Fabrication and Characterization of Hybrid Metal-Oxide/Polymer Light-Emitting Diodes
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Fabrication and Characterization of Hybrid Metal-Oxide/Polymer Light-Emitting Diodes Nurlan Tokmoldin Nanostructured Materials and Devices Group Department of Chemistry - November 2010 - Dissertation submitted for the degree of Doctor of Philosophy The material contained in this dissertation is a product of my own work, except for where specific reference is made. The thesis has not been submitted in whole or as part of any other thesis for the award of a degree at this or any other university, and does not exceed 100,000 words. Nurlan Tokmoldin, October 2010 2 In fond memory of my grandparents Zharylgap, Korebai and Turaqan ACKNOWLEDGEMENTS Time goes faster at Imperial than outside its walls. This is one thing I‟ve learnt here... apart from what I‟ve learnt in a dark room during long-hour measurements of OLEDs. This feeling grows bigger with an understanding that this time has in fact been one of the most enjoyable in my life, which essentially is thanks to a very large number of people I have met in Imperial, both those who are here now and those who have moved on for further adventures. Above all, I would like to thank one of the first people I met in the UK, whose energy and enthusiasm have captivated me and attracted into the field of OLEDs since we first met in October 2005, my supervisor Dr. Saif Haque for his constant support and advice during my work. I would also like to express my deep gratitude to my co-supervisor, Prof. Donal Bradley, for the access to an amazing variety of light-emitting polymers, his help and personal support throughout my studies. A very big “Thank you” goes to people I have worked with side by side during my time as an MPhil/PhD student (chronologically): Niki Yamazaki, Nicholas Griffiths, Dr. Eugenia Martinez, Simon Dowland, Neha Bansal, Dr. Xiangjun Wang. Among these, special thanks goes to Dr. Simon King for his help on building the spray pyrolysis setup and Simon Turner for his help on a number of technical issues. I would like to express my big affection to all the people in the “basement” offices C062 and C034, Room 134 and Room 541, who have individually been parts of the amazing working atmosphere during the past three and a half years (alphabetically): Adrian Nightingale, Alice Rolandini Jensen, Dr. Ana Morandeira, Angharad Edwards, Dr. Andrea Listorti, Dr. Andrea Maurano, Dr. Annalisa Bruno, Aqilah Zainullabidin, Assaf Anderson, Dr. Brian O‟Regan, Cecile Bouet, Dr. Chris Shuttle, Dr. Dan Credgington, Dr. Dong Seok Leem, Fiona Jamieson, Frederico Sanchez, Dr. Henry Leventis, Prof. James Durrant, Dr. Jungwang Tang, Dr. Mattias Eng, Mindaugas (Jo) Juozapavicius, Luke Reynolds, Dr. Monica Barroso, Neha Bansal, Dr. Pabitra Shakya Tuladhar, Dr. Piers Barnes, Dr. Richard Hamilton, Dr. Rui Jin, Dr. Safa Shoai, Dr. Sarah Koops, Simon Dowland, Dr. Simon King, Dr. Siva Krishnadasan, Stephanie Pendlebury, Sung Kim, Dr. Thierry Lutz, Thitikorn Boonkoom, Dr. Tracy Clarke, Tracy Dos Santos, Xiaoe Li, Ying (Yvonne) Soon, Yoojin Kim, Dr. Zi En Ooi. I would like to acknowledge the Bolashak scholarship of the Ministry of Education and Science of the Republic of Kazakhstan without which my study alongside all the above-mentioned people would not have been possible. Finally, I would like to thank my main examiners for life, grandma Kulzhatai, parents Serekbol and Panarkhan, sisters Madina and Aidana, girlfriend Aliya, and all of my close relatives and friends for the love and support they have given. ABSTRACT Hybrid metal-oxide/polymer light-emitting diodes (HyLEDs) are a novel class of electronic devices based on a combination of electroluminescent organic and charge- injecting metal-oxide components. These devices employ air-stable electrodes, such as ITO and Au, and are therefore well suited for fabrication of encapsulation-free light- emitting devices. The current work is intended to provide an insight into operating mechanisms and limitations of the HyLEDs, and, on the basis of this knowledge, aims at modifying the device architecture in order to improve the performance. The choice of optically transparent metal-oxide charge-injection layers appears to be critical in this respect in order to optimize the electron-hole balance within the polymer layer. Starting from the original device architecture, ITO/TiO2/F8BT/MoO3/Au, which uses ITO as a cathode and Au as an anode, we follow different approaches, such as the use of dipolar self-assembled monolayers and nanoscale structuring of the electron-injecting interface, pursuing the goal of enhancing electron injection into the emissive layer. However, substitution of the electron-injecting layer of TiO2 with ZrO2 is demonstrated to be the most efficient of the approaches employed herein. Further, optimization of the device utilizing the latter metal oxide is demonstrated in terms of deposition and post- deposition treatment of the electron-injecting and electroluminescent layers. Substrate temperature during spray pyrolysis deposition of the electron-injecting layer is found to have a strong influence on the HyLED performance, as well as the precursor solution spraying rate and the layer thickness. On the other hand, post-deposition annealing of the polymer layer is shown to improve the device efficiency and brightness significantly, possible explanations lying in enhancement in polymer luminescence efficiency and formation of a more intimate contact between the electron-injecting and the active polymer layers. Combining electron-transporting (TiO2 and ZnO) and hole- blocking (Al2O3 and ZrO2) materials into a single electron-injecting layer is demonstrated to be an effective strategy of enhancing efficiency in the HyLEDs. The search for a hole-injecting electrode alternative to the conventionally used MoO3/Au leads to the device employing the PEDOT:PSS/VPP-PEDOT system, which though resulting in a poorer device efficiency, provides route for fabrication of vacuum deposition-free organic light-emitting devices. Finally, the HyLED architecture is demonstrated to offer better stability than the conventional architecture using LiF/Al as a cathode. It is hoped that the current work provides a better understanding of the requirements for fabrication of encapsulation-free organic light-emitting devices. TABLE OF CONTENTS TABLE OF CONTENTS ACKNOWLEDGEMENTS .......................................................................................................... 4 ABSTRACT .................................................................................................................................. 5 LIST OF ABBREVIATIONS ....................................................................................................... 9 LIST OF FIGURES ..................................................................................................................... 11 LIST OF TABLES ...................................................................................................................... 17 INTRODUCTION AND MOTIVATION .................................................................................. 18 Thesis motivation and aims ..................................................................................................... 20 Chapter 1. RELEVANT THEORETICAL BACKGROUND..................................................... 23 1.1. History of inorganic and organic LEDs ...................................................................... 23 1.2. Conjugated polymers................................................................................................... 25 1.2.1. Electronic structure of conjugated polymers ............................................................. 26 1.2.2. Charge injection into conjugated polymers ............................................................... 28 1.2.3. Charge transport in conjugated polymers .................................................................. 31 1.2.4. Recombination in conjugated polymers .................................................................... 32 1.2.5. Example of conjugated polymers: Polyfluorenes ...................................................... 32 1.2.6. Polymer treatment techniques. Thermal treatment .................................................... 34 1.3. Metal oxides ................................................................................................................ 35 1.3.1. Electronic structure ................................................................................................... 35 1.3.2. Charge transport ........................................................................................................ 37 1.3.3. Metal oxide deposition techniques ............................................................................ 38 1.4. OLED design and performance ................................................................................... 42 1.4.1. Single-layer devices .................................................................................................. 43 1.4.2. Multilayer devices ..................................................................................................... 44 1.4.3. OLED electrodes ....................................................................................................... 45 1.4.4. OLED efficiency ....................................................................................................... 47 1.4.5. OLED fabrication cost .............................................................................................. 49 1.4.6. Stability of OLEDs ...................................................................................................