar cells to become a viable technology.   In this work, the relation between morphology and solar cell performance is studied as well as the material stability for polymer:fullerene blend films. A combination of microscopic and spectroscopic methods is used to investigate the lateral and vertical morphology as well as the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed surface enrichment of polymer does not affect the performance. Changes to the unoccupied molecular states as a result of illumination in ambient air are observed for the fullerene, but not for the polymer, and fullerenes in a blend change more than pristine fullerenes. Solar cells in which the active layer has been illuminated exhibit greatly reduced electrical performance, mainly attributed to fullerene degradation at the active layer surface. / <p>Paper 2 ingick som manuskript i avhandlingen. Nu publicerad. </p>