含咔唑基團與二氫吖啶取代之1,3,2-苯并二氮雜硼衍生物合成、性質探討及其在藍色磷光有機發光二極體與電致變色之應用

Synthesis and Characterization of 1,3,2-Benzodiazaboroles Substituted carbazole group and 9,9-dimethyl-9,10-dihydroacridine and Applied in Blue PhOLEDs and Electrochromism

吳思樺(Si-Hua Wu)

指導教授 ： 梁文傑

國立臺灣大學/理學院/化學研究所/碩士(2021年)

https://doi.org/10.6342/NTU202103994

摘要

本論文研究分成兩大部分，其一為有機發光二極體的探討及應用上之表現，其二為化合物電致變色之實驗與特性。
在以往有機發光二極體，以碳氮兩種原子為基礎進行研發，含硼的原子較少出現在材料當中，而硼原子其具有低電負度且具有有空Pz軌域，因此透過等電子體的概念，將其引入分子結構當中，可以改變材料的電化學特性，並應用於藍色磷光有機發光二極體中，因此合成出一系列1,3,2-苯并二氮雜硼為主體之材料，透過將吲哚結構中的碳-碳雙鍵取代為硼-氮單鍵，使整個結構同樣具有10個π電子，並引入三咔唑、七咔唑及二氫吖啶等基團，來調整分子傳電洞及電子的能力，並展現出特有的光電性質，期許此系列化合物能有效應用於藍色磷光有機發光二極體中。元件部分，以 dmBN-tcbz 作為主發光材料，FIrpic 為客發光材料之有機發光二極體元件，其表現如下：最大亮度為13980 cd/m2，最大發光效率為 49.87 cd/A，最大發光功率為 44.47 lm/W，最大外部量子效率為 22.58 %；以 dmBN-acridine 作為主發光材料，FIrpic 為客發光材料之有機發光二極體元件，其表現如下：最大亮度為9959 cd/m2，最大發光效率為 49.44 cd/A，最大發光功率為 40.68 lm/W，最大外部量子效率為 21.66 %。
電聚合薄膜部分，利用電化學實驗將a7cb聚合在ITO 上，形成具有電致變色現象的電聚合薄膜，可隨著施加電壓改變，肉眼可以很明顯觀察顏色在深淺綠色和透明間來回變化多次，透過紫外光-可見光-近紅外光吸收光譜儀檢測其顏色是否改變，並利用 Electrochromic switchimg 實驗得知薄膜之穩定性與著色速度。

關鍵字

硼氮吲哚 ； 有機含硼化合物 ； 1,3,2,-苯并二氮雜硼 ； 有機化發二極體 ； 電致變色

並列摘要

The thesis is divided into two part. One is the properties and application performance of organic light-emitting diodes, and the other is the experiment based on electrochromic properties of these compounds.
In the past, carbon and nitrogen atoms in organic light-emitting materials has been widely studied and developed. However, synthesis and applications of boron-containing compounds are few in organic chemistry. This thesis introduces boron atoms into the molecular structure, and through the low electronegativity and empty Pz orbital characteristics, hoping to change the properties of organic materials and apply them to blue phosphorescent organic light-emitting diodes. Through the concept of isoelectronics, we designed a series of 1,3,2-benzodiazaborole derivatives as backbone that replaced the carbon-carbon double bond with a boron-nitrogen single bond in the indole structure. A series of 1,3,2-benzodiazaborole derivatives have 10π electrons and empty Pz orbital of boron and introduce molecules such as carbazole and 9,9-dimethyi-9,10-dihydroacridine that exhibits unique photoelectric properties. The PhOLED device using dmBN-tcbz as host and FIrpic as guest, shows maximum luminance of 13980 cd/m2, maximum current efficiency of 49.87 cd/A, maximum power efficiency of 44.47 lm/W, and maxium external quantum efficiency of 22.58% and using dmBN-acridine as host and FIrpic as guest, shows maximum luminance of 9959 cd/m2, maximum current efficiency of 49.44 cd/A, maximum power efficiency of 40.68 lm/W, and maxium external quantum efficiency of 21.66%.
In the part of the electropolymerization film, compound a7cb is polymerized on ITO by electrochemical experiments to form an electropolymerization film with electrochromic phenomenon. The color of the film varied from transparent to straw yellow, and then to deep green as the applied potential changed, and the phenomenon is reversibile. Through the ultraviolet-visible-near-infrared light absorption spectrometer to detect whether the color changes, and use the Electrochromic switchimg experiment to know the stability and coloration speed of the film.

並列關鍵字

BN indole ； organoboron ； 1,3,2-benzodiazaborole ； organic light-emitting diodes(OLED) ； electrochromism

參考文獻

1. Pope, M.; Kallmann, H. P.; Magnante, P., Electroluminescence in organic crystals. The Journal of Chemical Physics 1963, 38 (8), 2042-2043.

2. Tang, C. W.; VanSlyke, S. A., Organic electroluminescent diodes. Applied Physics Letters 1987, 51 (12), 913-915.

3. Junsheng, Y.; Shuangling, L.; Yadong, J.; Lu, L.; Qing, L.; Xiaowei, Z. In Novel hole blocking material for organic light-emitting devices, Proc.SPIE, 2007.

4. Kim, J. L.; Kim, J. K.; Cho, H. N.; Kim, D. Y.; Kim, C. Y.; Hong, S. I., New polyquinoline copolymers: synthesis, optical, luminescent, and hole-blocking/electron-transporting properties. Macromolecules 2000, 33 (16), 5880-5885.

5. Kinoshita, M.; Kita, H.; Shirota, Y., A novel family of boron-containing hole-blocking amorphous molecular materials for blue- and blue–violet-emitting Oorganic electroluminescent devices. Advanced Functional Materials 2002, 12 (11‐12), 780-786.