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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 汪根欉(Ken-Tsung Wong) | |
dc.contributor.author | Shih-Chun Lin | en |
dc.contributor.author | 林士竣 | zh_TW |
dc.date.accessioned | 2021-06-07T18:00:41Z | - |
dc.date.copyright | 2020-09-16 | |
dc.date.issued | 2020 | |
dc.date.submitted | 2020-08-12 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/16090 | - |
dc.description.abstract | 近年有機發光材料發展蓬勃,目前已發展至第三代熱活化延遲螢光(Thermally Activated Delayed fluorescence, TADF) 材料。第二代磷光材料利用有機金屬錯合物放出磷光,但鉑及銥金屬的稀少性及高成本使得純有機TADF分子可望成為新的替代方案,然而要兼具TADF性質及放光的高效率也是其設計之難處。近期以物理性混摻電子予體及電子受體的激發活化錯合物 (Exciplex) 逐漸受到高度關注,比起 TADF 分子利用化學鍵連結電子予體及受體。激發活化錯合物將電子予體及受體分別設計不僅利於調控能階高低使單重/三重態能階差縮小,以熱活化的方式有效利用三重態激子,達到100% 的內部量子產率。 本論文中主要探討準線型及星狀結構對電子傳輸材料的影響。在激發錯合物中,作為電子受體並搭配合適的電子予體,使用於有機光電元件的主體材料或放光層。第二章探討吡啶及三嗪核心準線型電子受體,引入間位取代阻斷共軛,以維持高能階及三重激發態能量,並於末端修飾上氰基利於電子注入。利用此特質調控元件材層之分子排列,增強水平方向的躍遷偶極,進而提高元件出光效率。第三章利用三嗪及嘧啶星狀TADF分子作為電子受體,利用其分子內的雙極 (Bipolar) 設計有利電子及電洞良好的傳輸。以三嗪及嘧啶為核心,引入末端的氰基修飾延伸共軛,調整電子受體能階,並與合適電子予體搭配,可將激發錯合物的放光由綠光調整至橘光。 第四章以七員氮呯為主體,相對於五六員環的分子設計,氮呯具非芳香化特性因此具有十分強的推電子特質,有助於提高分子能階,作為薄膜光電偵測元件之阻擋層使用可降低暗電流提高偵測動態範圍。合成出的p-Az分子擁有高HOMO能階及可見的n-pi*吸收峰顯示分子容易氧化且激發後能藉快速的系間轉換產生三重激發子,文獻中常利用於光聚合反應催化劑之應用。七環分子構型扭曲,且尚未有文獻詳細探討結構之特殊性,此系列後續極具有開發潛能。 | zh_TW |
dc.description.abstract | OLEDs are widely applied in modern display recently. However, the cost is still high due to the adoption of rare metals. Thermally activated delayed fluorescence (TADF) materials become a popular research topic since it can harvest all excitons to give nearly 100% quantum efficiency. A strategy of synthesizing TADF molecules is to control the HOMO-LUMO overlap. Nevertheless, the synthesis is challenged and suffered from the lack of reliable prediction of energy level of the effective moiety in these molecules. In contrast to TADF materials, the exciplex-based system having the electron and hole distribute on different molecules not only can realize nearly zero ΔEST, which maximizes the exciplex with theoretical 100% quantum yield as TADF molecules did, but also can reduce the synthetic difficulty and provides flexible manipulation of energy level. My research mainly focuses on the influence between quasi-linear star-shaped Electron Transporting Materials (ETMs) as electron acceptors for exciplex-based system. These materials can be utilized as host materials or emitting layers in exciplex-based OLEDs. The research of ETMs is mainly focused on its thermal stability and electron mobility. In second chapter, the quasi-linear configuration is applied to the ETMs for conjugation interruption to elevate triplet energy and maintain large energy bandgap. According to literature, the introduction of cyano group has a beneficial effect to electron injection and mobility. On the other hand, the star-shaped molecules are known for its high thermal stability in electron semiconducting materials. In third chapter, the research involves the star-shaped structure with pyrimidine- and triazine-building blocks which have the advantage of strong electron-deficient characteristics, thermal stability and suitable energy level. The introduction of cyano group extends conjugation, contributing to the red-shifted emission in exciplex-based system. In the last chapter, a novel N-seven-membered ring, Azepine, has been synthesized and applied to organic optoelectronic materials. Azepine derivatives are non-aromatics with strong electron-donating abilities to elevate the energy levels. p-Az has great potential as electron-blocking materials in organic photodetectors for dynamic range enhancement. It has been treated as photocatalysts for atom-transfer radical polymerization (ATRP). The research on azepine is limited by far, and the structure-property relationship of its derivatives have not been identified. This research elucidates the structural-property relationship of azepine derivatives and provides useful information for the development of N-heteroatomic derivatives to ETMs. | en |
dc.description.provenance | Made available in DSpace on 2021-06-07T18:00:41Z (GMT). No. of bitstreams: 1 U0001-3107202000013500.pdf: 34478891 bytes, checksum: 89f47e7cec44cbf998efd8d0a5cc781d (MD5) Previous issue date: 2020 | en |
dc.description.tableofcontents | Content 中文摘要 III Abstract V Content VII Index of Schemes IX Index of Figures X Index of Tables XVI Molecular Structure Index XVIII Chapter 1. The introduction of Optoelectronics 1 1-1 Introduction 1 1-2 The development and basic principle in OLEDs 3 1-3 Host-guest system and energy transfer 9 1-4 Organic photodetectors 14 Chapter 2. Quasi-Linear Electron Transporting Materials (ETMs) 22 2.1 Introduction 22 2.2 Molecular Design 28 2.3 Thermal Properties 32 2.4 Theoretical Calculation 33 2.5 Electrochemical Properties 34 2.6 Photophysical Properties 35 2.7 Exciplex Film 37 Chapter 3. Star-Shaped Thermally Activated Delayed Fluorescence Electron. Acceptors for Exciplex 41 3-1 Introduction 41 3-2 Molecular Design and Synthesis 45 3.3 Thermal Properties 50 3.4 Theoretical Calculation 50 3.5 Electrochemical Properties 52 3.6 Photophysical Properties 53 3.7 Exciplex Film and Device 58 Chapter 4. Photo-application of Novel Azepine Derivatives 66 4-1 Introduction 66 4-2 Azepine Donor Series 71 4-2-1 Synthesis 72 4-2-2 Thermal Properties 73 4-2-3 Crystal Structures 74 4-2-4 Theoretical Calculation 76 4-2-5 Electrochemical Properties 78 4-2-6 Photophysical Properties 80 4-2-7 Photocatalysts for ATRP 82 4.3 Synthesis of Azepine-based Emitters 85 4-3-1 Thermal Properties 86 4-3-2 Crystal Structures 87 4-3-3 Theoretical Calculation 88 4-3-4 Electrochemical Properties 90 4-3-5 Photophysical Properties 91 4-3-6. Application in exciplex OLEDs 93 Chapter 5. Experimental Section 100 General Information 100 Thermal Properties 100 Cyclic voltammetry 100 Photophysical measurements 101 OLED Device Fabrications 102 Quasi-linear ETMs Synthesis 103 Star-Shaped TADF Electron Acceptors for Exciplex 114 Novel Azepine Derivatives Synthesis 120 References 130 Appendix A 137 Appendix B 154 Index of Schemes Scheme 2-1. Molecular structures of quasi-linear ETMs 30 Scheme 2-2. Synthesis pathways of intermediates 31 Scheme 2-3. Synthesis pathways of quasi-linear ETMs 32 Scheme 3-1. Synthesis routes of CzPym, p-CzPym, CzTrz and p-CzTrz 49 Scheme 4-1. The cycloaddition of dibenzo[b,f]azepine[79] 67 Scheme 4-2. Molecule structures of p-Az and m-Az 72 Scheme 4-3. The synthesis routes of p-Az and m-Az 73 Scheme 4-4. The synthesis routes of Trz-NAz and Trz-NAzMe 86 Index of Figures Figure 1-1. Commercial Optoelectronics (a.) RI-DPD 80 laser photodetectors[5] (b.) RGB LEDs.[6] 1 Figure 1-2. OLED-based commercially available products (a.) iPhone 11 Pro (b.) Apple Watch 5 (c.) Samsung Galaxy Fold (d.) LG OLED TV (E8 55inch).[7-9] 3 Figure 1-3. Schematic diagram of an OLED device. (a) Basic structure proposed by Tang in 1987. (b) Multi-layer normal structure employed in recent OLEDs.[12] 5 Figure 1-4. Energy-level diagrams for the doped DMAc-Trz device.[13] 5 Figure 1-5. A simplified Perrin–Jablonski diagram where the rate constants are as follows: kf (fluorescence), knr (nonradiative processes), kdf (delayed fluorescence), kp (phosphorescence), kISC (inter-system crossing), kRISC (reverse intersystem crossing). DEST (the energy difference between S1 and T1)[14] 6 Figure 1-6. The respective mechanism of different OLED generations. 6 Figure 1-7. Ambipolar Blue-light emitter with Spirobifluorene spacer . [16] 7 Figure 1-8. HT materials (top) and ET materials (bottom) 10 Figure 1-9. Schematic diagrams of (a) Förster energy transfer and (b)(c) Dexter energy transfer.[25] 13 Figure 1-10. (a.) OPD architecture where EEL and HEL stands for electron and hole extraction layers (b.) Energy band diagram of OPD under reverse bias (c.) Working principle of reflectance pulse oximeter array[27] (d.) Organic pulse oximeter array to determine blood pulsation and oxygenation levels[29] 15 Figure 1-11. Methods to reduce dark current: (1) a deep HOMO energy of the donor increases the energy barrier for hole injection; 2) a PHJ architecture, 3) vertical phase segregation both reduce charge injection from both electrodes; and 4) blocking layers increase the energetic barrier for charge carrier injection.[28] 16 Figure 1-12. Influence of individual materials parameter of dark current: the energetic disorder (i), effective injection barrier (b), the active layer thickness (L), and charge carrier mobility (o), where b =|LUMOA-HOMOD| for BHJ without blocking layers and b =|LUMOEBL- HOMOD | or |LUMOA- HOMOHBL | for BHJ with blocking layers.[29] 17 Figure 1-13. Reported ClAlPc device performance (a.) Molecular structure and calculated excited state electrostatic potential maps of ClAlPc (b.) Energy-level diagram for photodetector with ClAlPc as charge generation layer. The device structure is ITO/ClAlPc (10nm)/TAPC (90 nm)/MoO3 (15 nm)/Al (120 nm). (c.) Current gain, defined as the photocurrent divided by dark current, is shown as function of bias. 19 Figure 2-1. characteristics of the OLEDs with m-MTDATA:3TPYMB emitting layer 23 Figure 2-2. Structures of common donors and acceptors in exciplex system 24 Figure 2-3. (a) Molecular structures of CBP and TmPyPB; (b) CBP, TmPyPB, and CBP:TmPyPB mixture in THF with 90% water fractions under UV light; (c) normalized PL spectra of the tested compounds and the mixture in THF with 90% water fraction; (d)transient PL profiles of the tested compounds and the mixture. 25 Figure 2-4. (a) The illustration of the pump (266 nm)-probe (IR) Step-Scan FTIR experiment combine with the optimized CN-Cz2:PO-T2T exciplex structure in its S1 and T1 state. (b) A Schematic of exciton, exciplex and polaron generation in CN-Cz2:PO-T2T 26 Figure 2-5. (a) Schematic of a multi-layer OLED structure[48]. (b) General relationship between the anisotropies of molecular shape and molecular orientation in vacuum-deposited amorphous organic films[47]. (c) Effect of the horizontal orientation of BDAVBi and PEBA emitters, and the arrows roughly indicate the direction of the transition dipole moment. 27 Figure 2-6. Angle-dependent PL patterns of TCTA:B4PyMPM exciplex by (a) thermal evaporation (b) spin-coating (c) Schematic diagrams illustrating the relationship between exciplex energies and dimer configurations (d) Singlet transition energies depending on dimer arrangements and their natural transition orbital (NTOs) (hole: green and purple surfaces, particle: red and blue surfaces)[43]. 28 Figure 2-7. Cyclic voltammograms of 2-CNPyr, 5-CNPyr, dphCN-2-Pyr, dphCN-4-Pyr and DmTrz. 35 Figure 2-8. The UV-Vis absorption spectra of quasi-linear ETMs 36 Figure 2-9. (a) Emission spectra of DCA exciplexes with Dur. PMB. and HMB. in cyclohexane. The Dur. and PMB. spectra are shifted to superimposed with that of HMB. (b) Measured exciplex spectra of DCA and alkylbenzene donors in cyclohexane. (c) Effect of solvent fluctuation on emission spectra of exciplexes with 10%, 50% and 90% CT character.[61] 39 Figure 2-10. (a) UV-Vis absorption spectra and photoluminescence spectra of Ntol2:DmTrz (b) Time-resolved transient photoluminescence spectra of Ntol2:DmTrz 40 Figure 3-1. Energy diagram of a conventional organic molecule. 42 Figure 3-2. Molecular structures of CzT and BCzT. The schematic illustrates PLQY and EQE enhancement by insertion of phenyl group 44 Figure 3-3. Chemical Structures and geometric optimization of BCzT and CzT. 44 Figure 3-4. A schematic concept for TADF-type acceptor in exciplex-based systems. 45 Figure 3-5. Proposed mechanism to improve a device stability of exciplex-based OLEDs. 46 Figure 3-6. Normalized luminance of the OLEDs as a function of operating time at a constant current density 47 Figure 3-7. Sy and Asy molecular structures 48 Figure 3-8. Molecular structure and frontier orbital distribution of Asy[69]. 50 Figure 3-9. Computation ground state optimized structures and spatial distributions of HOMO and LUMO of CzPym, p-CzPym, CzTrz and p-CzTrz. 51 Figure 3-10. Cyclic voltammograms of CzPym, p-CzPym, CzTrz and p-CzTrz. 53 Figure 3-11. The UV-Vis absorption spectra and photoluminescence spectra of (a) CzPym, p-CzPym (b) CzTrz, p-CzTrz in DCM (5 x 10-6 M) 55 Figure 3-12. Neat Film absorption and emission (PL) spectra of CzPym, p-CzPym, CzTrz and p-CzTrz. 56 Figure 3-13. (a) CzPym absorption, PL and phosphorescence spectra. (b) CzPym 10% in mCP absorption and PL spectra (c) Transient PL decay of CzPym, p-CzPym, CzTrz and p-CzTrz (d) Transient PL decay of CzPym 10% in mCP 57 Figure 3-14. UV-Vis absorption spectra and photoluminescence spectra of (a) CzPym with fluorene-based donors blend films (b) Time-resolved transient photoluminescence spectra of blend films 59 Figure 3-15. The UV-Vis absorption spectra and photoluminescence spectra of (a) tBuS3/CzPym, tBuS3/p-CzPym, tBuS3/ CzTrz and tBuS3/p-CzTrz blend films (b) Time-resolved transient photoluminescence spectra of blend films 60 Figure 3-16. Gaussian fit and measured PL spectra of tBuS3 neat film and 10-3 M tBuS3 DCM solution indicating the excimer formation. 61 Figure 3-17. Molecular structures applied to devices and energy level alignments 62 Figure 3-18. (a) EL profile under different voltage(b) Power efficiency as a function of voltage (c) V-L characteristics (d) EQE performance 64 Figure 4-1. Mechanisms of ATRP (top) and O-ATRP (bottom). [90, 94] 69 Figure 4-2. Timeline for the development of select families of photocatalysts utilized in metal-free ATRP.[92] 70 Figure 4-3. X-ray structure of p-Az (a) the single molecule geometry (b) the dihedral angle of ∠C21N1C24 (c) the dihedral angle between C4N1C1 plane and phenylene plane (d) the distance between dimer pair (d) the brick packing of p-Az 75 Figure 4-4. Computation ground state optimized structure and spatial distributions of HOMO and LUMO of m-Az and p-Az 77 Figure 4-5. DFT-optimized structures along the view of phenyl axis of p-Az, together with values for the bending angle (a) Top view (b) side 77 Figure 4-6. Cyclic voltammograms of m-Az and p-Az. Oxidation scan was performed in CH2Cl2 solution with 0.1M of nBu4NPF6 as a supportive electrolyte. A glassy carbonelectrode was used as the working electrode; scan rate 300mv s-1 78 Figure 4-7. (a)-(b) Cyclic voltammograms of N-Tol and N-Ph. Oxidation scan was performed in CH2Cl2 solution with 0.1M of nBu4NPF6 as a supportive electrolyte. A glassy carbon electrode was used as the working electrode; scan rate 300 mv s-1. (c) The molecule structure of N-Tol and N-Ph (d) The proposed mechanism of oxidative dimerization of N-Ph 80 Figure 4-8. Absorption and emission spectra of p-Az and m-Az measured in CH2Cl2 solutions (5x10-6M) 81 Figure 4-9. (a) Molecular structures of PC3 and p-Az. (b) GPC analysis (c) NMR spectra in CDCl3 after 8 hours reaction 84 Figure 4-10. X-ray structure of Trz-NAz (a) the single molecule geometry (b) the dihedral angle of specific plane (c) the distance between antiparallel pair and between dimer pair (d) the herringbone packing 88 Figure 4-11. Computation ground state optimized structures and spatial distributions of HOMO and LUMO of Trz-NAz and Trz-NAzMe 89 Figure 4-12. Cyclic voltammograms of Trz-NAz and Trz-NAzMe 90 Figure 4-13. Absorption and emission spectra of Trz-NAz and Trz-NAzMe measured in 10-5M toluene, DCM and DMF solutions 92 Figure 4-14. AIE examination of Trz-NAzMe blended with acceptors 56p-QN and 56m-QN. 94 Figure 4-15. Photophysical properties of Trz-NAz exciplex blend film with quinoxaline-based acceptors 94 Figure 4-16. Molecular structures applied to devices and energy level alignments. 97 Figure 4-17. (a)/(d) J–V–L characteristics (b)/(e) external quantum efficiencies (EQE) and power efficiencies (PE) as a function of luminance, and (c)/(f) EL spectra of Trz-NAz:56p-QN and Trz-NAz:56m-QN based exciplex device. 98 Figure 4-18. (a) The electroluminescence of Trz-NAz:56p-QN and Trz-NAz:56m-QN, (b) The electroluminescence of Trz-NAz:56p-QN and Trz-NAz:56m-QN doped TTDCz 3% and 5%, (c) J-V-R characteristics (d) correlation profile of radiance, Power efficiency and EQE. 98 Index of Tables Table 2.1. Frontier molecular orbitals of quasi-linear ETMs 33 Table 2-2. Computational potential with DFT and electrochemical properties 35 Table 2-3. UV-Vis absorption spectra and optical bandgap of quasi-linear ETMs 37 Table 2-4. Photophysical properties of NTol2:DmTrz exciplex blend film 40 Table 3-1. Computational energy and electrochemical properties of star-shaped ETMs 53 Table 3-2. The absorption and emission spectra of CzPym, p-CzPym, CzTrz and p-CzTrz in CH2Cl2 solutions as well as their absolute PLQY 55 Table 3-3. Photophysical properties of CzPym, p-CzPym, CzTrz and p-CzTrz in neat film 57 Table 3-4. Photophysical properties of CzPym exciplex blend film with fluorene donors. 59 Table 3-5. Photophysical properties of TADF ET exciplex blend film 60 Table 3-6. EL performance of FS1 : CzPym exciplex devices with different ETLs 64 Table 4-1. Computed and electrochemical energy levels of p-Az and m-Az 79 Table 4-2. Photophysical Properties and electrochemical parameters of m-Az and p-Az 82 Table 4-3. Computational SOMO energy for p-Az and PC3 reported values. 84 Table 4-4. ATRP MMA polymerization on different light sources 85 Table 4-5. The electrochemical properties of Trz-NAz and Trz-NAzMe 91 Table 4-6. Photophysical Properties and electrochemical parameters of Trz-NAz and Trz-NAzMe in toluene solution as well as their absolute PLQY 92 Table 4-7. Electroluminescence data of Trz-NAz exciplex-based OLED devices. 98 | |
dc.language.iso | en | |
dc.title | 氮取代雜環為主體之電子傳輸材料設計、合成及應用 | zh_TW |
dc.title | Design, Synthesis and Characterization of N-heteroaromatic-based Derivatives and Application to Electron Transporting Materials | en |
dc.type | Thesis | |
dc.date.schoolyear | 108-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 洪文誼(Wen-Yi Hung),劉舜維(Shun-Wei Liu) | |
dc.subject.keyword | 電子傳輸材料,ATRP光催化劑,近紅外光,熱活化延遲螢光,激發錯合物, | zh_TW |
dc.subject.keyword | Electron transporting materials,ATRP Photocatalyst,NIR-OLEDs,TADF,exciplex, | en |
dc.relation.page | 182 | |
dc.identifier.doi | 10.6342/NTU202002138 | |
dc.rights.note | 未授權 | |
dc.date.accepted | 2020-08-13 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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