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研究生: 陳佑誠
Chen, Yu-Cheng
論文名稱: 超薄緩衝層與元件結構(共主體與量子井)之探討及其應用於高效率有機發光元件
Investigation of the Effects of Ultra-Thin Buffer Layer and Device Structure (Co-Host and Multiple Quantum-Wells) for Efficient Organic Light-Emitting Devices
指導教授: 朱聖緣
Chu, Sheng-Yuan
學位類別: 博士
Doctor
系所名稱: 電機資訊學院 - 電機工程學系
Department of Electrical Engineering
論文出版年: 2013
畢業學年度: 101
語文別: 英文
論文頁數: 109
中文關鍵詞: 有機發光二極體表面能緩衝層量子井共主體
外文關鍵詞: OLED, buffer layer, surface energy, quantum-well, co-host
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  • 有機發光二極體被認為是目前有機會作為大面積、全彩,平面化顯示器之元件,由於它具有一些優點如:製程簡易、高應答速度、高對比、輕、薄及應用便利等。因此,許多研究探討改善其元件結構之及了解其操作機制。本研究利用增加載子注入效率以及採用特殊元件結構調整載子的特性來改進整體元件之效率。
    首先我們將各種不同的超薄緩衝層熱蒸鍍於ITO基板上並予以紫外光臭氧處理,藉此來探討其對於元件載子注入特性的影響。利用X射線和紫外線光電子光譜儀來測定其功函數以及使用表面能量化來研究其接面特性。當緩衝層厚度以及紫外光臭氧處理時間最佳化後,元件的驅動電壓降低、電流效率與最大亮度增加且同時可消除共振穿隧效應。能帶、表面能以及表面極性的量測指出利用紫外光臭氧處理過之超薄緩衝層來同時提高ITO之功函數與表面特性可大幅的提升元件之表現。
    再來,我們將改進元件的結構來調變載子於元件內的再結合與傳輸特性。首先我們採用兩種不同型態(陷阱式與阻擋式)的量子井結構來平衡正負載子的數量,陷阱式量子井擁有較佳的效果,可大幅的提升元件效率達36%,並可減輕於高壓操作下效率驟降的效應。此外共主體結構被採用來侷限載子再結合區域以提升整體元件效率,利用電洞傳輸材料(NPB)與藍光發光材料(p-DMDPVBi)以最佳比例(20/80)混成共主體發光層,並搭配橘光摻雜體(Rubrene)即可製做出高效率白光元件。能帶圖、螢光光譜、吸收光譜、電激發光譜以及空間電荷量測則被使用來探討此二種結構的背後物理機制。結果顯示量子井與共主體結構為簡易且有效增進元件效率的方法。

    Organic light-emitting diodes (OLEDs) are currently considered as promising candidates for large-area, full-color and flat-panel displays due to their prominent advantages such as easy fabrication and convenient use in applications. A lot of effort has, therefore, been made to improve device structures and to understand their operating mechanisms. This thesis focuses on improving the device performance by using the anode ultra-thin buffer layer, quantum-well and co-host structure.
    At first part of this thesis, various ultra-thin buffer layer film was thermally deposited between ITO and NPB as the buffer layer and then treated with the ultraviolet (UV) ozone, then the fabrication of organic light emitting diodes (ITO/buffer layer/NPB/Alq3/LiF/Al) to study its effect on hole-injection properties. Work function was estimated from X-ray photoelectron spectroscopy, and surface properties were calculated from measured contact angles using water and CH2I2 as test liquids. With optimized buffer layer thickness, device performance such as turn-on voltage, current efficiency and maximum luminance are significantly improved. Moreover, eliminate the resonant tunneling effect. Measurements of energy band, surface energy and surface polarity indicated device improvement came from the simultaneous increase in work function and surface energy of ITO by adding treated ultra-thin buffer layer film between ITO and the hole-transporting layer.
    Secondly, device structures are modified to manipulate the carrier characteristics of transporting and recombination. To investigate two different types of multiple-quantum-well (MQW) structure on emission characteristics of white organic light-emitting diodes (WOLEDs), we fabricate trapping-type and blocking-type MQWs by inserting C545T (green dye) and TPBi, respectively, into hole transport NPB layer (ITO/CuPc/NPB/MADN:rubrene/TPBi/LiF/Al). Bright efficient and stable fluorescent white emission was obtained for the OLED with 2 trapping-type MQWs formed with C545T (thickness: 2 nm). The device current and power efficiency were greatly raised 36% relative to that of reference device. Furthermore, the improvement remained even beyond the roll-off effect caused by high current density. Besides, efficient co-host emission layer has been demonstrated by mixing blue-emitting p-DMDPVBi and hole-transporting NPB in optimal weight ratio (w/w = 80/20). First, efficiency enhancement was observed in the fabrication of blue organic light-emitting diodes (ITO/NPB/p-DMDPVBi:NPB/TPBi/LiF/Al). Then, bright, efficient and stable fluorescent white organic light-emitting diodes (WOLEDs) were obtained by doping the optimal co-host emissive layer with orange dye (rubrene). The device performance was significantly improved. The all improvement mechanisms were elucidated using energy level diagrams, photoluminescence spectra, absorption spectra, electroluminescence spectra and SCLC measurement. Current results show that forming the trapping-type MQW structure and the co-host emission layer are promising ways to improve device performance, making it applicable for facile fabrication of efficient OLEDs.

    ABSTRACT 1 中文摘要 3 LIST OF JOURNAL PAPER PUBLICATIONS 4 TABLE OF CONTENTS 5 圖目錄 8 表目錄 11 CHAPTER 1: INTRODUCTION 12 1.1 INTERFACE BETWEEN ELECTRODE AND ORGANIC MATERIAL 12 1.2 CARRIERS BALANCE AND CONFINEMENT IN OLEDS 13 CHAPTER 2: THEORY AND LITERATURE REVIEW 16 2.1 BASIC CONCEPTS OF OLEDS 16 2.1.1 Structures of OLEDs 16 2.1.2 Principles of OLED Operation 17 2.1.3 Energy transfer 18 2.2 THE CHARGE INJECTION MECHANISM IN BUFFER LAYER 22 2.2.1 Tunneling effect 22 2.2.2 Band bending at the organic/metal interface 22 2.2.3 Interfacial dipoles 23 2.3 FUNDAMENTAL OF SURFACE ENERGY 25 2.3.1 Capillarity theory of heterogeneous nucleation 25 2.3.2 Estimation of the surface free energy 27 CHAPTER 3: EXPERIMENTAL PROCEDURE 31 3.1 DEVICE FABRICATION OF ORGANIC LIGHT-EMITTING DEVICES 31 3.1.1 Substrate cleaning procedures 31 3.1.2 OLEDs configuration 31 3.1.3 OLEDs fabrication 32 3.2 THERMAL EVAPORATING SYSTEM 35 3.3 MEASUREMENT OF OLEDS CHARACTERISTICS 37 3.4 MEASUREMENT OF ORGANIC FILM AND METAL FLUORIDE FILM CHARACTERISTICS 37 3.4 MEASUREMENT OF METAL FLUORIDE FILM DEPOSITED ITO SURFACE PROPERTIES 37 CHAPTER 4: IMPROVE THE PERFORMANCES OF ORGANIC LIGHT-EMITTING DEVICES BY USING UV-OZONE TREATED ULTRA-THIN METAL FLUORIDE BUFFER LAYER 39 4.1 UV-OZONE-TREATED ULTRA-THIN NAF FILM AS ANODE BUFFER LAYER ON ORGANIC LIGHT EMITTING DEVICES 39 4.1.1 Electro-optical characteristics of devices with the NaF/ITO anode 39 4.1.2 Energy band analysis of NaF/ITO film 40 4.1.3 Contact angle measurement and surface energy analysis 41 4.1.4 XPS analysis of NaF/ITO film 42 4.2 UV-OZONE-TREATED ULTRA-THIN CUF2 FILM AS ANODE BUFFER LAYER ON ORGANIC LIGHT EMITTING DEVICES 48 4.2.1 Electro-optical characteristics of devices with the CuF2/ITO anode 48 4.2.2 Energy band analysis of CuF2/ITO film 49 4.2.3 Contact angle measurement and surface energy analysis 49 4.2.4 XPS analysis of CuF2/ITO film 50 4.3 TIME-DEPENDENT UV-OZONE TREATMENT ON AN ULTRA-THIN AGF ANODE BUFFER LAYER FOR ORGANIC LIGHT-EMITTING DIODES 55 4.3.1 Morphology investigation on AgF/ITO film 55 4.3.3 Energy band analysis 56 4.3.4 Contact angle measurement and surface energy analysis 57 4.3.5 XPS analysis of AgF/ITO film 60 4.3.5 Resonant tunneling diode model 60 4.4 SUMMARY OF OLEDS WITH VARIOUS ULTRA-THIN BUFFER LAYERS 69 CHAPTER 5: IMPROVE THE PERFORMANCES OF WHITE OLEDS BY MANIPULATING STRUCTURES OF THE DEVICES 70 5.1 CO-HOST COMPRISING HOLE-TRANSPORTING AND BLUE-EMITTING COMPONENTS FOR EFFICIENT FLUORESCENT WHITE OLEDS 70 5.1.1 Carriers characteristics of co-host structure analysis 70 5.1.2 Electro-optical characteristics of devices with blue co-host emitters 71 5.1.3 Optical properties analysis of co-host emitting layers 72 5.1.4 Electro-optical characteristics of WOLEDs with rubrene doped co-host emitter 73 5.1.4 Electro-optical characteristics of WOLEDs with rubrene doped co-host emitter 75 5.1.5 Summary 76 5.2 THE INVESTIGATION OF TWO DIFFERENT TYPES OF MULTIPLE-QUANTUM-WELL STRUCTURE ON FLUORESCENT WHITE ORGANIC LIGHT EMITTING DEVICES 84 5.2.1 Fabrication of optimized WOLEDs 84 5.2.2 UPS spectra analysis of two different types of MQW structure 84 5.2.3 Electro-optical characteristics of devices with two different types of MQW structure 86 5.2.4 SCLC analysis of holes transport layer with two different types of MQW structure 88 5.2.5 Summary 90 CHAPTER 6: CONCLUSION AND RECOMMENDATIONS FOR FUTURE WORK 99 6.1 CONCLUSIONS 99 6.1.1 Ultra-thin buffer layer 99 6.1.2 Multiple quantum-well structure 99 6.1.3 Co-host structure of emitting layer 100 6.2 SUGGESTIONS FOR FUTURE WORK 100 REFERENCES 102

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