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姓名 林青鳳(Chin-Fung Lin) 查詢紙本館藏 畢業系所 化學學系 論文名稱 含嘧啶配位基的銥金屬磷光材料
(Phosphorescent Bis-Cyclometalated Iridium Complexes Containing Pyrimidine-Based Ligands)相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 我們合成一系列的pyrimidine (py)化合物,這些化合物可以與三氯化銥以cyclometalation的方式配位,形成具有強磷光性質的銥金屬化合物。我們針對這些化合物進行光物理,電化學性質的探討,並選取部分銥金屬化合物製備成元件進行測試。
在光物理方面,配位基py的吸收光譜範圍從290~313 nm,發射光譜仍在紫外光範圍。當配位基與銥金屬形成錯化物後,其吸收光譜中360~500 nm的範圍歸屬為S0 →1MLCT、S0 →3MLCT和3π - π*的躍遷;這幾種躍遷是因為銥金屬具有強的spin-orbit coupling的特性讓彼此能階相互混合,才可使得原本自旋禁制的三重態躍遷吸收較強。同時也因為銥金屬強spin-orbit coupling的特性使得這些錯化物於室溫時,在無氧溶液中多有不錯的量子產率;其放射出黃綠到橘紅色的磷光,波長範圍為522~558 nm。電化學方面,銥錯化物也可以測得銥(III)氧化成銥(IV)之氧化還原電位,並且可由此與吸收光譜得知化合物的HOMO與LUMO之能階。我們也發現到以上這些光物理和電化學性質都與配位基上之推拉電子基以及其所在位置有很大的關係。摘要(英) We have synthesized a new series of pyrimidine compounds. These compounds undergo cyclometalation with iridium trichloride to form iridium (III) complexes which exhibit strong phosphorescence. The photophysical and electrochemical properties of these compounds were investigated. Electroluminescent devices were fabricated from selected iridium complexes.
The absorption wavelengths of the py ligands range from 290 to 313 nm, and their emission wavelengths remain in the ultraviolet region. The 1MLCT, 3MLCT and 3π – π transition bands of these iridium complexes have been resolved in the range of 360~500 nm of the absorption spectrum. The 3MLCT and 3π – π transition gain intensity by mixing with higher lying 1MLCT state through the spin-orbit coupling of iridium(III). These iridium complexes emit yellow-green to orange-red phosphorescence with wavelengths ranging from 522 to 558 nm . Also the strong spin-orbit coupling leads to good quantum yields in air-free solution at room temperature. The iridium complexes exhibit a reversible oxidation due to Ir(III)→Ir(IV), and the HOMO and LUMO energy levels for each complex can be obtained from the cyclic voltammogram and the UV-vis absorption edge. We also found that the photophysical and electrochemical properties can be correlated with the electronic characters and the relative locations of the substituents on the ligands.關鍵字(中) ★ 磷光材料 關鍵字(英) ★ Phosphorescent Bis-Cyclometalated Iridium Comple 論文目次 目錄
中文摘要--------------------------------------------------------------------------I
英文摘要-------------------------------------------------------------------------II
目錄 --------------------------------------------------------------------------IV
圖目錄 -------------------------------------------------------------------------VI
表目錄 ------------------------------------------------------------------------VIII
壹、 緒論 ------------------------------------------------------------------------1
1-1 前言-------------------------------------------------------------------------1
1-2 OLED的優缺點----------------------------------------------------------2
1-3 OLED的發光原理-------------------------------------------------------3
1-4 有機電機發光二極體材料----------------------------------------------4
1-5 螢光與磷光----------------------------------------------------------------9
1-6 磷光材料與原件的優勢-----------------------------------------------12
1-7 磷光材料的介紹與近年發展-----------------------------------------14
1-8 研究動機-----------------------------------------------------------------17
貳、 實驗部分 --------------------------------------------------------------19
2-1 實驗儀器 ----------------------------------------------------------------19
2-2 實驗藥品及溶劑 ------------------------------------------------------ 21
2-3 量子產率的計算------------------------------------------------------- 22
2-4 外部量子效率的計算--------------------------------------------------23
2-5 合成流程-----------------------------------------------------------------25
2-6 合成步驟-----------------------------------------------------------------29
參、 結果與討論 ----------------------------------------------------------54
3-1 實驗流程-----------------------------------------------------------------54
3-2 合成討論-----------------------------------------------------------------57
3-3 電化學部分
3-3-1循環伏安法(CV)的探討------------------------------------59
3-3-2 HOMO與LUMO的計算--------------------------------------64
3-4 光學性質討論
3-4-1紫外光吸收光譜-------------------------------------------------66
3-4-2放光光譜(PL)------------------------------------------------69
3-4-3磷光的半生期與量子產率-------------------------------------74
3-5 元件的製備與討論-----------------------------------------------------77
肆、 結論 -------------------------------------------------------------------86
伍、 參考文獻 -------------------------------------------------------------87
附錄------------------------------------------------------------------------------92
圖目錄
圖一 目前最為普遍使用的OLED元件結構------------------------- 4
圖二 OLED元件發光原理示意圖-------------------------------------- 4
圖三 常見的電洞注入材料----------------------------------------------- 5
圖四 Biphenyl diamine衍生物------------------------------------------- 6
圖五 星狀非結晶型電洞傳輸材料-------------------------------------- 7
圖六 常見的電子傳輸材料----------------------------------------------- 7
圖七 電子能階躍遷及能量轉換-----------------------------------------10
圖八 磷光發光材料------------------------------------------------------- 16
圖九 化合物DBQ與MDQ ---------------------------------------------- 17
圖十 含isoquinoline的磷光材料--------------------------------------- 17
圖十一 Suzuki cross coupling反應機構圖--------------------------------57
圖十二 (UpyU)B2BIr(acac) 結構圖---------------------------------------------- 60
圖十三 (UpyU)B2BIr(acac) 在dichloromethane下測得的 CV圖形------ 64
圖十四 py與(UpyU)B2BIr(acac)的Uv-vis光譜圖比較----------------------- 66
圖十五 py 配位基的結構一覽-------------------------------------------- 67
圖十六 (UpyU)B2BIr(acac)化合物的PL光譜-----------------------------------74
圖十七 元件結構--------------------------------------------------------------77
圖十八 IrpyF元件I、II的EL光譜圖-----------------------------------78
圖十九 IrpyCFB3B元件I、II的EL光譜圖---------------------------------79
圖二十 IrpyCFB3B(m)CFB3B元件I、II的EL光譜圖-----------------------79
圖二十一 元件I、II的外部量子產率與電流密度關係圖--------------81
圖二十二 元件I、II的發光效率與電流密度關係圖-------------------82
圖二十三 元件I、II的能量效率與電流密度關係圖-------------------82
圖二十四 元件I、II電流密度與電壓關係-------------------------------84
圖二十五 元件I、II亮度與電壓關係圖----------------------------------84
圖二十六 元件I、II 的CIE座標圖---------------------------------------85
表目錄
表一 OLED與TFT-LCD之比較-------------------------------------------2
表二 實驗所用之化學藥品------------------------------------------------21
表三 (UbiU)B2BIr(acac)循環伏安電位的資料---------------------------------59
表四 Hammett σ-parameter ------------------------------------------------62
表五 化合物的HOMO及LUMO ----------------------------------------65
表六 py配位基在各溶劑之吸收波長一覽表--------------------------68
表七 py)B2BIr(acac)光學性質一覽表---------------------------------------69
表八 (UpyU)B2BIr(acac)半生期一覽----------------------------------------------76
表九 IrpyF、IrpyCFB3B與IrpyCFB3B(m)CFB3B元件I,II特性----------80參考文獻 1. M. Pope, H. P. Kallmann, P. Magnante, J. Chem. Phys. 1963, 38, 2042.
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