Thiophene Based Conjugated Polymers for Optoelectronic Applications


Book Description

In the last three decades, conjugated polymers have attracted much attention as active materials for optoelectronic applications, such as PLEDs, field-effect transistors, photovoltaic cells, optical switching devices, data storage devices etc. However, design and synthesis of -conjugated polymers with low oxidation potential, broad absorption spectrum, low band gap, efficient photoinduced charge transfer and separation, and ambipolar charge transport with high mobilities, effective -electron delocalization are crucial for the fabrication of the devices. In particular, tuning of the HOMO/LUMO energy levels of these polymers is of great importance for directing material properties towards the desired applications. A deeper understanding of structure-property relationship would help in designing new organic conjugated molecules by the judicious choice of functional substituents, and thus to tune their optical properties for applications in optoelectronic devices. In this context a series of donor-acceptor conjugated polymers are designed and are synthesized in this work. These polymers with good material properties are potential candidates for optoelectronic device applications."




Design and Synthesis of Conjugated Polymers and Small Molecules Based on Thiophene-substituted Isoindigo, 5-acetyl-4H-cyclopenta[c]thiophene-4,6(5H)-dione, and Diketopyrrolopyrrole Electron-deficient Units


Book Description

Pi-Conjugated polymers and small molecules are useful for their semiconductor properties in organic electronic devices such as organic photovoltaics, light emitting diodes, and thin film transistors. They also find application in chemical detection for their high sensitivity to fluorescence quenching species. Described herein are the syntheses of two new electron deficient monomer units for polymers and small molecules. 5-acetyl-1,3-dibromo-4H- cyclopenta[c]thiophene-4,6(5H)-dione was synthesized for the first time. It can be conveniently polymerized by Stille coupling to form polymers initially insoluble in common solvents, which can be rendered soluble by deprotonation with various organic amines. Solutions in methanol are highly fluorescent and show strong quenching when exposed to Ni2+ and Cu2+. Additionally, films can be cast from chloroform or dichlorobenzene solutions with triethylamine. New polymers and small molecules based on the recently reported thiophene substituted isoindigo were also synthesized and employed in photovoltaic devices reaching a maximum of 3.75 % power conversion efficiency, the highest yet reported for this unit. Also discussed is a series of low band gap small molecule semiconductors incorporating two diketopyrrolopyrrole units and their photovoltaic applications. The best power conversion efficiency for a molecule in this series was 2.22 %.













Functionalized Conjugated Polymers Promoted High Performance Materials for Organic Electronic Devices


Book Description

Conjugated polymers, representing a new generation of semiconductors, have attracted tremendous attention in the past few decades attributed to their conspicuous properties, such as flexibility, light weight, stretchability and solution processability, which is promising for manufacturing low-cost, large-area, and flexible electronic devices. Moreover, performance of semiconducting behaviors could be readily modulated via manipulating chemical structure and morphology. Organic field-effect transistors (OFETs) are the elemental components in electrical circuits. Although considerable materials were synthesized and investigated, there are still numerous approaches either in novel materials or morphological control which have not been explored. Therefore, in this research, five different strategies were proposed to attain conjugated polymer-based higher performance materials for OFETs, including novel pigment monomers, polymerization method and morphological manipulation by hydrogen bonding and conjugated cross-linking. In Part I, a blue/violet pigment, benzimidazolone-dioxazine-based molecule, was employed into donor−acceptor based conjugated polymers. Through the molecular modulation, the donors with matched size for donor-acceptor packing in the conjugated polymer thin films were uncovered, revealing refined charge carrier mobilities owing to the extended conjugated length of benzimidazolone-dioxazine structure. Part II discloses the diketopyrrolopyrrole(DPP)-quaterthiophene-based donor-acceptor copolymers with latent hydrogen bonding isoindigo-bithiophene to amend the charge transport in amorphous phase via hydrogen bonding-induced aggregation after thermal treatment. Part III applied the robust hydrogen bonding interaction to directly patterning conjugated polymer thin films and their OFETs with exceptional balance of mobilities and resolution of patterns, which is compatible with conventional photolithography in integrated circuit. Part IV introduces a newfangled method to obtain conjugated polymers with controlled molecular weight in the solid state, consisting of conventional anionic-polymerization and topochemical reaction. Moreover, this strategy could be further utilized to prepare the high-performance semiconducting material, graphene nanoribbons. Part V coalesced the concepts of Part II and IV to construct conjugated cross-linking between polymer backbones through topochemical reactions on diketopyrrolopyrrole(DPP)-quaterthiophene-based copolymers with latent cross-linkable diacetylene-bithiophene moieties, ameliorating the charge transport without demolishing the favorable packing of donor-acceptor conjugated polymers.







Synthesis of Metal-Containing Thiophene-Based Conjugated Polymers for Photovoltaic Applications


Book Description

This dissertation, "Synthesis of Metal-containing Thiophene-based Conjugated Polymers for Photovoltaic Applications" by Yiu, Koo, 顧耀, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b4189726 Subjects: Polythiophenes Polymeric composites Conjugated polymers Conducting polymers Photovoltaic power systems