笓衍生物之同分異構物有機發光二極體材料的合成、鑑定及光電子性質研究

Synthesis, Identification, and Opto-electronic Property of Pyrene Derivative Isomers for Organic Light Emitting Diode Material

張瓅心(sandy chang)

指導教授 ： 鄭建業

中原大學/理學院/化學研究所/碩士(2010年)

https://doi.org/10.6840/cycu201000847

摘要

本論文以笓為主體製作有機發光二極體元件中藍光系統材料的藍光客發光體材料，即分別在笓兩側1,6-及1,8-位置上導入溴取代基形成同分異構物後，再將溴取代基以不同芳香族的分子基團進行反應，以增加其分子量、分子體積、分子間的立體障礙，減少分子間的堆疊，進而減低高濃度摻雜分子間的相互作用。所合成的藍光系列材料，分別為氮1,氮1,氮6,氮6-四(3,4-二甲基苯基)笓-1,6-二胺(簡稱D1-1,6)、氮1,氮1,氮6,氮6-四(3,4-二甲基苯基)笓-1,8-二胺(簡稱D1-1,8)、氮1,氮6-二(1-萘)-氮1,氮6-二苯基笓-1,6-二胺(簡稱D2-1,6)和氮1,氮8-二(1-萘基)-氮1,氮8-二苯基笓-1,8-二胺(簡稱D2-1,8)。此些化合物可利用其1,6-及1,8-同分異構物之溶解度及昇華性不同進行分離，其分子合成與結構則經高效液相層析、核磁共振頻譜與質譜的鑑定，並進行螢光性質以及熔點(Tm)與裂解點(Td)的熱穩定性質探討。然後將D1-1,6、D1-1,8 、D2-1,6及D2-1,8四種藍光材料分別以蒸鍍製成薄膜型態元件以亮度5000 cd m-2進行測試。在導入相同體積百分比濃度(4%，v/v)的客發光體，發現D1-1,6、D1-1,8、D2-1,6、D2-1,8的發光效率分別為7.5 cd A-1、7.7 cd A-1、8.1 cd A-1及8.5 cd A-1。因同分異構物1,8-分子結構較不具對稱性，立體障礙又較大，故1,8-比1,6-系列的發光效率高。而D2系列化合物分子結構之立體障礙比D1系列化合物大，造成D2系列化合物平均發光效率較D1系列化合物高。所合成的四種笓衍生物的同分異構物，在元件發光顏色上雖無法達到深藍色，但運用在單色有機發光產品上仍有很大的利用價值。

關鍵字

有機發光二極體 ； 笓 ； 笓之衍生物 ； 光電子特性 ； 藍光客發光體材料

並列摘要

In this study, pyrene was used to manufacture the blue light guest emitter for organic light emitting diode (OLED) elements. Bromine was first reacted with pyrene to form its 1,6- and 1,8-isomer. Then, different aromatic groups to increase its molecular volume, molecular weight, and molecular steric hindrance that can reduce the accumulation of molecules and decrease the interaction between molecules in a heavily doped material substituted bromine in the pyrene molecule. The blue OLEDs synthesized in this study are N1,N1,N6,N6-tetrakis(3,4-dimethylphenyl) pyrene-1,6- diamine (symboled as D1-1,6),N1,N1,N6,N6-tetrakis(3,4-dimethylphenyl)pyrene-1,8-
diamine (symboled as D1-1,8), (N1,N6-di(naphthalenelyl)-N1,N6-diphenyl 1,6-diamine (symboled as D2-1,6), and N1,N8-di(naphthalenelyl)-N1,N8- diphenyl pyrene-1,8- diamine (symboled as D2-1,8). The 1,6- and 1,8-pyrene derivative isomers can be separated by their different properties of solubility and sublimation. High-performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR), and mass spectrometry (MS) were used for monitoring the synthesis and identifying the structure of pyrene derivative isomers. The fluorescence property and the thermal stability with the melting point (Tm) and the degradation point (Td) of these blue light emitting materials were also studied in this work. Isomers of D1-1,6 and D1-1,8 and isomers of D2-1,6 and D2-1,8 were fabricated individually to make different types of blue light emitting thin film elements by the process of thermal evaporation and deposition, then, they were tested at the luminance of 5000 cd cm-2. With the same guest light emitting material and the same volume percentage of dopant (4%), the current efficiency of the four blue light emitting materials D1-1,6, D1-1,8, D2-1,6, and D2-1,8 is 7.5 cd A-1, 7.7 cd A-1, 8.1 cd A-1and 8.5 cd A-1, respectively. Because the molecular structures of 1,8-isomers are asymmetry and their steric hindrance is stronger, the light emitting efficiency of 1,8-isomers is better than that of the 1,6-isomers. In addition, the steric hindramce between the molecules of D2 compounds is stronger than that of D1 compounds so that the light emitting efficiency of D2 compounds is better than that of D1 compounds. Although the luminescent color of the fabricated elements from the four pyrene derivative isomers cannot reach a deep blue color, they are still valuable in the production of mono-chromatic OLED products.

並列關鍵字

pyrene ； Organic light emitting diodes (OLEDs) ； guest blue light emitting materials ； optoelectronic property ； pyrene derivatives

參考文獻

1. 陳俊宏，生活科技教育月刊，2004年三十七卷第三期，119-126頁。

3. C.W. Tang, S.A. VanSlyke, Appl. Phys. Lett, 51, 913 (1987).

4. 陳金鑫，黃孝文，OLED有機電激發光材料與元件，五南圖書出版公司， 2006年7月出版，中華民國，台北市。

8. C. Adachi, S. Tokito, T. Tsutsui, S. Saito, Jpn. J. Appl. Phys., 27, L713 (1988).

9. C. Adachi, S.Tokito, T. Tsutsui, S. Saito, Jpn. J. Appl. Phys., 27, L269 (1988).