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

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。

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.