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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 劉貴生(Guey-Sheng Liou) | |
| dc.contributor.author | Huan-Shen Liu | en |
| dc.contributor.author | 劉桓升 | zh_TW |
| dc.date.accessioned | 2021-07-11T14:42:05Z | - |
| dc.date.available | 2021-11-09 | |
| dc.date.copyright | 2016-11-09 | |
| dc.date.issued | 2016 | |
| dc.date.submitted | 2016-08-18 | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/78095 | - |
| dc.description.abstract | 本論文分成四個章節，第一章為總體序論。第二章為高對比度雙極式電致變色元件之製備，此元件以TPPA及TPB為變色中心的聚醯胺及紫精衍生物分別為陽極和陰極變色材料，讓陽極及陰極變色材料作為互相之電荷儲存基層，達到穩定及降低工作電壓的效果，並藉由三種材料在UV-Vis吸收光譜上的互補，使可見光區吸收完全，達到全波段遮蔽之效果。第三章是以簡易及方便的方式製備透明可拉伸電極進行電致變色元件的應用。第四章節為結論。此研究探討應用於光電元件中之電致變色材料的搭配及導電材料的製程改進，所製備出的雙極式電致變色元件在透明態時具有高度的透明性，而在著色態時展現紫外光-可見光-近紅外光區全光譜吸收的優異結果，並在長時間使用下仍具有良好的穩定性。此外，以簡易方法轉印奈米銀線至聚二甲基矽氧烷基材所製備出的可拉伸複材電極，同時具備高透明性及高導電度，且在拉伸、扭轉及彎曲情形下仍具有導電性，而我們由此可拉伸複材電極進一步製備出彈性電致變色元件，在透明態及著色態的切換也展現出良好的穩定性。 | 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 electrochromic materials (ECMs) and fabrication of high contrast electrochromic devices (ECDs). Chapter 3 describes the preparation of stretchable electrodes based on silver nanowires (AgNWs) and polydimethylsiloxane (PDMS) hybrid for elastomeric ECDs. Chapter 4 is conclusions.
The fabrication, basic characterization, electrochromic properties of a novel ECD was investigated and improved. The ECD combined three different kinds of ECMs, TPPA-PA, TPB-PA and HV. By introducing HV as an efficient charge trapping layer, the working voltage could be greatly reduced and the performance of overall system was also enhanced. The ECD of Blending-A system exhibits ultra-high contrast from bleaching state with transmittance in visible region up to 85% to coloring state with transmittance only 6% both in visible and NIR regions. High ΔL* (88.2) and ΔT (79.0% at visible light region) could be achieved by the colorless ECD. Thus, it could claim to be a truly “transmissive-to-black” ECD, implying high potential of application as shutter for transparent displays and energy saving devices. In another part, an effective method to transfer AgNWs into PDMS by sacrificial substrates which has hydrophobic surface, and successfully prepare stretchable AgNWs/PDMS hybrid electrodes having high transparency and low sheet resistance at the same time. The prepared electrodes could be stretched, twisted, and bended without significant loss of conductivity. Furthermore, a novel elastomeric HV ECD was fabricated based on these stretchable AgNWs/PDMS hybrid electrodes. This elastomeric HV ECD could exhibit excellent electrochromic behavior and transform the color between colorless and blue even after 100 switching cycle. It was the first ECD based on full AgNWs system. | en |
| dc.description.provenance | Made available in DSpace on 2021-07-11T14:42:05Z (GMT). No. of bitstreams: 1 ntu-105-R03549019-1.pdf: 10533353 bytes, checksum: 5e0b1d8213701ec01f49717038e86be5 (MD5) Previous issue date: 2016 | en |
| 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 CHAPTER 1……………………………………………………………………1 CHAPTER 2……………………………………………………………………81 CHAPTER 3……………………………………………………………………122 CHAPTER 4………………………………………………………………153 CHAPTER 1 General Introduction 1.1 HIGH PERFORMANCE POLYMERS 2 1.1.1 Preparation of Aromatic Polyamides 4 1.1.1-1 High-temperature solution method 4 1.1.1-2 Low-temperature solution method 6 1.1.2 Preparation of Aromatic Polyimides 7 1.1.3 Modification of Aromatic Polyamides and Polyimides 9 1.2 ELECTROCHROMISM 13 1.2.1 Electrochromic Systems 17 1.2.1-1 Transition-metal Oxides 17 1.2.1-2 Inorganic Coordination Complexes 18 1.2.1-3 Organic Molecules 20 1.2.1-4 Conducting Polymers 23 1.2.1-5 Arylamine-based Polymers 25 1.2.2 The Structure of Electrochromic Device 28 1.2.2-1 Transparent conducting layer 28 1.2.2-2 Electrochromic layer 28 1.2.2-3 Electrolyte layer 28 1.2.2-4 Ion-storage layer 29 1.2.3 High Contrast Electrochromic Devices 30 1.3 TRANSPARENT CONDUCTIVE ELECTRODES 32 1.3.1 Transparent and Conductive Material 35 1.3.1-1 Doped Metal Oxides 36 1.3.1-2 Conducting Polymers 37 1.3.1-3 Carbon Nanostructures 38 1.3.1-4 Metallic Nanostructures 41 1.3.2 Silver Nanowires (AgNWs) 42 1.3.2-1 Growth mechanism of polyol method 43 1.3.2-2 Synthetic factors of AgNW 43 1.3.3 AgNWs/ Polymer Hybrid Transparent Electrodes 46 1.3.3-1 Aspect ratio of AgNWs 46 1.3.3-2 Pre-treatments 46 1.3.3-3 Coating methods 47 1.3.3-4 Post-treatments 47 1.3.4 Protection of AgNWs 54 1.4 RESEARCH MOTIVATION 56 REFERENCES AND NOTES 59 CHAPTER 2 Highly Transparent to Truly Black Electrochromic Devices Based on Ambipolar System of Polyamides and Viologen ABSTRACT 82 2.1 INTRODUCTION 83 2.2 EXPERIMENT SECTION 86 2.2.1 Materials 86 2.2.2 Polymer synthesis 88 2.2.3 Fabrication of the Electrochromic Devices 92 2.2.4 Characterization 93 2.3 RESULT AND DISCUSSION 94 2.3.1 Basic Properties of Polyamides 94 2.3.2 Electrochemical Properties of the ECMs 99 2.3.3 Electrochemical Properties of the ECDs 101 2.3.4 Spectroelectrochemistry 104 2.3.5 Materials Integration 108 2.3.6 Thickness Effects 111 2.3.7 Chemical Structure Effects 113 2.4 SUMMARY 118 REFERENCES AND NOTES 119 CHAPTER 3 Highly Transparent Silver Nanowires/ Polydimethylsiloxane Electrode for Elastomeric Electrochromic Device ABSTRACT 123 3.1 INTRODUCTION 124 3.2 EXPERIMENT SECTION 126 3.2.1 Materials 126 3.2.2 Silver nanowires synthesis 126 3.2.3 AgNWs-PDMS stretchable electrode fabrication 127 3.2.4 Elastomeric electrochromic device fabrication 128 3.2.5 Characterization 129 3.3 RESULT AND DISCUSSION 130 3.3.1 Basic characterization 130 3.3.2 Properties of flexible and transparent AgNWs/PDMS hybrid electrodes 133 3.3.3 Stretching, twisting, and bending behavior of the transparent AgNWs/PDMS hybrid electrodes 137 3.3.4 Properties of Elastomeric Electrochromic Device 142 3.4 SUMMARY 149 REFERENCES AND NOTES 150 LIST OF TABLES CHAPTER 1 Table 1.1 Some Typical Aromatic High Performance Polymers 3 Table 1.2 Commercially Available Aromatic Polyamides 6 Table 1.3 Commercially Available Aromatic Polyimides 9 Table 1.4 Some Soluble Aromatic Polyamides 11 Table 1.5 Some Soluble Aromatic Polyimides 12 Table 1.6 Color of viologens based on different substituted structure 21 Table 1.7 Color of quinone systems 22 Table 1.8 The advantages and drawbacks of conducting polymer 24 Table 1.9 Publish papers. (Web of Science. Key word: transmissive-to-black) 31 Table 1.10 List of various applications, their key features, and the suitability of each material 34 Table 1.11 Examples and comparisons for AgNWs-polymer hybrid systems 51 Table 1.12 A partial list of performance of AgNWs-PI films reported in literatures 53 CHAPTER 2 Table 2.1 Inherent Viscosity and Molecular Weights of Polyamides 95 Table 2.2 Solubility Behaviors of Polyamides 95 Table 2.3 Thermal Properties of Polyamides 96 CHAPTER 3 Table 3.1 Thermal properties of PDMS 131 Table 3.2 Solubility Behaviors of PDMS 131 Table 3.3 Optical and Electrochemical Data Collected for Coloration Efficiency Measurements of HV ECD based on the AgNWs/PDMS hyvrid electrode 148 LIST OF FIGURES CHAPTER 1 Figure 1.1 Electrochromic products application categories. 15 Figure 1.2 Photographs of (a) smart windows (b) anti-glare back mirrors (c) and E-papers. 16 Figure 1.3 Switching sequence of the electrochromic glass. 16 Figure 1.4 Representative electrochromic polymers. Color swatches are representations of thin films based on measured CIE 1931 Yxy color coordinates. Key: 0 = neutral; I = intermediate; + = oxidized; − and − − = reduced. 25 Figure 1.5 High-performance polymers (e.g., polyimide types, polyamide types, and epoxy types) utilizing the triarylamine units as an electrochromic functional moiety. 27 Figure 1.6 The schematic of typical ECD structure. 29 Figure 1.7 Potential transparent conductive materials applications and corresponding resistance range required for each application. 33 Figure 1.8 (a) Global demand for resistive style touch panels by area (Source: Displaybank “In depth analysis: Touch screen panel industry trends and business strategies”) (b) Average price of Indium over the last several decades (Source: Alex Freundlich of the University of Houston citing data from the U.S. Geological Survey). 34 Figure 1.9 (a) The transparent electrode based on ITO. (b) The s transparent solar cells made by ITO. 37 Figure 1.10 (a) The OLED based on conducting polymers. (b) Demonstration of a deformable LED fabricated on a PEDOT:PSS circuit. 38 Figure 1.11 (a) The transparent electrode based on CNT.192 (b) The skin-like pressure sensors made by CNT. 39 Figure 1.12 The transparent graphene electrode and the application in touch screen. 41 Figure 1.13 Demonstration of flexible, transparent films by the combination of (a) copper nanowires,211 and (b) silver nanowires with polymer substrates.134 42 Figure 1.14 The schematic diagram of (a) growing silver nanowires,219 and (b) the function of oxygen scavenger. 45 Figure 1.15 Representative TEM images of titania coated silver nanowires with increasing titania shell thickness: (a) 10, (b) 22, (c) 44, (d) 65 and (e) 85 nm. 55 Figure 1.16 Transparent display material market. 58 Figure 1.17 Schematic diagram of transparent display based on OLED with ECD as shutter. 58 CHAPTER 2 Figure 2.1 Schematic diagram of the transparent display regulated by ECD. 85 Figure 2.2 IR spectrum of polyamide films 91 Figure 2.3 Schematic diagram of ECD based on the ambipolar ECMs. 92 Figure 2.4 TGA traces of the polyamides. 97 Figure 2.5 DSC traces of polyamides with a heating rate of 20 °C /min in nitrogen. 98 Figure 2.6 Cyclic voltammetric diagrams of (a) polyamide thin films and (b) HV on the ITO-coated glass substrate (working electrode area: 12 mm × 5 mm, film thickness: 250nm) in 0.1 M TBAP/CH3CN at scan rate of 50 mV s-1. 100 Figure 2.7 Cyclic voltammetric diagrams of (a) TPPA-O ECD, (b) TPB-O ECD on the ITO-coated glass substrate (coated area: 25 mm × 20 mm, thickness: 250 nm) in propylene carbonate with lithium tetrafloroborate (LiBF4) as the supporting electrolyte. ECD composition diagrams of (c) TPPA-O ECD, (d) TPB-O ECD. 102 Figure 2.8 Cyclic voltammetric diagrams of (a) TPPA-O/HV ECD, (b) TPB-O/HV ECD on the ITO-coated glass substrate (coated area: 25 mm × 20 mm, thickness: 250 nm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte. ECD composition diagrams of (c) TPPA-O/HV ECD, (d) TPB-O/HV ECD. 103 Figure 2.9 Electrochromic behavior of (a) TPPA-O, (b) TPB-O, (c) TPPA-A, and (d) TPB-A thin film on the ITO-coated glass substrate (coated area: 12 mm × 5 mm, thickness: 250 nm) in 0.1 M TBAP/CH3CN at applied related potentials. 106 Figure 2.10 Electrochromic behavior of HV on the ITO-coated glass substrate (working electrode area: 12 mm × 5 mm, concentration: 0.001 M) in 0.1 M TBAP/CH3CN at applied a potential of -0.42 V. 106 Figure 2.11 UV-Vis spectra of (a) TPPA-O ECD, (b) TPB-O ECD, (c) TPPA-O/HV ECD, and (d) TPB-O/HV ECD. 107 Figure 2.12. Overlapping absorption spectra of TPPA-PA ECD, TPB-PA ECD and HV ECD. 107 Figure 2.13 Cyclic voltammetric diagrams of Copolymer-O ECD and Blending-O ECD on the ITO-coated glass substrate (coated area: 25 mm × 20 mm, thickness: 250 nm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte. 109 Figure 2.14 UV-Vis spectra of (a) Blending-O ECD and (b) Copolymer-O ECD on the ITO-coated glass substrate (coated area: 25 mm × 20 mm, thickness: 250 nm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte. 110 Figure 2.15 (a) UV-vis spectra of Blending-O ECD with different thickness (250 nm, 1 μm) on the ITO-coated glass substrate (coated area: 25 mm × 20 mm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte, and (b) photos of ECDs at bleached state and colored state. 112 Figure 2.16 Cyclic voltammetric diagrams of Blending-O ECD with different thickness (250 nm, 1 μm) on the ITO-coated glass substrate (coated area: 25 mm × 20 mm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte. 112 Figure 2.17 (a) UV-vis spectra of TPPA-TPB PA blending ECD with different backbone structure (aromatic Blending-O, aliphatic Blending-A) on the ITO-coated glass substrate (coated area: 25 mm × 20 mm, thickness: 1 μm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte, and (b) photos of ECDs at bleached state and colored state. 114 Figure 2.18 Cyclic voltammetric diagrams of TPPA-TPB PA blending ECD with different backbone structure (aromatic Blending-O, aliphatic Blending-A) on the ITO-coated glass substrate (coated area: 25 mm × 20 mm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte. 114 Figure 2.19 (a) 3D spectroelectrochemical diagram, and (b) CIE 1976 color diagram of Blending-A ECD (coated area: 25 mm × 20 mm, thickness: 1 μm) at applied potential of 1.5V for 20 s. 115 Figure 2.20 Electrochromic switching between 1.5 V and -1.5 V of Blending-A ECD (coated area: 25 mm × 20 mm, thickness: 1 μm) in 3 wt% of LiBF4/propylene carbonate electrolyte with HV containing 0.5 mg as the supporting electrolyte with a cycle time of (a) 200 s, and (b) 5 hr and 5 min for coloring and bleaching processes, respectively. 116 Figure 2.21 UV-vis-NIR spectra of Blending-A ECD (coated area: 25 mm × 20 mm, thickness: 1 μm). 117 CHAPTER 3 Figure 3.1 SEM of the AgNWs. Inset shows the photograph of AgNWs dispersed in 20 mL of ethanol. 127 Figure 3.2 Schematic diagram for the fabrication of AgNW/PDMS hybrid electrodes and Elastomeric HV ECDs. 128 Figure 3.4 UV-Vis spectra of different substrate. 132 Figure 3.5 SEM morphology of the AgNWs/PDMS hybrid electrode. 135 Figure 3.6 Schematic representation of the transfer process. 136 Figure 3.7 The electrical and optical behavior of the prepared AgNWs/PDMS hybrid electrodes. (a) UV-Vis transmittance spectra of the obtained electrodes with various sheet resistance (the transmittance based on the air as reference), and FOM value plotted with sheet resistance and transmittance (T550nm) (b) (the transmittance based on the air as reference), and (c) (the transmittance based on the PDMS as reference) of the stretchable electrodes. 136 Figure 3.8 The resistance variation of the AgNWs/PDMS hybrid electrode for different test. (a) Stretching test, (b) twisting test, and (c) bending test. 139 Figure 3.9 Optical microscope images of the AgNWs/PDMS hybrid electrode at (a) releasing, and (b) 25% strain. 139 Figure 3.10 LED applications of AgNWs/PDMS hybrid electrodes. Photographic images of working LEDs with (a) releasing, (b) twisting, (c) strain of 50%, (d) strain of 50% AgNWs-PDMS hybrid electrodes. 140 Figure 3.11 The resistance variation of the AgNWs-PDMS electrode for different test. (a) Releasing state of different percentages of stretching test, (b) stretching test, (c) twisting test, and (d) bending test for 1000 cycles. 141 Figure 3.12 Schematic diagram of HV ECD based on the AgNWs/PDMS hybrid electrodes. 144 Figure 3.13 (a) Cyclic voltammetric diagrams of AgNWs on the different substrates (working electrode area: 12 mm × 5 mm, sheet resistance: 20 Ω/sq) in 0.1 M TBAP/CH3CN at scan rate of 50 mV s-1. (b) SEM of the AgNWs/PI hybrid electrode scanned over 0.4 V. 145 Figure 3.14 Cyclic voltammetric diagrams of HV ECD based on AgNWs-PDMS electrodes (electrochromic material: 1 mg, working area: 20 mm × 20 mm, gap thickness: 1 mm) in 0.1 M TBAP/CH3CN at scan rate of 50 mV s-1. 146 Figure 3.15 (a) UV-vis spectra of HV ECD based on the AgNWs/PDMS hybrid electrode (electrochromic material: 1 mg, working area: 20 mm × 20 mm, gap thickness: 1 mm) in 0.1 M TBAP/CH3CN at applied related potentials, and (b) photos of ECDs at bleached state and colored state. 146 Figure 3.16 (a) Calculation of optical switching time at 603 nm at the applied potential, and (b) electrochromic switching between 0.00 V and 0.65V with a cycle time of 100s of HV ECD based on the AgNWs/PDMS hybrid electrode (electrochromic material: 1 mg, working area: 20 mm × 20 mm, gap thickness: 1 mm) in 0.1 M TBAP/CH3CN. 147 | |
| dc.language.iso | en | |
| dc.subject | 三苯胺 | zh_TW |
| dc.subject | 電致變色 | zh_TW |
| dc.subject | 可見光全光譜吸收 | zh_TW |
| dc.subject | 奈米銀線 | zh_TW |
| dc.subject | 可拉伸電極 | zh_TW |
| dc.subject | Electrochromic | en |
| dc.subject | Stretchable electrode | en |
| dc.subject | Silver nanowires | en |
| dc.subject | Transmissive-to-black | en |
| dc.subject | Triarylamine | en |
| dc.title | 應用於光電元件之高性能電致變色材料及導電材料之合成、製備及性質探討 | zh_TW |
| dc.title | Synthesis, Preparation, and Characterization of High-Performance Electrochromic and Conductive Materials for Optoelectronic Devices | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 104-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 蕭勝輝(Sheng-Huei Hsiao),李宗銘(Tzong-Ming Lee),龔宇睿(Yu-Ruei Kung) | |
| dc.subject.keyword | 三苯胺,電致變色,可見光全光譜吸收,奈米銀線,可拉伸電極, | zh_TW |
| dc.subject.keyword | Triarylamine,Electrochromic,Transmissive-to-black,Silver nanowires,Stretchable electrode, | en |
| dc.relation.page | 157 | |
| dc.identifier.doi | 10.6342/NTU201603027 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2016-08-19 | |
| 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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