Since their discovery over two decades ago, single-walled carbon nanotubes (SWNTs) have become one of the most investigated nanomaterials in materials science. Their exotic optical, electrical, thermal and mechanical properties afford them amazing potential in a variety of different fields. Current SWNT synthetic processes produce heterogeneous mixtures of both semiconducting and metallic SWNTs. The mixed electronic nature of these materials, combined with their limited solubility, has significantly hampered the realization of many applications and necessitates the development of post-synthetic purification techniques. Conjugated polymers offer a significant advantage over other proposed strategies in that not only do they provide a cheaper and scalable route towards the isolation of SWNTs, but they also allow for the preparation of materials with novel properties. Polyfluorenes have been extensively investigated in the literature due to their preference towards dispersing semiconducting SWNTs; however, these dispersions are often quite dilute, and the polyfluorene structure is incompatible with certain device applications for SWNTs. Poly(2,7-carbazole)s offer a viable alternative to polyfluorenes for the purification of bulk SWNT material. At the time of this thesis, there have been relatively few reports investigating the interactions of poly(2,7-carbazole)s with SWNTs, and the majority of examples in the literature have suffered from poor stability and complex dispersal procedures due to the inherent insolubility of the 2,7-carbazole structure. The work presented in this thesis involved the preparation and characterization of a novel poly(2,7-carbazole) structure that displayed excellent solubility in a variety of organic solvents, allowing for the preparation of extremely stable and relatively concentrated dispersions of SWNTs. Thorough characterization of the supramolecular complexes through absorbance, photoluminescence and Raman spectroscopies determined that this polymer preferentially disperses semiconducting SWNTs. A second objective of this work was to investigate how modification of various parameters (including polymer structure, molecular weight and the type of SWNTs) can influence the quality of the resultant composite dispersions. One important study performed was to investigate how the electronic nature of the polymer backbone can affect the separation of SWNTs by electronic type. We demonstrate for the first time that by incorporating an electron-poor functionality into a polyfluorene it is possible to change from dispersing only semiconducting SWNTs to solubilizing both electronic types. This investigation highlights the potential importance of incorporating electron-poor functionalities in the development of polymeric systems that can selectively discriminate metallic SWNTs, which remains a challenging endeavor at the time of this thesis publication. / Thesis / Doctor of Philosophy (PhD)

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24964号 / 理博第4989号 / 新制||理||1712(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 倉重 佑輝, 教授 渡邊 一也, 教授 林 重彦 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Single-walled carbon nanotubes (SWNTs) have excellent electronic, mechanical, and optical properties that make them promising materials for various applications. However, SWNT production methods produce a mixture of semiconducting and metallic species and non-SWNT impurities limiting their incorporation into devices. Among the different purification methods, conjugated polymer sorting has proven to be a scalable and cost-effective method. Conjugated polymers can easily be tuned to disperse SWNT species and obtain solubility in target solvents. They are multifunctional structures that enable the purification and extraction of specific SWNTs while simultaneously enhancing their processability. Therefore, they are suitable as purification methods for the fabrication of SWNT-based devices, particularly for printed electronics. However, the polymer backbone and the non-conductive side-chains negatively impacts the performance of SWNT devices by preventing good contact between the nanotubes. We first functionalized our polymer with thermally cleavable side-chains and demonstrated that the removal of the side-chains leads to a higher conductivity. We obtained stable dispersions in two green solvents compatible with inkjet printing. We also functionalized our polymer with photocleavable side-chains and showed efficient cleavage in solution. These investigations represent a proof-of-concept that could be used for the development of SWNT-based devices where the removal of the side-chains will improve the device performance. Lastly, we synthesized a fluorene-based polymer that contains a photocleavable ortho-nitrobenzylether unit and is functionalized with hydrophilic side-chains. We demonstrated the degradation of the polymer in organic and aqueous solvents. These investigations highlight the challenges of dispersing SWNTs in aqueous solvents using conjugated polymer. / Thesis / Doctor of Philosophy (PhD) / The objective of this thesis is to develop cleavable complexes between conjugated polymers and single-walled carbon nanotubes (SWNTs) to maximize the potential performance of printed devices post-processing. We functionalized a conjugated polymer with cleavable side-chains and investigated the impact on the conductivity after their removal. In addition, this work also focuses on dispersing SWNTs in green solvents that are compatible with printing processes such as inkjet printing. Lastly, we synthesized a degradable and water-soluble conjugated polymers to produce dispersant free-SWNTs.

The thesis work described herein explores two avenues of post-functionalization of conjugated polymers using ‘click’ chemistry. The first avenue utilizes the Strain-Promoted Alkyne-Azide Cycloaddition (SPAAC) and the second an Inverse Electron-Demand Diels-Alder (IEDDA). In the first part of this thesis, various azide moieties were SPAAC ‘clicked’ onto a dibenzocyclooctyne-containing polymer, such as small molecules like para-phenyl-nitroazide, as well as larger azide-terminated chains like polystyrene and polyethylene glycol. Host-guest chemistry and self-healing organogels were also explored. The synthesis of each component, including the cyclooctyne diamine monomer, dialdehyde comonomer, resulting polymer, various azide moieties, as well as the SPAAC click reactions, are all described in detail along with extensive characterization. Similarly, the second part of this thesis involved the synthesis and characterization of several components, including the tetrazine monomer, fluorene comonomer, resulting polymer, and various TCO derivatives for the post-polymerization IEDDA ‘click’ reactions onto the backbone. Some of the click reactions described include small molecule TCO derivatives, polymeric PEG TCO, and a difunctional linker to generate a crosslinked foam. / Conjugated polymers attract significant attention due to their interesting optoelectronic and physical properties. Over the past few decades, tremendous effort has been devoted to expanding the structural diversity and applications of this class of macromolecules. The pursuit of structural variability of conjugated polymers has resulted in a broad range of research to understand their structure-property relationships via functionalization. This functionalization is crucial for tailoring performance in any given application. Thus, the ability to synthesize a library of homologous polymers would prove very useful. Efficiency is of utmost importance when creating a library of homologous conjugated polymers, as the faster a library can by synthesized, the sooner said polymers can be screened for any desirable properties. Such an approach requires a post-polymerization functionalization strategy, whereby a progenitor polymer undergoes efficient reactions at each repeat unit of the backbone. The work presented in this thesis involves synthesizing a reactive conjugated polymer scaffold, followed by efficiently post-polymerization functionalization via “click” chemistry. Two elegant click reactions are described in this work; the Strain-Promoted Alkyne-Azide Cycloaddition (SPAAC) and Inverse Electron-Demand Diels-Alder (IEDDA). The SPAAC reaction allowed for rapid functionalization of triazole moieties on a dibenzocyclooctyne-containing polymer backbone, creating a small polymer library with a consistent degree of polymerization (DP). Grafting with polystyrene and polyethylene glycol azide-terminated polymers allowed the efficient syntheses of a series of graft-co-polymers with Mn values up to 800 kDa and varying solubilities. Secondly, The IEDDA reaction was applied to a poly(tetrazine-co-fluorene) conjugated polymer, which resulted in the rapid and quantitative functionalization of the polymer backbone with trans-cyclooctene derivatives. These reactive conjugated polymers were explored in a variety of applications, including supramolecular chemistry and gel formation. / Thesis / Doctor of Philosophy (PhD) / Conjugated polymers are a class of macromolecular materials that attract significant attention due to their interesting behaviors and properties. Under certain conditions, these polymers even display conductivities like that of metals. As such, they show promise in applications such as organic solar cells, chemical sensors, organic light-emitting diodes, and supercapacitors. Over the past few decades, tremendous effort has been devoted to expanding on the types of conjugated polymers as well as their structural diversity. This, of course, has resulted in polymers that exhibit vastly different behaviours depending on what they are made of. As certain applications (e.g.: solar cells) require polymers with very specific properties, being able to ‘tune’ a conjugated polymer to ‘match’ a required property would be extremely useful. This tuning of polymer properties can be successfully accomplished by attaching different structures onto the polymer chain by utilizing a reaction known as ‘post-polymerization functionalization’. In doing so, a starting reactive polymer can be transformed into an entirely different polymer with specific chemical properties and behaviors. The work presented in this thesis involves synthesizing two types of conjugated polymers and attaching various structures onto their backbones to yield different properties. The synthesis, characterization, and potential applications of said polymers are described herein.

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The development of future electronics depends on the availability of suitable functional materials. Printed electronics, for example, relies on access to highly conductive, inexpensive and printable materials, while strong light absorption and low carrier recombination rates are demanded in photocatalysis industry. Despite all efforts to develop new materials, it still remains a challenge to have all the desirable aspects in a single material. One possible route towards novel functional materials, with improved and unprecedented physical properties, is to form composites of different selected materials. In this work, we report on hydrothermal growth and characterization of graphene/zinc oxide (GR/ZnO) nanocomposites, suited for electronics and photocatalysis application. For conductive purposes, highly Al-doped ZnO nanorods grown on graphene nanoplates (GNPs) prevent the GNPs from agglomerating and promote conductive paths between the GNPs. The effect of the ZnO nanorod morphology and GR dispersity on the nanocomposite conductivity and GR/ZnO nanorod bonding strength were investigated by conductivity measurements and optical spectroscopy. The inspected samples show that growth in high pH solutions promotes a better graphene dispersity, higher doping and enhanced bonding between the GNPs and the ZnO nanorods. Growth in low pH solutions yield samples characterized by a higher conductivity and a reduced number of surface defects. In addition, different GR/ZnO nanocomposites, decorated with plasmonic silver iodide (AgI) nanoparticles, were synthesized and analyzed for solar-driven photocatalysis. The addition of Ag/AgI generates a strong surface plasmon resonance effect involving metallic Ag0, which redshifts the optical absorption maximum into the visible light region enhancing the photocatalytic performance under solar irradiation. A wide range of characterization techniques including, electron microscopy, photoelectron spectroscopy and x-ray diffraction confirm a successful formation of photocatalysts. Our findings show that the novel proposed GR-based nanocomposites can lead to further development of efficient photocatalyst materials with applications in removal of organic pollutants, or for fabrication of large volumes of inexpensive porous conjugated GR-semiconductor composites.