臺灣博碩士論文加值系統

高分子發光二極體(PLED)是共軛高分子近年來最具有工業發展潛力之應用之一。比較小分子發光二極體(OLED)具有製程簡單、低成本、可大面積化、可做曲饒性面板、輕薄化等優點。但目前遇到了操作壽命短、操作電壓高、量子效率低、電極介面接和差等問題。本研究探討利用鋰鹽(dopant)與高分子固態電解質(PEO)混摻入發光材料MEHPPV之方法，發現可以有效降低PLED工作電壓。鋰鹽經由電解質柔軟鏈鍛順利進入MEHPPV，並且效能比未添加高分子固態電解質(僅添加鋰鹽或純MEHPPV)之樣品具有較低之操作電壓，較高極子數目，而亮度也相當。
本文經由7Li NMR觀察混摻樣品之離子運動性，並了解鋰離子之分布狀況。研究發現MEHPPV/(PEO+Li) =60/40相容性最好有較多的鋰離子進入發光材料主結構因其具有較低活化能，在結構上鋰鹽有效的經由PEO的鏈鍛doping進入MEHPPV並且doping於陰電性較高之烷氧基與苯環之間，生成極子(polaron)與雙極子(bipolaron)，因此降低能帶差，並增加共軛長度，使得操作電壓因此降低了將近2V。導電度相較於未添加PEO者，增加了101~105，並且因為共軛長度經由PEO的添加而增長，UV及PL發現了光譜往紅位移方向移動將近10nm。在放光效率中以MEHPPV/(PEO+Li)=50/50具有最高螢光強度者具有最佳螢光效率，高於50%MEHPPV之樣品因PEO鏈段的捲繞反而降低了螢光性質。
本研究對於鋰離子的配位，運動性，活化能及表面紋理對於光性元件之關連性作探討，希望對將來高分子發光二極體之改質有個參考依據。

Polymer light-emitting diode (PLED), entails problems such as short lift time, low quantum yield, high running voltage and insufficient interface adhesion between electrode and light emitting materials. In current study we explore a tunable doping by composite a polymer electrolyte, with the light emitting materials, MEHPPV. The study showed that the flexible PEO’s chain motion facilitated the ion doping with MEHPPV, which are otherwise immiscible with ion salt. As a result of the modification, it enhances electron and hole recombination, lowered the work potential and improved the quantum efficiency.
The dynamics and local structures of lithium ion in the electrolyte composite PLED polymer composite is well illustrated by 7Li NMR. The best miscibility is achieved with MEHPPV/(PEO+Li)=60/40 wt% with the highest amount of lithium doped in MEHPPV. The doping forms polaron and bipolaron and decreased energy band gap, and successively lowered the work potential of about 2V with the conductivity increases 101~105 fold. UV and PL spectra indicated increasing conjugated length resulting form the more effective doping. Surface analyses from AFM and activation energy (Ea) measured from NMR line width provided detailed understanding of the coordination structures and exchange of lithium between MEHPPV and PEO, which contributes to the optical properties. The approach serves as a guidance to improve PLED optical and physical properties with tunable doing by polymer electrolytes.

目 錄
目錄…………………………………………………………………….……I表目錄………………………………………………...…………………….V圖目錄…………………………………………………….………………VII中文摘要…………………………………………………………….....ⅩIV英文摘要………………………………………………………………ⅩV
第一章 緒論………………………………………………………….……..1
1-1前言………………………………….……………………………….….1
1-2有機共軛導電高分子之發展…….….....……………………………….1
1-3有機共軛高分子的電子狀態…………….……….…………………….2
1-3-1 古典半導體之帶結構理論理論...………...……………..…………..2
1-3-2 共軛高分子之帶傳導理論…………..…...………………..…...3
1-3-3 Doping and Dopants...……………………….…………………….4
1-4 發光理論……………..……..…………………………………………..6
1-4-1 EL與PL發光原理………………………………………….………...6
1-4-2 影響螢光之因素..…………..………………………………………9
1-5 本文架構與目的…..……………………..……………………………11
1-6 第一章參考文獻………..……………………………………………..18
第二章 文獻回顧………………………………………………………….20
2-1 發光材料：PPV系及MEHPPV……………………………………….20
2-1-1 MEHPPV之發展近況………………...……………………………..20
2-1-2 MEHPPV高分子發光二極體……...………………………………..21
2-1-3 MEHPPV高分子發光二極體之改質-結構上………..…………….21
2-1-4 MEHPPV之改質-混摻型發光元件…………………………..…….23
2-2 有激發光二極體之發展.………………..…………………………….26
2-1-1 光色的發展…………………………..………………….………….27
2-2-2 效率及亮度改進的發展…………..…………………….………….28
2-2-3 電極修飾……………………………………………………….….29
2-3 文獻分析…………..………………..…………………………………30
2-4第二章參考文獻……..………………….……………………………..32
第三章 實驗及其技術原理……………………………………………….36
3-1 樣品製備…………..………..…………………………………………36
3-1-1 MEHPPV合成實驗過程…………………..………………...……...36
3-1-1-1單體合成………………………..…………………………….…...36
3-1-1-2 聚合反應………………..………………………………………...38
3-1-1-3 單體與高分子之鑑定………………..…………………………...38
3-1-2 高分子溶液的製備…………………..………………….………….41
3-1-3 元件製作……………………..……………………………………..42
3-1-3-1 基材的選擇與清潔…………………..…………………………...42
3-1-3-2 高分子的塗膜…………………..………………………………...43
3-1-2-3 電極選擇與蒸鍍……………….……………………….…..43
3-1-4 實驗藥品…………..…………………………………………….….44
3-2 分析儀器應用理論及操作程序…………..…………………..………47
3-2-1 結構分析………………..…………………………………………..47
3-2-1-1 傅立葉式紅外線吸收光譜儀(FT-IR)………………..…………..47
3-2-1-2 固態核磁共振儀(Solid state NMR)………………..………….....48
3-2-1-3 微差式掃描熱卡計(DSC)…………………………..…………....57
3-2-1-4 熱重分析儀(TGA)………………………………..……………....59
3-2-2 表面紋理分析……………………………………..………………..60
3-2-2-1掃描式電子顯微鏡(SEM)………………………...……………….60
3-2-2-2 原子力學電子顯微鏡(AFM)…………………..…………………61
3-2-3 電性分析…………………………………………………………..62
3-2-3-1 交流阻抗儀(AC Impendence)……………..……………………..62
3-2-4 光性分析…………………………………..………………………..65
3-2-4-1 紫外光-可見光吸收光譜儀(UV-Vis)…………………...………..65
3-2-4-2 光激發光螢光光譜(PL)與電激發光光譜(EL)..……………..…..65
3-2-5 元件性質分析……………………..……………………………......66
3-2-5-1 電特性分析儀………………..……………………………...……66
3-3 第三章參考文獻…………………………………………………..77
第四章 結果與討論……………………………………………………….80
4-1 材料結構特性之分析…...……..……...………………………………83
4-1-1熱重損失分析………………...…………………...………..………..83
4-1-2 微差掃描卡計之研究分析………………..……..…………....……86
4-1-3 傅立葉紅外線光譜儀之研究分析………..………………………..92
4-1-4 固態核磁共振光譜分析………………..………………………....104
4-1-4-1 CP/MAS NMR光譜…………….……………..………………....104
4-1-4-2 7Li NMR光譜…………………………………..………………..108
4-1-4-3 Li動態動力學-T1及T2 NMR…………………..………………..116
4-2 材料電性特性之分析………………………………………………..134
4-2-1 Li動態動力學-T1及T2 NMR………………………………………134
4-3 材料表面結構分析…………………..………………...…………….143
4-3-1 掃描式電子顯微鏡………………………………………………..143
4-3-2原子力學顯微鏡…………………………………………………....151
4-4 光學特性分析…………………………..……………………………155
4-4-1紫外光-可見光光譜分析…………….…………………………….155
4-4-2螢光光譜分析………………………………………………..……..161
4-5元件特性分析………………………………………………………...166
4-6第四章參考文獻………...………………………………………...….170
第五章 總結……………………………………………………………...174
表目錄
Table 1-1 Typical maximum doping levels.………....………………………6
Table 1-2 The influence of substituents on fluorescence…..………………10
Table 2-1 Polymer LED and LEC…………………...……………………..25
Table 3-1 NMR Chemical shift of monomers and MEHPPV………..……40
Table 3-2 Assignment of the peaks in IR spectrum of MEHPPV………….41
Table 3-3 Weight and mole ratios of composite electrolytes….…………...42
Table 3-4 Chemical structure and supplier in this investigate……………..44
Table 4-1 The symbolize of samples that contents of composition in blending system…………………………………………………82
Table 4-1-2-1 PEOχ%、ΔH、Tm of MEHPPV Blending PEO/LiClO4 System, which have different percentage…..…….………...……89
Table 4-1-3-1 PEO結晶與非結晶相及摻雜LiClO4之紅外線光譜吸收峰位置表………………………………………………………………98
Table 4-1-3-2 純MEHPPV、PEO、LiClO4紅外線光譜主要吸收峰位置表…………………………………………………………………99
Table 4-1-4-1 TCH and T1ρ of different carbon from pure MEHPPV…….106
Table 4-1-4-2 The △1/2 in MEHPPV/[PEO/LiClO4(10%)] system at 238K…………………………………………………………….112
Table 4-1-4-3 The active energy of lithium in every component of every different blending samples…………………………...…………115
Table 4-2-1-1 The conductivity and PEO crystallinity of blend system….139
Table 4-2-1-1 Conductivity and Activation Energy(eV) of Li ion conduction in 10%LiClO4 system…………………….…………………….140
Table4-3-2-1 The morphology of blending sample MEHPPV/PEO/Li(10%) spinning coating on ITO glass obtained from AFM………..….152
圖目錄
Figure 1-1 conjugated structure of 1,3-butene……………………………..13
Figure 1-2 The representation of energy levels of π MOs with increasing size of the molecules for PA, (CH)n…………………………....13
Figure 1-3 Band gap of insulator,semiconductor and metal………………14
Figure 1-4 Actual structures of polarons/bipolarons in Poly(p-phenylene)..14
Figure 1-5 Band structure evolution for Poly(pyrrole)(P(Py))……….…….15
Figure 1-6 A schematic summary of the methods of doping and related chemical and physical phenomena ………………….…………15
Figure 1-7 Photoluminescence(PL) Theory………………………………..16
Figure 1-8 Electroluminescene(EL) Theory………………………………..16
Figure 1-9 Contrast between EL and PL…………………………………17
Figure 1-10 EL Self-absorption of PPV and UV、PL spectra of PPV……..17
Figure 2-1 Flexibility polymer light emitting diode ……………………….31
Figure 2-2 Schematic diagrams of the electrochemical processes in a solid -state light-emitting electrochemical cell………...…………….31
Figure 2-3 interpenetrating network, IPN………………….………………31
Figure 3-1 1H liquid state NMR of monomer of MEHPPV………………..68
Figure 3-2 1H liquid state NMR of MEHPPV…………………………...…68
Figure 3-3 13C liquid state NMR of 1-Methoxy-4-(2-Ethyl-hexyloxy) Benzene………………………………...………………………69
Figure 3-4：13C liquid state NMR of 2,5-bis(Bromomethyl)-1-Methoxy-4-(2- Ethyl-hexyloxy) Benzene………….…………………………...70
Figure 3-5 13C Solid-state NMR Spectra of poly[2-Methoxy-5-(2’-Ethyl- hexyloxy)-p-(phenylene vinlene)](MEHPPV) ………………...71
Figure 3-6 IR spectra of 2,5-bis(Bromomethy)- 1-Methoxy-4-(2-Ethyl— hexyloxy)Benzene and poly[2-Methoxy-5-(2’-Ethyl-hexyloxy)- p-(phenylene vinlene)] (MEHPPV) …………………………...72
Figure 3-7 MEHPPV sample spin coating on ITO glass…………………..73
Figure 3-8 single layer polymer light emitting diode……………………....73
Figure 3-9 Situation of sample and NMR roter…………………………….73
Figure 3-10 the model of Bozeman energy ,and single is recovery by exponent………………………………………………………..74
Figure 3-11 Inversion-Recovery pluse plot………………………….……..74
Figure 3-12 Relaxation time,T1 get from relation of intensity and correlation time……………………………………………………………..74
Figure 3-13 Schematic structure of AFM………………………………….75
Figure 3-14 The formation of fluorescence and phosphorescence of molecules……………………………………………………….76
Figure 3-15 Relaxation constant TCH and T1ρ from different contact time and intensity…...……………………………………………….76
Figure 4-1本論文研究架構之流程圖…………………………………….81
Figure 4-1-1-1 TGA thermogram of MEHPPV and PEO………………….84
Figure 4-1-1-2 TGA thermogram of various percentages of MEHPPV blending samples, which have PEO and 10%LiClO4 of PEO….84
Figure 4-1-1-3 TGA thermogram of various percentages of MEHPPV blending samples, which have PEO and 20%LiClO4 of PEO….85
Figure 4-1-2-1 DSC thermogram of various percentages of MEHPPV blending sample, which have PEO and 10%LiClO4 of PEO…..90
Figure 4-1-2-2 DSC thermogram of various percentages of MEHPPV blending sample, which have PEO and 20%LiClO4 of PEO…..90
Figure 4-1-2-3 DSC thermogram of pure MEHPPV………………………90
Figure 4-1-3-1 The IR spectra of different ratios of PEO and LiClO4……100
Figure 4-1-3-2 IR spectra of pure LiClO4 and PEO………………………101
Figure 4-1-3-3 IR spectra of MEHPPV, MEHPPV/LiClO4 MEHPPV/PEO/Li…………………………………………….101
Figure 4-1-3-4 IR Spectra of various percentages of MEHPPV blending samples, which have PEO and 10%LiClO4 of PEO…………..102
Figure 4-1-3-5 IR Spectra of various percentages of MEHPPV blending samples, which have PEO and 20%LiClO4 of PEO………..…103
Figure 4-1-4-1 Pure MEHPPV at Different Contact time from solid-state 300 Hz NMR spectra…………...………………………………….119
Figure 4-1-4-2 Different situation carbon of Pure MEHPPV in different contact time……...………...………………………………….120
Figure 4-1-4-3 13C NMR spectra in various percentage MEHPPV/(PEO+Li+)………………………………………...121
Figure 4-1-4-4 7Li NMR Spectra of 50 % MEHPPV at various spinning rate (500~4500 Hz). (obtained by 300 MHz solid NMR)…………122
Figure 4-1-4-5 7Li NMR Spectra of 5% MEHPPV at various temperature (208K~348K).…...………...………………………………….123
Figure 4-1-4-6 7Li NMR Spectra of 20% MEHPPV at various temperature (208K~348K).…...………...………………………………….124
Figure 4-1-4-7 7Li NMR Spectra of 40% MEHPPV at various temperature (208K~348K).…...………...………………………………….125
Figure 4-1-4-8 7Li NMR Spectra of 50% MEHPPV at various temperature (208K~348K).…...………...………………………………….126
Figure 4-1-4-9 7Li NMR Spectra of 60% MEHPPV at various temperature (208K~348K).…...………...………………………………….127
Figure 4-1-4-10 7Li NMR Spectra of 80% MEHPPV at various temperature (208K~348K).…...………...………………………………….128
Figure 4-1-4-11 7Li NMR Spectra of MEHPPV/LiClO4 at various temperature (208K~348K)……………………………………129
Figure 4-1-4-12 The Li+ relative weight(%)add to polymer or forming ion pair of blending sample from 7Li NMR Spectra……………..130Figure 4-1-4-13 The △1/2 (full width of a half maximum)in various MEHPPV content in MEHPPV/[PEO/LiClO4(10%)] system from 7Li NMR Spectra……………………………………….131
Figure 4-1-4-14 Variable temperature T1 for different MEFPPV content blending sample...………...……………………..…………….132
Figure 4-1-4-15 The schemematic diagram of the blended electrolyte...…133
Figure 4-2-1-1 Conductivity vs. inverse temperature in the rang from 25℃ to 75 ℃ for 10%LiClO4 system……………………………..141
Figure 4-2-1-2 Conductivity of rising and dropping temperature processes………………………………………………………142
Figure 4-2-1-3 Conductivity of different salt blending 60%MEHPPV/40% [PEO+Salt(10%)] system…..…………………………………142
Figure 4-3-1-1 SEM photo of 10p-50% blending sample film ×1000(a) dissolve it by heating and prepare film in dry box；(b) dissolve it by heating and prepare film in the room；(c) dissolve it by room temperature and prepare film in dry box；(d) dissolve it by room temperature and prepare film in the room…………………….146
Figure 4-3-1-2 SEM photo of 60%MEHPPV/40%(PEO/LiClO4(10%)) blending sample film ×1000 prepare from using different solvents(a)toluene;(b)cyclohexane;(c)Chloroform……..…….147
Figure 4-3-1-3 SEM photo of blending sample film×1000(a)Pure MEHPPV;(b)MEHPPV+LiClO4;(c)MEHPPV+PEO………...148
Figure 4-3-1-4 SEM photo of blending sample film×1000(a)5%(b)20% (c )40%;(d )50%;(e )60%;(f )80% of MEHPPV content in MEHPPV/(PEO/LiClO4(10%))……………………………….149
Figure 4-3-1-5 SEM photo of blending sample film ×1000 (a)5% ；(b) 20% ；(c )40% ； (d )50% ； (e )60% ； (f )80% of MEHPPV content in MEHPPV/(PEO/LiClO4(20%))…………………...150
Figure 4-3-2-1 AFM Micrographs of different blending sample on ITO glass (25μm ×25μm) (a)ITO glass after cleaning;(b)MEHPPV+Li(c) 20% MEHPPV content in MEHPPV/[PEO/LiClO4 (10%)]…..153
Figure 4-3-2-2 AFM Micrographs of different blending sample on ITO glass (25μm ×25μm) (d)40%；(d)60%；(f )80% MEHPPV content in MEHPPV/[PEO/LiClO4(10%)]……………………………....154
Figure 4-4-1-1 UV-Vis spectra of 40%、60%、80% MEHPPV in MEHPPV/ PEO/LiClO4(10%) system using different solvent (chloroform or toluene)………………………………………………………..159
Figure 4-4-1-2 UV-Vis spectra of Pure MEHPPV, MEHPPV/PEO,MEHPPV /Li and MEHPPV/PEO/LiClO4(10%)…………….………..159
Figure 4-4-1-3 UV spectra of various MEHPPV/[PEO/Li+(10%)] blending sample and Pure MEHPPV……………………………...…160
Figure 4-4-1-4 UV spectra of 60% MEHPPV add PEO and different salt.160
Figure 4-4-2-1 PL spectra of 40%、60%、80% MEHPPV contents in MEHPPV/PEO/LiClO4(10%) system use different solvent (chloroform or toluene)…………………………………….164
Figure 4-4-2-2 PL spectra of Pure MEHPPV, MEHPPV/PEO, MEHPPV/Li and MEHPPV/PEO/LiClO4(10%)………………………….164
Figure 4-4-2-3 PL spectra of various MEHPPV/[PEO/Li+(10%)] blending sample and Pure MEHPPV…………………………...……165
Figure 4-4-2-4 PL spectra of 60% MEHPPV add PEO and different salt (Mg(ClO4)2、LiClO4、LiPF6)…..………………………….165
Figure 4-5-1 IV curve of Pure MEHPPV and 20%,40%,60%,80%MEHPPV content in MEHPPV/PEO/Li (10%) blending sample…..…168
Figure 4-5-2 Brightness and apply voltage of Pure MEHPPV and 60%,80% MEHPPV content in MEHPPV/PEO/Li (10%) blending sample……………………………………………………....168

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