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DC 欄位 | 值 | 語言 |
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dc.contributor.advisor | 劉貴生(Guey-Sheng Liou) | |
dc.contributor.author | Tzu-Tien Huang | en |
dc.contributor.author | 黃子恬 | zh_TW |
dc.date.accessioned | 2021-06-15T11:23:28Z | - |
dc.date.available | 2019-11-03 | |
dc.date.copyright | 2016-11-03 | |
dc.date.issued | 2016 | |
dc.date.submitted | 2016-08-17 | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/49318 | - |
dc.description.abstract | 本論文分為五個章節,第一章為總體序論,簡述高性能高分子、有機-無機複合材料及高分子複合材料記憶體元件的應用及發展。第二章中以生物性4ATA-diamine-salt合成具有高穿透度的新型低含碳量生物性聚醯亞胺 (4ATA-PI)。 位於 4ATA-PI 骨幹上的羧基提供有效的有機-無機物鍵結位置。第三章利用Michael polyaddition的方式合成一系列具有高穿透度且含有羥基的可溶性Polyimidothioethers (PITEs) 並由其製備具有可撓性的有機無機混成膜。第四章中以一步縮合聚合法製備含羥基的 Polyhydroxyimides (PHIs),並製成具有良好光學性質及熱性質的二氧化鈦或是二氧化鋯高分子複合薄膜。第五章為結論。
一系列的光學穿透性高分子皆具有有機-無機物鍵結位置,並利用控制丁醇鈦或丁醇鋯/羥基與羧基的莫耳比來製備獲得均勻之混成薄膜。這些高分子混成薄膜具有可調諧式的折射率 (在4ATA-PI/TiO2中由1.60至1.81,在4ATA-PI/ZrO2中由1.60至1.80;在S-OH/TiO2中由1.65至1.81,在S-OH/ZrO2中由1.65至1.80; PHI- 6F/TiO2中由1.63至1.84,PHI-6F/ZrO2中由1.63至1.81)。以外,由於ZrO2的能隙相較於TiO2較大,使PI/ZrO2混合膜在可見光區域具有較高阿貝數和透明性。 在高分子記憶體元件中導入具有較低LUMO的TiO2和ZrO2作為穩定電荷的電子接受者。在一系列的PI混成薄膜皆具有可調諧式的記憶行為,由DRAM,SRAM至WROM且具有高的開/關電流比(108)。由於TiO2和ZrO2能隙不同,而呈現出各自獨特的記憶行為,在未來高穿透度記憶體元件的應用上具有很大的潛能。 | zh_TW |
dc.description.abstract | This study has been separated into five chapters. Chapter 1 is general introduction of high performance polymer, organic-inorganic hybrid materials, and polymer hybrid memory. In chapter 2, a novel 4,4′-diamino-α-truxilic acid biobased polyimides (4ATA-PI) prepared by the biobased 4ATA-diamine-salt which is good for the sustainable low-carbon society and transparency of the obtained polyimide. The carboxylic acid groups in the backbone of the 4ATA-PI provided reaction sites for organic-inorganic bonding. In chapter 3, the highly transparent polyimidothioethers (PITEs) were prepared by Michael polyaddition from bismaleimides and dithiol which containing the hydroxyl groups in the backbone to develop the flexible hybrid films. In chapter 4, a novel polyhydroxyimides (PHIs) were prepared by one-step polycondensation and the corresponding polymer hybrids of TiO2 or ZrO2 contains excellent optical properties and thermal stability. Chapter 5 is conclusions.
These optical transparent polymers all have the reaction sites for organic-inorganic bonding and resulted homogeneous hybrid films by controlling the mole ratio of titanium butoxide or zirconium butoxide/hydroxyl or carboxylic acid group. In addition, these polymer hybrid films showed tunable refractive index (1.60–1.81 for 4ATA-PI/TiO2, 1.60–1.80 for 4ATA-PI/ZrO2, 1.65–1.81 for S-OH/TiO2, 1.65–1.80 for S-OH/ZrO2, 1.63–1.84 for PHI-6F/TiO2 and 1.63–1.81 for PHI-6F/ZrO2), and the PI/ZrO2 hybrid films revealed higher optical transparency and Abbe′s number than those of PI/TiO2 system due to a larger band gap of ZrO2. By introducing TiO2 and ZrO2 as electron acceptor into polymer system, the hybrid materials have a lower LUMO energy level that could facilitate and stabilize the charge transfer complex. Therefore, the memory devices derived from these PI hybrid films exhibited tunable memory properties from DRAM, SRAM, to WORM at different TiO2 or ZrO2 contents from 0 wt% to 50 wt% with a high ON/OFF ratio (108). In addition, the different energy level of TiO2 and ZrO2 revealed the specifically unique memory characteristics, implying the potential application of the prepared TiO2 and ZrO2 hybrids films in highly transparent memory devices. | en |
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dc.description.tableofcontents | TABLE OF CONTENTS
ACKNOWLEDGEMENTS II ABSTRACT (in English) III ABSTRACT (in Chinese) IV TABLE OF CONTENTS V LIST OF TABLES X LIST OF FIGURES XII LIST OF SCHEMES XXI CHAPTER 1 1 CHAPTER 2 77 CHAPTER 3 109 CHAPTER 4 141 CHAPTER 5 176 APPENDIX 179 LIST OF PUBLICATIONS 180 CHAPTER 1 General Introduction 1.1 High Performance Polymers 2 1.1.1 Preparation of Aromatic Polyimides 4 1.1.2 Modification of Aromatic Polyimides 8 1.1.3 Optically Transparent and High Refractive Index Polyimide 10 1.2 Function Hybrid Organic-Inorganic Nanocomposites 18 1.2.1 High Refractive Index Inorganic Materials 20 1.2.2 Polyimides with Hydroxyl Group 22 1.2.3 Synthetic method of Organic-Inorganic Nanocomposites 23 1.2.4 Titania-Polyimide Hybrids 28 1.2.5 Zirconia-Polyimide Hybrids 34 1.2.6 Application of the Optical Organic–Inorganic Nanocomposites 38 1.3 Polymer Memory Devices 42 1.3.1 Categories of Polymer Memory 43 1.3.2 Fundamentals of Resistor-Type Polymeric Memory 45 1.3.3 Mechanisms of Resistor-type Polymer Memory 47 1.3.4 Development of Polymer Memory 53 1.4 Research Motivation 58 REFERENCES AND NOTES 60 CHAPTER 2 Highly Transparent and Flexible Biobased Polyimide/TiO2 and ZrO2 Hybrid Films with Tunable Refractive Index, Abbe Number, and Memory Properties ABSTRACT OF CHAPTER 2 78 2.1 Introduction 79 2.2 Experimental section 82 2.2.1 Materials 82 2.2.2 Preparation of the 4ATA-PI polyimide 82 2.2.3 Preparation of the 4ATA-PI films 83 2.2.4 Preparation of 4ATA-PI/titania and 4ATA-PI/zirconia hybrid films 83 2.2.5 Measurements 84 2.2.6 Fabrication and measurement of the memory devices 85 2.2.7 Molecular simulation 85 2.3 Results and discussion 86 2.3.1 Polymer synthesis and characterization 86 2.3.2 Synthesis and characterization of PI hybrids 89 2.3.3 Thermal properties of 4ATA-PI, 4ATA-PI/TiO2 and 4ATA-PI/ZrO2 91 2.3.4 Optical properties of optical polymer and hybrid films 94 2.3.5 Memory device characteristics and switching mechanism 97 2.4 Summary 106 REFERENCES AND NOTES 107 CHAPTER 3 Optically Isotropic, Colorless, and Flexible Polyimidothioethers/TiO2 and ZrO2 Hybrid Films with Tunable Refractive Index, Abbe Number, and Memory Properties ABSTRACT OF CHAPTER 3 110 3.1 Introduction 111 3.2 Experimental section 113 3.2.1 Materials 113 3.2.2 Polymer synthesis 113 3.2.3 Preparation of the PITE films 114 3.2.4 Preparation of S-OH/titania and S-OH/zirconia hybrids 114 3.2.5 Measurements 115 3.2.6 Fabrication and measurement of the memory devices 116 3.2.7 Molecular simulation 116 3.3 Results and discussion 117 3.3.1 Polymer synthesis and characterization 117 3.3.2 Synthesis and characterization of PITE hybrids 119 3.3.3 Thermal properties of PITEs, S-OH/TiO2 and S-OH/ZrO2 121 3.3.4 Optical properties of optical polymer and hybrid films 124 3.3.5 Memory device characteristics and switching mechanism 128 3.4 Summary 138 REFERENCES AND NOTES 139 CHAPTER 4 Highly Transparent Polyhydroxyimide/TiO2 and ZrO2 Hybrids Films with High Glass Transition Temperature (Tg) and Low Coefficient of Thermal Expansion (CTE) for Optoelectronic Application ABSTRACT OF CHAPTER 4 142 4.1 Introduction 143 4.2 Experimental section 146 4.2.1 Materials 146 4.2.2 Synthesis of 4,4-damino-4-hydroxtriphenylmethane (DHTM) 146 4.2.3 Preparation of the polyhydroxyimides (PHIs) 147 4.2.4 Preparation of the PHIs films 147 4.2.5 Preparation of PHIs/titania and PHIs/zirconia hybrid films 147 4.2.6 Measurements 149 4.2.7 Fabrication and measurement of the memory devices 150 4.2.8 Molecular simulation 150 4.3 Results and discussion 151 4.3.1 Synthesis of 4,4-damino-4-hydroxtriphenylmethane (DHTM) 151 4.3.2 Polymer synthesis and characterization 152 4.3.3 Synthesis and characterization of PI hybrids 154 4.3.4 Thermal properties of PHIs, PHIs/TiO2 and PHIs/ZrO2 156 4.3.5 Optical properties of optical polymer and hybrid films 159 4.3.6 Memory device characteristics and switching mechanism 163 4.4 Summary 173 REFERENCES AND NOTES 174 CHAPTER 5 Conclusion 176 LIST OF TABLES CHAPTER 1 Table 1.1 Commercially available aromatic polyimides. 5 Table 1.2 Examples for modified organic soluble aromatic polyimides. 9 Table 1.3 Atomic refraction [R] and atomic dispersion [ΔR] 11 Table 1.4 Fluorine-containing polyimides. 13 Table 1.5 Sulfur-containing polyimides 15 Table 1.6 Comparisons of optical materials. 18 Table 1.7 Refractive index and absorption coefficients at three different wavelengths in the visible range for some inorganic materials. 20 Table 1.8 Components, synthesis method, and refractive index of some metal oxide–polymer nanocomposites with high refractive index 21 Table 1.9 Electronegativity (χ), coordination number (N), and degree of unsaturation (N - Z) of some metals (Z=4). 26 Table 1.10 The reaction constant K of tetralkoxysilane in acid hydrolysis 26 CHAPTER 2 Table 2.1 Inherent viscosity and GPC data of 4ATA-PI. 87 Table 2.2 The solubility behavior of 4ATA-PI. 87 Table 2.3 Reaction composition of the 4ATA-PI hybrid films 89 Table 2.4 Thermal properties of 4ATA-PI hybrid films with TiO2 and ZrO2 92 Table 2.5 Optical properties of 4ATA-PI hybrid films 95 Table 2.6 Redox potential and energy level of 4ATA-PI. 100 Table 2.7 Summary of 4ATA-PI, 4ATA-PI/TiO2, and 4ATA-PI/ZrO2 memory properties. 100 CHAPTER 3 Table 3.1 Inherent viscosity and GPC data of PITEs. 117 Table 3.2 The solubility behavior of PITEs. 117 Table 3.3 Reaction composition of the PITEs and S-OH hybrid films 119 Table 3.4 Thermal properties of PITEs and S-OH hybrid films with TiO2 and ZrO2 121 Table 3.5 Optical properties of S-OH and S-OH hybrid films with TiO2 and ZrO2 125 Table 3.6 Redox potential and energy level of PITE. 131 Table 3.7 Summary of S-OH, S-OH/TiO2, and S-OH/ZrO2 memory properties. 131 CHAPTER 4 Table 4.1 Inherent viscosity and GPC data of PHIs. 152 Table 4.2 The solubility behavior of PHIs. 153 Table 4.3 Reaction composition of the PHIs and PHIs hybrid films 154 Table 4.4 Thermal properties of PHIs and PHIs hybrid films with TiO2 and ZrO2 157 Table 4.5 Optical properties of PHIs, PHI-6F and PHI-BC hybrid films with TiO2 and ZrO2. 160 Table 4.6 Redox potentials and energy levels of PHIs. 166 Table 4.7 Summary of PHI-6F, PHI-6F/TiO2 and PHI-6F/ZrO2 memory properties. 167 LIST OF FIGURES CHAPTER 1 Figure1.1The structures of commercially available high-performance polymers. 3 Figure1.2 The chemical sructures were used to synthesized alicyclic polyimides 17 Figure 1.3 Schematic of in situ synthesis of metal nanoparticles in a polymer matrix. 24 Figure 1.4 Ex situ synthesis schemes for the preparation of nanocomposites from blen- ding route and in situ polymerization process. 25 Figure 1.5 Polymerization behavior of aqueous silica. 27 Figure 1.6 Thickness and refractive index of the sol-gel titania film at different anneal- ing temperatures, green dots are thickness, and purple triangles are refrac- tive index at 632.8 nm 28 Figure 1.7 Reaction scheme for hydrothermal crystallization of anatase 29 Figure 1.8 Variation in the refractive index of acrylic polymer–titania hybrid films with titania content, before and after hydrothermal treatment 30 Figure 1.9 Semi-alicyclic sulfur-containing PI and silica-modified anatase TiO2 31 Figure 1.10 Reaction scheme for the preparation of the aminoalkoxysilane capped PMDA–titania films. 32 Figure 1.11 (a) Reaction scheme for the preparation of the carboxylic acid end groups PI–titania films; (b) refractive index (c) UV-Vis-NIR absorption spectra. 32 Figure 1.12 Left: The reaction route for polyimide and titania precursors; Right: Trans- mittance UV-visible spectra of 6FPI hybrid thin films (thickness: 150–650 nm) 33 Figure 1.13 Left: The reaction route for polyimide and titania precursors; Right: Trans- mittance UV-visible spectra of 2,3-PHIc hybrid thin films (thickness: 150–650 nm) 33 Figure 1.14 Schematic representation of mechanism to fabricate the nanocomposites via UV-induced crosslinking polymerization. 35 Figure 1.15 Dispersion strategies to obtain a highly transparent nanocomposite of high refractive index. 35 Figure 1.16 Optical transmission spectra of F-6FTiX hybrid thick films (a), (c) (thickness: ~ 19 μm); and thin films (b), (d) (thickness: 500–600 nm). The inset figure shows the transmission spectra of hybrid thick and thin films in 450–700 nm of wavelength.. 37 Figure 1.17 Scheme of light scattering loss for traditional composites and nanocom- posites 38 Figure 1.18 Schematic of a display with protective and refractive index control polymer over layer films 39 Figure 1.19 Microlens array in CMOS image sensor device. 40 Figure 1.20 Escape cone of an LED without and with encapsulation (a) and light ex- traction efficiency ratio for GaN and GaP as a function of the encapsulant refractive index. 41 Figure 1.21 Classification of electronic memories. 43 Figure 1.22 The diagram of the memory device consisting of a polymer thin film sandwiched between an ITO bottom electrode and an Al top electrode. 45 Figure 1.23 Some evaluation parameters for molecular/polymer memories. (a) Stabili- ty under voltage stress and ON/OFF ratio (inset); (b) Number of read pulses; (c) Write–read–erase–read (WRER) cycles; (d) Switching time measure- ment 46 Figure 1.24 The formation of (a) carbon-rich filaments and (b) metallic filaments, and the relevant switching effects. 48 Figure 1.25 (a) Operational mechanism of the memory. Experimental and fitted J–V curves of the ITO/PFOxPy/Al device, (b) OFF state with the Ohmic current (<1.3 V) and SCLC (1.3–2.6 V) models, (c) ON state with the Ohmic current model (>2.8 V). 50 Figure 1.26 (a) I–V (in log scale) curves of the Al/Au:NP/Al bistable memory device. (b) Schematic band diagrams for the transport mechanism of trap-filled SCLC: (i) Region I: thermally generated carrier conduction, (ii) Region II: with traps, (iii) Region III: nearly filled, and (iv) Region IV: traps filled. 50 Figure 1.27 Schematic representation of the formation of ion-radical species and charge transfer complexes 51 Figure 1.28 Molecular orbitals (left) of the basic unit of TP6F–PI and the transitions (right) from the ground state to the charge transfer state induced by the electric field 52 Figure 1.29 Molecular structures of donor–acceptor polymer systems for advanced memory device applications 53 Figure 1.30 Current–voltage (I–V) characteristics of the ITO/polymer (~ 50 nm)/Al memory device. (a) DSPE (b) DSPET (c) DSPA (d) DSPI. And (e) chemical structures and memory device diagram 55 Figure 1.31 Memory properties and molecular structures of 3Ph-PIs, 5Ph-PIs, and 9Ph-PIs 55 Figure 1.32 The concept of the study………………………………………………..55 CHAPTER 2 Figure 2.1 Represent flexible and transparent (a) 4ATA-PI, (b) 4ATA-PITi30 and (c) 4ATA-PIZr30 optical films. (thickness: 30 ± 5μm) 87 Figure 2.2 IR spectrum of 4ATA-PI film. 88 Figure 2.3 1H NMR spectra of 4ATA-PI in DMSO-d6. 88 Figure 2.4 IR spectra of 4ATA-PITi50 and 4ATA-PIZr50 hybrid materials. 90 Figure 2.5 IR spectrums of 4ATA-PITi30 and 4ATA-PIZr30 at different curing temperatures. 90 Figure 2.6 TGA traces of 4ATA-PI/TiO2 and 4ATA-PI/ZrO2 hybrid materials (a) and (c) in N2, (b) and (d) in air. 92 Figure 2.7 TMA curves of (a) 4ATA-PI/TiO2 and (b) 4ATA-PI/ZrO2 hybrid films with the heating rate of 10 oC/min. 93 Figure 2.8 Optical transmission spectra of 4ATA-PITiX and 4ATA-PIZrX thick hybrid films (a), (b) (thickness: 20±5 μm); and thin films (c), (d) (thickness: 500-600 nm). The inset figures show the transmission spectra of hybrid thick and thin films in 450-700 nm of wavelength. 95 Figure 2.9 TEM images of (a) 4ATA-PITi50, (b) 4ATA-PIZr50 hybrid materials. 96 Figure 2.10 Variation of the refractive index for the (a) 4ATA-PITiX and (b) 4ATA- PIZrX hybrid films with wavelength. The inset figures show the refractive index at 633 nm with different titania and zirconia content. 96 Figure 2.11. UV-vis absorption spectrum of 4ATA-PI film. 100 Figure 2.12. Cyclic voltammetric diagram of the 4ATA-PI film on an ITO-coated glass substrate. 101 Figure 2.13 Current-voltage (I-V) characteristic of the ITO/4ATA-PI (50 ± 3nm)/Al memory device. 101 Figure 2.14 Calculated molecular orbitals and corresponding energy levels of the basic units for 4ATA-PI. 102 Figure 2.15 HOMO and LUMO energy levels of (a)4ATA-PI, (b) 4ATA-PI and TiO2, and (c) 4ATA-PI and ZrO2 along with the work function of the electrodes. 102 Figure 2.16 Current-voltage (I-V) characteristics of the ITO/4ATA-PI/TiO2 hybrid materials (50 ± 3nm)/Al memory device (a) and (b) 4ATA-PITi5, (c) 4ATA-PITi7, (d) 4ATA-PITi10, (e) 4ATA-PITi15, (f) and (g) 4ATA- PITi30. 103 Figure 2.17 Current-voltage (I-V) characteristics of the ITO/4ATA-PI/ZrO2 hybrid materials (50 ± 3nm)/Al memory device (a) and (b) 4ATA-PIZr5, (c) 4ATA-PIZr7, (d) 4ATA-PIZr10, (e) 4ATA-PIZr15, (f) 4ATA-PIZr30 and (g) 4ATA-PIZr50. 104 Figure 2.18 The stability of memory devices in the ON and OFF states of the ITO/ 4ATA-PI hybrid materials (50 ± 3nm)/Al devices (a) 4ATA-PITi30 and (b) 4ATA-PIZr30. 105 CHAPTER 3 Figure 3.1 Representative flexible and transparent (a) S-OH, (b) S-OHTi30 and (c) S-OHZr30 optical films. (thickness: 20 ± 5 μm) 118 Figure 3.2 IR spectra of PITEs 118 Figure 3.3 IR spectra of S-OHTi50 and S-OHZr50 hybrid materials 120 Figure 3.4 TGA traces of PITEs, S-OH/TiO2 and S-OH/ZrO2 hybrid materials (a), (c) and (e) in N2, (b), (d) and (f) in air 122 Figure 3.5 TMA curves of (a) PITEs, (b) S-OH /TiO2 and (c) S-OH /ZrO2 hybrid films with the heating rate of 10 oC/min. 123 Figure 3.6 Optical transmission spectra of PITE, S-OHTiX and S-OHZrX thick hybrid films (a), (b), (c) (thickness: 20±5 μm); and thin films (d), (e) (thickness: 500-600 nm). The inset figures show the transmission spectra of hybrid thick and thin films in 450-700 nm of wavelength. 126 Figure 3.7 TEM images of (a) S-OHTi30 and (b) S-OHZr30 hybrid materials. 127 Figure 3.8 Variation of the refractive index of the (a) S-OHTiX and (b) S-OHZrX hybrid films with wavelength. The inset figure shows the variation of the refractive index at 633 nm with different titania and ziconia content. 127 Figure 3.9 UV-vis absorption spectra of PITEs films 132 Figure 3.10 Cyclic voltammetric diagrams of the PITEs films on an ITO-coated glass substrate 132 Figure 3.11 Current-voltage (I-V) characteristics of the ITO/PITEs (50 ± 3 nm)/Al memory device (a) S-OH (b) CH2-OH and (c) SO2-OH. 133 Figure 3.12 Calculated molecular orbitals and corresponding energy levels of the basic units for PITEs (a) S-OH (b) CH2-OH and (c) SO2-OH. 133 Figure 3.13 HOMO and LUMO energy levels of (a) S-OH, (b) S-OH and TiO2, and (c) S-OH and ZrO2 along with the work function of the electrodes. 134 Figure 3.14 Current-voltage (I-V) characteristics of the ITO/S-OH/TiO2 hybrid materials (50 ± 3 nm)/Al memory device (a) and (b) S-OHTi5, (c) and (d) S-OHTi7, (e) S-OHTi10, (f) S-OHTi15, (g) and (h) S-OHTi30. 135 Figure 3.15 Current-voltage (I-V) characteristics of the ITO/S-OH/ZrO2 hybrid materials (50 ± 3 nm)/Al memory device (a) S-OHZr5, (b) S-OHZr7, (c) S-OHZr10, (d) S-OHTi15, (e) S-OHTi30 and (f) S-OHTi50. 136 Figure 3.16 The stability of memory devices at the ON and OFF states of the ITO/S-OH hybrid materials (50 ± 3nm)/Al devices (a) S-OHTi30 and (b) S-OH Zr30 136 CHAPTER 4 Figure 4.1 1H NMR spectra of DHTM in DMSO-d6. 151 Figure 4.2 Representative flexible and transparent (a) PHI-BC, (b) PHI-BCTi30, (c) PHI-BCZr30, (d) PHI-6F, (e) PHI-6FTi30 and (f) PHI-6FZr30 optical films . (thickness: 20 ± 5 μm) 153 Figure 4.3 IR spectra of PHIs film. 153 Figure 4.4 IR spectra of PHI-6FTi30 and PHI-6FZr30 hybrid materials. 155 Figure 4.5 TMA curves of (a) PHI-BCM30, (b) PHI-6F/TiO2 and (c) PHI-6F/ZrO2 hybrid films with the heating rate of 10 ℃/min. 157 Figure 4.6 TGA traces of PHI-6F/TiO2, PHI-6F/ZrO2 and PHI-BCM30 hybrid materials (a), (c) and (e) in N2, (b), (d) and (f) in air. 158 Figure 4.7 Optical transmission spectra of PHI-BCM50, PHI-6FTiX and PHI- 6FZrX thick hybrid films (a), (b), (c) (thickness: 20±5 μm) ; and thin films (d), (e), (f) (thickness: 200-300 nm) .The inset figure shows the transmis- sion spectra of hybrid thick and thin films in 450-700 nm of wavelength. 161 Figure 4.8 TEM image of the (a) PHI-6FTi30 and (b) PHI-6FZr30 hybrid material. 161 Figure 4.9 Variation of the refractive index of the (a) PHI-6FTiX, (b) PHI-6FZrX and (c) PHI-BCM50 hybrid films with wavelength. The inset figure shows the variation of the refractive index at 633 nm with different titania and ziconia content. 162 Figure 4.10 UV-vis absorption spectra of PHIs films. 167 Figure 4.11 Cyclic voltammetric diagrams of the PHIs films on an ITO-coated glass substrate. 167 Figure 4.13 Calculated molecular orbitals and corresponding energy levels of the basic units for PHIs. 168 Figure 4.14 Current-voltage (I-V) characteristics of the ITO/PHI-6F/TiO2 hybrid materials (50 ± 3nm) /Al memory device (a) and (b) PHI-6FTi5, (c) PHI- 6FTi7, (d) PHI-6FTi10, (e) PHI-6FTi15, (f) and (g) PHI-6FTi30. 169 Figure 4.15 Current-voltage (I-V) characteristics of the ITO/PHI-6F/ZrO2 hybrid materials (50 ± 3nm) /Al memory device (a) PHI-6FZr5, (b) PHI-6FZr7, (c) PHI-6FZr10, (d) PHI-6FZr15, (e) PHI-6FZr30 and (f) PHI-6FZr50. 170 Figure 4.16 HOMO and LUMO energy levels of (a) PHI-BC, (b) PHI-6F (c) PHI- 6F and TiO2, and (d) PHI-6F and ZrO2 along with the work function of the electrodes. 171 Figure 4.17 The stability of memory devices at the ON and OFF states of the ITO/ PHI-6F hybrid materials (50 ± 3nm)/Al devices (a) PHI-6FTi30 and (b) PHI-6FZr30. 172 LIST OF SCHEMES CHAPTER 1 Scheme 1.1 Two-step polymerization method of aromatic polyimides synthesis 6 Scheme 1.2 The sol-gel reaction of the hybrid synthesis. 22 Scheme 1.3 Sol-gel synthesis of organic-inorganic nanocomposites 23 Scheme 1.4 Synthesis of semialicyclic polyimides 31 Scheme 1.5 Synthesis and structures of the poly(o-hydroxy-imide)s and preparation of PI/zirconia hybrids 36 CHAPTER 2 Scheme 2.1 Synthesis of biobased polyimide 4ATA-PI. 82 Scheme 2.2 Synthesis and structures of 4ATA-PI/TiO2 and 4ATA-PI/ZrO2 hybrids. 83 Scheme 2.3 Chemical structures of 4ATA-PI, 4ATA-PI/TiO2 and 4ATA-PI /ZrO2 and the schematic diagram of the memory device consisting of a polymer thin film sandwiched between an ITO bottom electrode and an Al top electrode. 105 CHAPTER 3 Scheme 3.1 Synthesis of Polyimidothioethers 113 Scheme 3.2 Synthesis and Structure of S-OH/TiO2 and S-OH/ZrO2 Hybrids 114 Scheme 3.3 Chemical structures of S-OH, S-OH/TiO2 and S-OH/ZrO2 and the sch- ematic diagram of the memory device consisting of a polymer thin film sandwiched between an ITO bottom electrode and an Al top electrode. 137 CHAPTER 4 Scheme 4.1 Synthesis of 4,4-damino-4-hydroxtriphenylmethane (DHTM). 146 Scheme 4.2 Synthesis of polyhydroxyimides (PHIs). 147 Scheme 4.3 Synthesis and structure of PHI/TiO2 and PHI/ZrO2 Hybrid 148 Scheme 4.4 Chemical structures of PHIs, PHI-6F/TiO2 and PHI-6F/ZrO2 and the schematic diagram of the memory device consisting of a polymer thin film sandwiched between an ITO bottom electrode and an Al top electrode. 172 | |
dc.language.iso | en | |
dc.title | 新型高透明聚醯亞胺–二氧化鈦、二氧化鋯混成奈米複合光學材料設計、合成與光電元件應用之研究 | zh_TW |
dc.title | Design, Synthesis and Characterization of Novel Highly Transparent Polyimide/Titania and Zirconia Hybrid Materials for Optoelectronic Applications | en |
dc.type | Thesis | |
dc.date.schoolyear | 104-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 陳文章(Wen-Chang Chen),蕭勝輝(Sheng-Huei Hsiao),陳志堅(Jyh-Chien Chen) | |
dc.subject.keyword | 聚醯亞胺,二氧化鋯,複合材料,折射率,電阻式記憶體元件, | zh_TW |
dc.subject.keyword | polyimide,ZrO2,hybrid material,refractive index,resistive memory, | en |
dc.relation.page | 180 | |
dc.identifier.doi | 10.6342/NTU201602819 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2016-08-18 | |
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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ntu-105-1.pdf 目前未授權公開取用 | 14.04 MB | Adobe PDF |
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