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Synthesis and Characterization of New Conjugated Polymers for Application in Solar Cells

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Synthesis and Characterization of New Conjugated Polymers for Application in Solar Cells Synthesis and Characterization of New Conjugated Polymers for Application in Solar Cells Mohd Sani Bin Sarjadi A thesis submitted to The University of Sheffield as partial fulfillment for the degree of Doctor of Philosophy October 2014 Declaration This thesis is submitted for the degree of doctorate of philosophy (PhD) at the University of Sheffield, having been submitted for no other degree. It records the research carried out the University of Sheffield from November 2009 to October 2014. It is entirely my original work, unless where referenced. Signed:…………………………………………………….. 15 OCTOBER 2014 Date:…………………………………………………… i Abstract Plastic photovoltaic devices based on solution processed conjugated polymers have attracted much attention as potential candidates for the next generation of solar cells. Polymer solar cells based on blends of conjugated polymer donors and molecular acceptors such as PCBM (often referred to as bulk heterojunction solar cells) are attracting a great deal of interest. These systems have potential technological value due to their ease of fabrication and their relatively low production costs. This enabled devices to be produced that have solar power conversion efficiencies approaching 9%. The purpose of this research project is to develop new and more efficient materials for application in this area. A new class of alternating copolymers comprising carbazole units and thieno‐thiophene units for application in the area of bulk heterojunction solar cells is presented in this contribution. The polymers were prepared using Suzuki coupling methods. Three main classes of such polymers were prepared. The first class of polymers P1 ‐ P3 consisted of alternating co‐ polymers comprising thienothiophene repeat units and either 2,7‐linked 9‐alkyl carbazole units P1, or 2,7‐linked‐9‐alkyl carbazole repeat units with fluorine substituents at their 3,6‐ positions P2, or 2,7‐linked‐9,9‐dioctylfluorene P3. The second class of materials consisted of alternating copolymers comprising benzothiadiazole repeat units and 2,7‐linked carbazole repeat units flanked by thienothiophene repeat unit with or without fluorine‐ substituents at the 3,6‐positions on the carbazole repeat units (polymers P4 ‐ P7). The third class of materials consisted of alternating donor acceptor conjugated polymers which are similar to the second class of materials but have octyloxy‐substituents on the benzothiadiazole repeat units P8 ‐ P10. The presence of octyloxy‐substituents units on the benzothiadiazole electron accepting units along the polymer chains reduce the intramolecular charge transfer and provides materials with wider band gaps than those of the second class of materials prepared and hence have lower electronic delocalisation. The structures of the polymers have been confirmed by NMR spectroscopy, FT‐IR and elemental analysis, and their weight‐average molecular weights were estimated using gel permeation chromatography (GPC). The optical and electronic properties of the polymers were investigated by UV‐Vis absorption spectroscopy. Cyclic voltammetry measurements were used to investigate their electrochemical properties. The thermal properties of the materials were investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements. ii Acknowledgments First of all I must thank my parents, my wife Siti Normala Marimin and kids; Balqis Humairah and Bilal Haris for their continuous support, prayers, understanding, patience and encouragement not only during my time as a student, but throughout my entire life, this is for you. I am deeply grateful to my supervisor Dr. Ahmed Iraqi for his guidance throughout my PhD, without his advice and constant support fulfillment of this degree would not have been possible. I would like to acknowledge all the members of the Iraqi group past and present especially Dr. Hunan Yi, Dr. Harismah Kun, Dr. Noriko, Dr. Abdulaziz, Dr. Abdulqader, Dr. Reedy, Dr. Ryan Rees, Dr. Mohammed, Solyman Al Fifi, Abdulraheem Almalki, Luke Cartwright, Suguru Nakano, Ary R Murad, Ahmed Al‐Azzawi and Sulaiman A. Al‐Isaee for their invaluable help and time whenever needed. I am grateful to all my colleagues on F‐floor Dr. Paul Bonner, Dr. Adam Ellis, Dr. Georgia Mann, Azrul Zabidi, Kuljit, and Meshari for contributing to a relaxed working environment which often alleviated the inevitable stress associated with being a postgraduate. I would also like to thank all the admin, secretarial and accounting staff Ms. Elaine Fisher, Ms. Denise Richards, Ms. Louise Brown‐Leng, Ms. Rachel Myers, Ms. Elaine Frary for their kind support, Dr. Brian F. Taylor and Ms. Susan Bradshaw for NMR spectra measurements, Ms. Jennifer Louth and Ms. Melanie Hannah for elemental analysis, Mr. Simon Thorpe and Ms. Sharon Spey for mass spectroscopy analysis, Mr. Robert Hanson for GPC, TGA analysia, DSC and spectroscopy/chromatography analysis, Mr. Peter Farran, Mr. Nick Smith, Mr. Daniel Jackson and Mr. Keith Owen from chemical stores and Mr. Richard Wilkinson for the health and safety advice. Finally, I would like to acknowledge the financial support of the University of Malaysia Sabah and Ministry of Education Malaysia for their financial support over the period of my research. iii Table of Contents TABLE OF CONTENTS Declaration……………………………………………………………………………………………………………….. i Abstract…………………………………………………………………….…………………………………….…..…… ii Acknowledgments…………………………………………………………………………..………………………… iii Table of Contents………………………………………………………………………………………………..….… iv Table of Figures………………………………………………………………………………….………………..…… ix Table of Tables……………………………………………………………………………………………..………...… xi Table of Schemes…………………………………………………………………………….…………………..…… xii Glossary of Abbreviations and Terms………………………………………………………………………... xv CHAPTER 1 ‐ INTRODUCTION ................................................ 1 1.1 Conjugated Polymers ..................................................................................................... 1 1.2 Properties of Conjugated Polymers ............................................................................... 2 1.2.1 Conductivity of Conjugated Polymers ....................................................................... 2 1.2.2 Polymers band gap energy ................................................................................... 7 1.2.3 Solubility of Conjugated Polymers ..................................................................... 12 1.2.4 Stability of Conjugated Polymers ....................................................................... 14 1.3 Organic Photovoltaic Cells ........................................................................................... 15 1.3.1 Solar Cell Operational Principles .............................................................................. 16 1.3.2 Organic Solar Cells vs. Inorganic Solar Cells ............................................................. 17 1.3.3 Organic Photovoltaic device architectures .............................................................. 19 1.4 Synthesis of Conjugated polymers ............................................................................... 26 1.4.1 Oxidative preparation routes................................................................................... 26 1.4.2 Metal‐catalysed Routes to conjugated polymers .................................................... 28 1.4.3 Condensation polymerization routes ...................................................................... 33 1.5 Background on Carbazole Based Polymers .................................................................. 34 1.5.1 Synthetic routes to Polycarbazoles .......................................................................... 35 CHAPTER 2 ‐ AIMS AND OBJECTIVES ................................... 36 2.1 Carbazole and fluorene based copolymers containing thienothiophene.................... 36 2.2 Carbazole and fluorene based co‐polymers containing thienothiophene and benzothiadiazole units ....................................................................................................... 38 2.3 Carbazole and fluorene based copolymers containing thienothiophene and bis‐ octyloxy substituted benzothiadiazole units ..................................................................... 40 CHAPTER 3 ‐ EXPERIMENTAL ............................................... 42 3.1 Materials ...................................................................................................................... 42 3.2 Analysis and Characterisation ...................................................................................... 42 3.2.1 Thin Layer Chromatography (TLC) ........................................................................... 42 3.2.2 Nuclear Magnetic Resonance Spectroscopy (NMR) ................................................ 43 3.2.3 Melting Point Apparatus .......................................................................................... 43 3.2.4 Fourier Transform ‐ Infra Red Spectroscopy (FT‐IR) ................................................ 43 iv Table of Contents 3.2.5 Mass Spectrometry (MS) ......................................................................................... 43 3.2.6 Elemental Analysis ................................................................................................... 44 3.2.7 UV‐Visible Absorption Spectroscopy (UV‐Vis) ......................................................... 44 3.2.8 Thermo‐Gravimetric Analysis (TGA) .......................................................................
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