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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 劉貴生(Guey-Sheng Liou) | |
| dc.contributor.author | Wei-Hao Chen | en |
| dc.contributor.author | 陳偉豪 | zh_TW |
| dc.date.accessioned | 2021-06-17T06:22:48Z | - |
| dc.date.available | 2023-08-20 | |
| dc.date.copyright | 2018-08-20 | |
| dc.date.issued | 2018 | |
| dc.date.submitted | 2018-08-17 | |
| dc.identifier.citation | Chapter 1
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/72089 | - |
| dc.description.abstract | 本論文分成四個章節，第一章為總體序論。第二章為高透明度奈米銀線/聚二甲基矽氧烷電極於可拉伸式電致變色元件的製備及性質探討，此章節首先合成了高長徑比之奈米銀線，並搭配聚二甲基矽氧烷基材製備出高透明度且可拉伸之透明電極。利用此電極並搭配三苯胺衍伸物和紫精製備出雙極式可拉伸式電致變色元件，以五種具不同結構和氧化電位之三苯胺衍伸物為變色單元搭配紫精，使此可拉伸式電致變色元件在基態具有高透明度，而在外加電壓下時，可變為藍色、深咖啡色、綠色、淡黃色和黃綠色五種不同的電致變色型態。第三章為此可拉伸式電致變色元件之穩定度探討，利用低氧化還原電位之雙極式電致變色單體來降低工作電壓並改善其穩定度。此外更利用了具電活性之材料做為保護層覆蓋銀線電極使其不易受外加電壓影響，此方法不僅能將銀線隔絕於電化學反應外還能藉由保護層之電活性單元來達到電致變色效果。第四章節為結論。此研究利用高長徑比之奈米銀線與製程改進來提升銀線電極之表現，使其在未來應用上具有更大的潛力，並結合實驗室已開發多年之三苯胺系列電致變色材料與可拉伸式電極之應用，拓展了此類電致變色材料的應用層面。 | zh_TW |
| dc.description.abstract | This study has been separated into four chapters. Chapter 1 is the general introduction. Chapter 2 includes the synthesis of silver nanowire (AgNW) with high aspect ratio, preparation of highly transparent AgNW/PDMS hybrid electrodes and the fabrication of the stretchable ambipolar electrochromic devices (ECDs) with five different EC color performance. Chapter 3 describes the stabilities studies of the AgNW/PDMS stretchable ECDs and the ways for improvement. Chapter 4 is conclusions.
The synthesis of AgNW, basic characterization, fabrication parameters, optical and electrical properties, electrochemical and spectroelectrochemical properties of the novel stretchable ambipolar ECDs were investigated and improved. The AgNW/PDMS hybrid electrodes were prepared by a simple preparation process. Owning to the carefully controlled experimental conditions, the obtained stretchable electrodes showed great performance on both optical and electrical properties. Moreover, we applied these AgNW/PDMS electrode to fabricate the stretchable ECDs with five different triphenylamine (TPA) EC materials and heptyl viologen. The obtained stretchable ECDs all showed transparent at neutral state and switched to various colors according to the different redox pair under applied potential. In another part, we firstly examined the electrochemical stabilities of the above ambipolar ECDs. There were an improvement on their electrochemical stability while utilizing the ambipolar EC pair with lower redox potential. Besides, we also find out another approach for improvement by covering the exposed AgNW with electroactive EC films. By this sensible combination, we can not only increase the stability of AgNW/PDMS electrode but also get the EC behavior on these stretchable electrode. | en |
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| dc.description.tableofcontents | TABLE OF CONTENTS
ACKNOWLEDGEMENTS....…………………………………………………i ABSTRACT (in English)……………………………………………………………ii ABSTRACT (in Chinese)………………………………………………………iii TABLE OF CONTENTS………………………………………………………iv LIST OF TABLES…………………………………………………………ix LIST OF FIGURES…………………………………………………………x LIST OF SCHEMES……………………………………………………xvii CHAPTER 1……………………………………………………………1 CHAPTER 2………………………………………………………51 CHAPTER 3…………………………………………………………104 CHAPTER 4………………………………………………………………126 APPENDIX………………………………………………………………………129 LIST OF PUBLICATION…………………………………………………………130 CHAPTER 1 General Introduction 1.1 Electrochromism...2 1.2 Electrochromic System...5 1.2.1 Inorganic Electrochromic System...5 1.2.2 Organic Electrochromic System...9 1.2.3 The Structure of Electrochromic Device...20 1.3 Electrochromism in Ambipolar System...22 1.4 Transparent Conductive Electrodes...25 1.4.1 Conductive materials...26 1.4.2 Silver Nanowire...30 1.4.3 Silver Nanowire/Polymer Hybrid Electrode...34 1.4.4 Electrochromism in Stretchable Electrode...37 1.5 Research Motivation...40 Reference and Notes...42 CHAPTER 2 Preparation and Characterization of Stretchable Ambipolar Eletrochromic Devices Based on Highly Transparent AgNW/PDMS Hybrid Electrodes ABSTRACT OF CHAPTER 2...52 2.1 Introduction...53 2.2 Experimental Section...55 2.2.1 Materials...55 2.2.2 Synthesis of Silver Nanowires (AgNW)...56 2.2.3 Preparation of AgNW/PDMS Stretchable Electrode...57 2.2.4 Fabrication of Stretchable Electrochromic Device...58 2.2.5 Monomer Synthesis...59 2.2.6 Characterization...61 2.3 Results and Discussion...62 2.3.1 Characterization of High Aspect Ratio AgNW...62 2.3.2 Properties of Transparent and Stretchable AgNW/PDMS Hybrid Electrodes...64 2.3.3 Monomer Synthesis and Characterization...70 2.3.4 Electrochemical Properties of Electrochromic Materials Cooperating with AgNW/PDMS Hybrid Electrode...77 2.3.5 Electrochromism and Spectroelectrochemistry...85 2.3.6 Electrochemical properties of Ambipolar Electrochromic Device (ECD)...91 2.3.7 Electrochromism and Spectroelectrochemistry of Ambipolar Electrochromic Devices...97 2.4 Summary...101 Reference and Notes...102 CHAPTER 3 Electrochemical Stability Studies of AgNW/PDMS Stretchable Electrochromic Devices and Approaches for Improvement ABSTRACT OF CHAPTER 3...105 3.1 Introduction...106 3.2 Experimental Section...108 3.2.1 Materials...108 3.2.2 Preparation of AgNW/PDMS Hybrid Electrode Covered by Electroactive Films...109 3.2.3 Characterization...111 3.3 Results and Discussion...112 3.3.1 Basic Electrochemical Stability on AgNW/PDMS Hybrid Electrodes...112 3.3.2 Electrochemical Stabilities of AgNW/PDMS ECDs Based on Ambipolar Electrochromic Materials...114 3.3.3 Enhanced Electrochemical Stability by Covering AgNW with Electroactive Films...120 3.4 Summary...124 Reference and Notes...125 LIST OF TABLES CHAPTER 1 Table 1.1 Color of viologens based on different substituted structure41...11 Table 1.2 Advantages and disadvantages of conjugated conducting polymers...15 Table 1.3 Comparisons for AgNWs/polymer hybrid electrode systems...35 CHAPTER 2 Table 2.1 Electrical, optical properties and FoM value of AgNW/PDMS hybrid electrodes without binder at 400 nm and 550 nm (based on air as background)....68 LIST OF FIGURES CHAPTER 1 Figure 1.1 Electrochromic applications of smart window and car rear-view mirror.17-19...4 Figure 1.2 Viologen numbering scheme...10 Figure 1.3 (a) EC cell atswitched off, intermediate state, and switched on state. (b) Photochromic properties of HPG-V2+ transmission spectra of HPG-V2+ film at bleached and colored states after 30 s UV irradiation (c) Synthesis of hyperbranched and viologen-functionalized polyglcidol.42...12 Figure 1.4 Photographs and absorption spectrum of the electrochromic switching of a Ruthenium purple/methyl viologen ECD, in (a) its colorless and (b) its colored state.43...13 Figure 1.5 Some conducting polymers....15 Figure 1.6 Color performance of EC conducting polymers47...16 Figure 1.7 Polyamide types EC material and its color changes52,55-57,61...18 Figure 1.8 Polyimide types EC material and its color changes53...18 Figure 1.9 Epoxy types EC materials and their color changes54...19 Figure 1.10 Triphenylamine based ECD shows color changing from transparency to black.59...19 Figure 1.11 The schematic diagram of typical ECD structure.62...22 Figure 1.12 Chemical structure of EC conducting polymer and their color changing.63...24 Figure 1.13 Chemical structure of PI containing pyrene and its color changes64...24 Figure 1.14 Chemical structure of PI containing BDATA and its color changes68...25 Figure 1.15 (a) Schematic diagram of electrochemical process based on TPA-Vio. (b) Spectroelectrochemistry and photographs of TPA-Vio based ECD.71...25 Figure 1.16 (a) The transparent electrode based on ITO. (b) The structure of a projective touch panel.72,73...27 Figure 1.17 The OLED device based on conductive polymer.76...27 Figure 1.18 (a) The transparent electrode based on CNT.84 (b) CNT/PET electrode applied to organic light-emitting diodes (OLEDs).85...29 Figure 1.19 (a) The transparent graphene electrode and the application in touch screen.93 (b) Graphene/PDMS stretchable electrode.94...30 Figure 1.20 Demonstration of flexible, transparent films by the combination of (a) copper nanowires98, and (b) silver nanowires with polymer substrates99....31 Figure 1.21 The schematic diagram of (a) growing silver nanowires, and (b) the function of oxygen scavenger101,102...33 Figure 1.22 (a) (b) Electrochromism of WO3 on stretchable AgNW/PDMS hybrid electrode.129,130...38 Figure 1.23 Electrochromism of heptyl viologen in elastomeric ECD based on AgNW/PDMS hybrid electrode.118...39 CHAPTER 2 Figure 2.1 Schematic diagram for preparation of AgNW/PDMS hybrid electrodes....57 Figure 2.2 Fabrication process of stretchable electrochromic device....58 Figure 2.3 SEM images of the AgNW coated on glass slide....63 Figure 2.4 Optical microscopy image of the AgNW/PDMS hybrid electrode....67 Figure 2.5 FoM value plotted with sheet resistance and transmittance (refer to air) without binder at 550 nm and 400 nm...69 Figure 2.6 The appearance of AgNW/PDMS hybrid electrode 70 Figure 2.7 1H NMR spectrum of SNTPPA in DMSO-d6...72 Figure 2.8 13C NMR spectrum of SNTPPA in DMSO-d6...72 Figure 2.9 1H-1H COSY spectrum of SNTPPA in DMSO-d6...73 Figure 2.10 13C-1H HSQC spectrum of SNTPPA in DMSO-d6 74 Figure 2.11 FT-IR spectrum of SNTPPA...75 Figure 2.12 1H NMR spectrum of TPA-3DMA in DMSO-d6...75 Figure 2.13 Differential pulse voltammetry diagram of SNTPPA. Scan rate: 2 mV/s; pulse amplitude: 50 mV; pulse width: 25 ms; pulse period: 0.2 s...76 Figure 2.14 Differential pulse voltammetry diagram of TPA-3DMA. Scan rate: 2 mV/s; pulse amplitude: 50 mV; pulse width: 25 ms; pulse period: 0.2 s...76 Figure 2.15 The schematic diagram of setting CV and UV-Vis measurement which AgNWs/PDMS hybrid electrode serving as working electrode, Pt wire serving as counter electrode and Ag/AgCl serving as reference electrode....80 Figure 2.16 Cyclic voltammetric diagrams of 0.017 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 50 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting direction)...81 Figure 2.17 Cyclic voltammetric diagrams of 0.017 mmole TPA-3OMe and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 50 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting scanning direction)...81 Figure 2.18 Cyclic voltammetric diagrams of 0.017 mmole TPPA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 15 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting scanning direction)...82 Figure 2.19 Cyclic voltammetric diagrams of 0.017 mmole NTPPA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 15 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting scanning direction)...82 Figure 2.20 Cyclic voltammetric diagrams of 0.017 mmole SNTPPA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 50 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting scanning direction)...83 Figure 2.21 Cyclic voltammetric diagrams of 0.017 mmole TPA-3DMA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 50 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting scanning direction)...83 Figure 2.22 Cyclic voltammetric diagrams of 0.017 mmole HV and 0.017 mmole TBABF4 in 2.8 mL propylene carbonate at scan rate of 25 mV s-1 which AgNW/PDMS served as working electrode. (Red arrow indicates the starting scanning direction)...84 Figure 2.23 Absorbance spectrum and color appearance of 0.017 mmole TPA-3OMe and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at 0 V and 0.7 V (vs. Ag/AgCl) which AgNW/PDMS served as working electrode....87 Figure 2.24 Absorbance spectrum and color appearance of 0.017 mmole TPPA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at 0 V and 0.45 V (vs. Ag/AgCl) which AgNW/PDMS served as working electrode....87 Figure 2.25 Absorbance spectrum and color appearance of 0.017 mmole NTPPA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate/GBL 1:1 co-solvent at 0 V, 0.3 V and 0.4 V (vs. Ag/AgCl) which AgNW/PDMS served as working electrode....88 Figure 2.26 Absorbance spectrum and color appearance of 0.017 mmole SNTPPA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at 0 V, 0.1 V, 0.2 V and 0.3 V (vs. Ag/AgCl) which AgNW/PDMS served as working electrode....88 Figure 2.27 Absorbance spectrum and color appearance of 0.017 mmole TPA-3DMA and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at 0 V, 0.1 V and 0.2 V (vs. Ag/AgCl) which AgNW/PDMS served as working electrode....89 Figure 2.28 Absorbance spectrum and color appearance of 0.017 mmole HV and 0.068 mmole TBABF4 in 2.8 mL propylene carbonate at different applied potential which AgNW/PDMS served as working electrode....89 Figure 2.29 Summary of electrochromic color diversity on stretchable AgNW/PDMS hybrid electrodes while served as working electrode....90 Figure 2.30 Schematic diagram of injecting electrochromic material solution....93 Figure 2.31 Cyclic voltammetric diagrams of AgNW/PDMS device containing 3 μmole TPA-3OMe and 3 μmole HV and in 0.2 mL PC solution at scan rate of 50 mV s-1. (Red arrow indicates the starting scanning direction)...94 Figure 2.32 Cyclic voltammetric diagrams of AgNW/PDMS device containing 3 μmole TPPA and 3 μmole HV in 0.2 mL PC solution at scan rate of 50 mV s-1. (Red arrow indicates the starting scanning direction)...94 Figure 2.33 Cyclic voltammetric diagrams of AgNW/PDMS device containing 3 μmole NTTPA and 3 μmole HV in 0.2 mL PC/GBL (1:1) co-solvent at scan rate of 50 mV s-1. (Red arrow indicates the starting scanning direction)...95 Figure 2.34 Cyclic voltammetric diagrams of AgNW/PDMS device containing 3 μmole SNTTPA and 3 μmole HV in 0.2 mL PC/GBL (1:1) co-solvent at scan rate of 50 mV s-1. (Red arrow indicates the starting scanning direction)...95 Figure 2.35 Cyclic voltammetric diagrams of AgNW/PDMS device containing 3 μmole TPA-3DMA and 3 μmole HV in 0.2 mL PC solution at scan rate of 50 mV s-1. (Red arrow indicates the starting scanning direction)...96 Figure 2.36 Absorbance spectrum and color appearance of AgNW/PDMS device containing 3 μmole TPA-3OMe and 3 μmole HV in 0.2 mL PC solution at different applied potential....98 Figure 2.37 Absorbance spectrum and color appearance of AgNW/PDMS device containing 3 μmole TPPA and 3 μmole HV in 0.2 mL PC solution at different applied potential....99 Figure 2.38 Absorbance spectrum and color appearance of AgNW/PDMS device containing 3 μmole NTPPA and 3 μmole HV in 0.2 mL PC/GBL 1:1 co-solvent at different applied potential....99 Figure 2.39 Absorbance spectrum and color appearance of AgNW/PDMS device containing 3 μmole SNTPPA and 3 μmole HV in 0.2 mL PC/GBL 1:1 co-solvent at different applied potential....100 Figure 2.40 Absorbance spectrum and color appearance of AgNW/PDMS device containing 3 μmole TPA-3DMA and 3 μmole HV in 0.2 mL PC solution at different applied potential....100 CHAPTER 3 Figure 3.1 Chemical structures of BDATA-TEOSPIC....108 Figure 3.2 Fabrication procedure of electroactive film/AgNW/PDMS electrode....110 Figure 3.3 Cyclic voltammetric diagrams of AgNW/PDMS electrode served as working electrode for (a) positive scans and (b) negative scans in 2.8 mL PC solution with 0.28 mmole TBABF4 (0.1 M) at scan rate of 50 mV/s....113 Figure 3.4 Cyclic voltammetric diagrams of AgNW/PDMS ECDs (working area: 2*2 cm2; gap thickness: 0.5 mm) with (a) 0.03 mmole TPA-3OMe and 0.03 mole HV (b) 0.03 mmole TPPA and 0.03 mole HV in 0.2 mL PC. (c) 0.03 mmole NTPPA and 0.03 mole HV (d) 0.03 mmole SNTPPA and 0.03 mole HV in 0.2 mL PC/GBL 1:1 co-solvent. (e) 0.03 mmole TPA-3DMA and 0.03 HV in 0.2 mL PC at scan rate of 50 mV/s....115 Figure 3.5 Cyclic voltammetric diagrams of AgNW/PDMS ECDs (working area: 2*2 cm2; gap thickness: 0.5 mm) with (a) 0.03 mmole TPA-3OMe and 0.03 mole HV (b) 0.03 mmole TPPA and 0.03 mole HV in 0.2 mL PC at scan rate of 50 mV/s for 10 cycle scans....117 Figure 3.6 Cyclic voltammetric diagrams of AgNW/PDMS ECDs (working area: 2*2 cm2; gap thickness: 0.5 mm) with (a) 0.03 mmole NTPPA and 0.03 mole HV in 0.2 mL PC/GBL 1:1 co-solvent. (b) 0.03 mmole TPPA and 0.03 mole HV in 0.2 mL PC at scan rate of 50 mV/s...118 Figure 3.7 Summary of the electrochromic devices based on AgNW/PDMS hybrid electrode....119 Figure 3.8 (a) Photograph of BDATA-TEOSPIC coated on ITO glass and its light emitting performance upon irradiating at 365 nm. (b) Alpha-step profile of BDATA-TEOSPIC coated on ITO glass....121 Figure 3.9 Cyclic voltammetric diagrams of BDATA-TEOSPIC coated on ITO glass which immersed in 0.1 M TBAP/acetonitrile solution. (Working area: 0.7*2 cm2; film thickness: 700 ± 40 nm)...121 Figure 3.10 Photograph of BDATA-TEOSPIC coated on AgNW/PDMS hybrid electrode and its light emitting performance upon irradiating at 365 nm....123 Figure 3.11 Cyclic voltammetric diagrams of BDATA-TEOSPIC coated on AgNW/PDMS hybrid electrode which immersed in 0.1 M TBAP/acetonitrile solution....123 LIST OF SCHEMES CHAPTER 1 Scheme 1.1 Color change of WO3 in electrolyte containing univalent metal cations10...3 Scheme 1.2 Structure of PEDOT...3 Scheme 1.3 Color change of WO3 in electrolyte containing univalent metal cations...6 Scheme 1.4 Oxidation route of Ir(OH)3...6 Scheme 1.5 Mechanism of anionic process...7 Scheme 1.6 Oxidation route of Ir(OH)3...7 Scheme 1.7 Oxidation route of Prussian blue to Prussian green...7 Scheme 1.8 Oxidation route of Prussian blue to Prussian yellow...7 Scheme 1.9 Reduction route of Prussian blue...8 Scheme 1.10 Metallophthalocyanine (Pc)...9 Scheme 1.11 The redox states of viologen.23...11 Scheme 1.12 Coloring process of Iron(II) hexacy anoruthenate(II) and Bipyridylium...13 Scheme 1.1360...17 Scheme 1.14 The reduction of ionic silver by polyol method.100...33 CHAPTER 2 Scheme 2.1 Synthesis route of SNTPPA and TPA-3DMA...71 | |
| dc.language.iso | en | |
| dc.subject | 奈米銀線 | zh_TW |
| dc.subject | 聚二甲基矽氧烷 | zh_TW |
| dc.subject | 電致變色 | zh_TW |
| dc.subject | 雙極式 | zh_TW |
| dc.subject | 三苯胺 | zh_TW |
| dc.subject | Silver nanowire | en |
| dc.subject | Polydimethylsiloxane | en |
| dc.subject | Ambipolar | en |
| dc.subject | Electrochromism | en |
| dc.subject | Triphenylamine | en |
| dc.title | 高透明度奈米銀線/聚二甲基矽氧烷電極應用於可拉伸式電致變色元件之製備及性質探討 | zh_TW |
| dc.title | Novel Stretchable Ambipolar Electrochromic Devices Based on Highly Transparent Silver Nanowire/PDMS Hybrid Electrodes | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 106-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 蕭勝輝(Sheng-Huei Hsiao),陳志堅(Jyh-Chien Chen),許聯崇(Lien-Chung Hsu),張嘉文(Cha-Wen Chang) | |
| dc.subject.keyword | 奈米銀線,聚二甲基矽氧烷,電致變色,雙極式,三苯胺, | zh_TW |
| dc.subject.keyword | Silver nanowire,Polydimethylsiloxane,Electrochromism,Ambipolar,Triphenylamine, | en |
| dc.relation.page | 130 | |
| dc.identifier.doi | 10.6342/NTU201803302 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2018-08-18 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
| 顯示於系所單位： | 高分子科學與工程學研究所 | |
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