TWI480279B - Novel carbazole derivatives and organic light emitting diode devices for their applications - Google Patents

Novel carbazole derivatives and organic light emitting diode devices for their applications Download PDF

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TWI480279B
TWI480279B TW099127288A TW99127288A TWI480279B TW I480279 B TWI480279 B TW I480279B TW 099127288 A TW099127288 A TW 099127288A TW 99127288 A TW99127288 A TW 99127288A TW I480279 B TWI480279 B TW I480279B
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Hsiao Chan Liu
Min Sheng Chen
Chin Yi Lee
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Description

新穎咔唑衍生物及其應用之有機發光二極體裝置
本發明係關於一種新穎咔唑(Carbazole)衍生物，其可作為有機發光二極體裝置之電洞傳輸層、發光層之主體(host)或客體(guest)、或電子傳輸層使用，以及關於此種有機發光二極體裝置。
有機發光二極體(Organic Light-Emitting Diode,OLED)具有主動發光、高對比、無視角限制、回應速度快等優點，被視為是下一世代的顯示器。OLED元件包含陰陽二極及有機層，有機層由電洞傳輸材料、電子傳輸材料及發光材料所組成。咔唑類衍生物因具有平面性佳、π鍵共軛程度高、可有效傳遞電荷、結構具剛性可提升材料的玻璃轉移溫度等特性，常被用作OLED的電洞傳輸層或發光層材料。
舉例來說，CN 1978441中揭示了具有優異電荷傳輸能力的苯基咔唑化合物，可用作電洞注入層、電洞傳輸層或發光層材料。WO 2007/069607中則揭示了可作為藍光磷光發光體之主體的咔唑化合物，以該專利材料與FIrpic(雙(4,6-二氟苯基吡啶)吡啶甲酸銥(III)(iridium(III)bis(4,6-difluorophenylpyridinato)picolate))共蒸鍍所製作的薄膜，磷光量子效率幾乎可達100%。JP 2006-69962揭示了可用在綠光磷光發光體之主體的咔唑化合物。TW I297038中則揭示了具有高玻璃轉移溫度的咔唑化合物，該專利將咔唑材料作為電洞傳輸層及發光層，並以TPBI(1,3,5-叁(N-苯基苯并咪唑-2-基)苯(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene))當作電子傳輸層，其元件發光效能在5伏特時為2.5 lm/W。EP 1972625揭示了一系列具咔唑及噁二唑結構的材料，其化合物結構特點為咔唑的三、六位置為氫或脂肪族官能基，該專利雖然指出其材料適合用做發光層的主體結構，但並無實際數據佐證。Angew. Chem. Int. Ed. 2008,47,8104. 中提及一種適合用在綠光磷光發光體之主體的咔唑化合物，其元件效率可達20.2%。
在上述文獻報導中，咔唑衍生物廣泛應用在電洞傳輸層或發光層中，卻未被當作電子傳輸層材料使用。有鑑於此，本發明開發一種可作為電子傳輸層材料的新穎咔唑衍生物，可同時作為電洞傳輸層、電子傳輸層及發光層使用，有效減化元件製作流程。
本發明之目的在於提供一種新穎咔唑衍生物有機材料並將其應用於有機發光二極體裝置中。參考第1圖有機發光二極體裝置之結構示意圖，有機電激發光元件主要包括一陽極60、一有機發光層(EML)40和一陰極10。陽極60是由在一玻璃基板70上所鍍上的一層透明可導電的氧化銦錫(ITO)層所構成。陰極10為例如由鋁(Al)所組成之金屬層。有機發光層40和陽極60之間包括一電洞傳輸層(HTL)50。有機發光層40和陰極10之間包括一電子傳輸層(ETL)30及一電子注入層(EIL)20。
本發明之另一目的在於提供一種有機發光二極體裝置，在該OLED裝置中，至少使用一種本發明前述之咔唑衍生物有機材料作為發光層之主體或客體、電洞傳輸層或電子傳輸層。在後述的應用例中，係含有本發明之咔唑衍生物作為有機發光二極體裝置的電洞傳輸層、發光層之主體或客體及電子傳輸層其中至少一層的材料。
本發明之咔唑衍生物係如下式(1)所表示者：
式(1)中，R1 ~R10 分別選自於氫、OH、NH2 、NO2 、CN、C1~6 烷氧基、C1~10 烷基、C1~20 氟化烷基、C2~10 烯基、C2~10 炔基、C6~20 芳香基、C6~20 氟化芳香基、C4~20 雜環芳香基；X1 ~X2 係選自下式(2)~(4)所表示之任一結構，
其中，R11 ~R33 分別選自於氫、OH、NH2 、NO2 、CN、C1~6 烷氧基、C1~10 烷基、C1~20 氟化烷基、C2~10 烯基、C2~10 炔基、C6~20 芳香基、C6~20 氟化芳香基、C4~20 雜環芳香基；X3 係選自下式(5)~(7)所表示之任一結構，
其中，R34 ~R37 及R39 ~R48 分別選自於氫、OH、NH2 、NO2 、CN、C1~6 烷氧基、C1~10 烷基、C1~20 氟化烷基、C2~10 烯基、C2~10 炔基、C6~20 芳香基、C6~20 氟化芳香基、C4~20 雜環芳香基，以及R38 選自於氫、C1~4 烷基、C6~10 芳香基。
底下將以實施例具體說明根據本發明之一系列咔唑衍生物的合成以及將其應用於OLED元件的測試。本發明之實施例旨在協助對本發明內容的瞭解，並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可對其作各種更動與變化，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
根據本發明之較佳具體實施例，合成底下一系列的咔唑衍生物，並將其應用於OLED元件的測試。
當X1 、X2 選自於咔唑基(carbazol)，X3 選自於5-(4-第三丁基苯基)-1,3,4-噁二唑基(5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole)時，此咔唑衍生物之化學式如下：
當X1 、X2 選自於苯基(phenyl)，X3 選自於5-(4-第三丁基苯基)-1,3,4-噁二唑基時，此咔唑衍生物之化學式如下：
當X1 、X2 選自於二苯基氨基(N,N-diphenylamino)，X3 選自於5-(4-第三丁基苯基)-1,3,4-噁二唑基時，此咔唑衍生物之化學式如下：
當X1 、X2 選自於苯基，X3 選自於2-甲基-1氫-四唑-5-基(2-Methyl-1H-tetraazol-5-yl)時，此咔唑衍生物之化學式如下：
當X1 、X2 選自於苯基，X3 選自於4,5-二苯基-1,3-噁唑-2-基(4,5-diphenyl-1,3-oxazol-2-yl)時，此咔唑衍生物之化學式如下：
以下係對本發明之咔唑衍生物的合成方法作詳細說明。
(化合物1的合成)
在一個250毫升雙頸瓶中，加入80毫升二甲基甲醯胺(N,N-Dimethyl formamide,DMF)、2.92克(6.85毫莫耳)3-(3,6-二溴-9氫-咔唑-9-基)苯甲腈(3-(3,6-Dibromo-9H-carbazol-9-yl)benzonitrile)、0.98克(15.08毫莫耳)疊氮化鈉(Sodium azide,NaN3 )、0.81克(15.08毫莫耳)氯化銨(Ammonium chloride,NH4 Cl)及磁石，在氮氣下迴流反應24小時，反應完成後，加入20毫升10%氫氯酸(Hydrochloric acid,HCl)後過濾，使用管柱層析予以純化，得3.21克白色固體3,6-二溴-9-(3-2氫-四唑-5-基苯基)-9氫-咔唑(3,6-Dibromo-9-(3-2H-tetraazol-5-yl-phenyl)-9H-Carbazole)(產率82.9%)。
在一50毫升雙頸瓶中，加入2.5克(5.33毫莫耳)3,6-二溴-9-(3-2氫-四唑-5-基苯基)-9氫-咔唑、4.19毫升(21.45毫莫耳)4-第三丁基苯甲醯氯(4-tert-Butylbenzoyl chloride)、35 毫升吡啶(pyridine)及磁石，氮氣下迴流反應八小時後進行萃取，使用管柱層析予以純化，得白色固體3,6-二溴-9-(3-(5-(4-第三丁基苯基)-1,3,4-噁二唑-2-基)苯基)-9氫-咔唑(3,6-Dibromo-9-(3-(5-(4-tert-butyl-phenyl)-1,3,4-oxadiazol-2-yl)phenyl)-9H-carbazole)(產率69.1%)。
在250毫升雙頸瓶中，加入75毫升甲苯(Toluene),0.15克(0.62毫莫耳)醋酸鈀(Palladium acetate,Pd(OAc)2 )觸媒、2.00克(20.79毫莫耳)第三丁醇鈉(Sodium tert-butoxide,NaOt Bu)、50毫升(2.5毫莫耳)三第三丁基膦(Tri-tert-butylphosphine,Pt Bu3 )、1.74克(10.39毫莫耳)咔唑、2.5克(4.16毫莫耳)3,6-二溴-9-(3-(5-(4-第三丁基苯基)-1,3,4-噁二唑-2-基)苯基)-9氫-咔唑及磁石，反應迴流30個小時，反應完成後加入10%氫氯酸，再以水及乙酸乙酯(Ethyl acetate,EA)進行萃取，將得到之有機層濃縮後，使用管柱層析予以純化，得白色固體(產率31.7%)。
(化合物2的合成)
在250毫升的雙頸瓶中加入50毫升甲苯、2.7毫升水、0.144克(0.125毫莫耳)肆(三苯膦基)鈀(Tetrakis(triphenylphosphine)palladium,Pd(pph3 )4 )觸媒、0.75克(5.4毫莫耳)碳酸鉀(Potassium Carbonate)、0.67克(5.48毫莫耳)苯基硼酸(Phenylboronic acid)、1.5克(2.49毫莫耳)3,6-二溴-9-(3-(5-(4-第三丁基苯基)-1,3,4-噁二唑-2-基)苯基)-9氫-咔唑、5毫升(0.25毫莫耳)Pt Bu3 及磁石，氮氣下迴流並攪拌24小時，反應完成後，以二氯甲烷(Dichloromethane)與水萃取，將得到之有機層再一次濃縮得固體，使用管柱層析予以純化，得白色固體(產率37%)。
(化合物3的合成)
在250毫升雙頸瓶中，加入75毫升甲苯，0.15克(0.62毫莫耳)醋酸鈀觸媒、2.00克(20.79毫莫耳)NaOt Bu、50毫升(2.5毫莫耳)Pt Bu3 、1.76克(10.39毫莫耳)二苯胺(Diphenylamine)、2.5克(4.16毫莫耳)3,6-二溴-9-(3-(5-(4- 第三丁基苯基)-1,3,4-噁二唑-2-基)苯基)-9氫-咔唑及磁石，反應迴流30個小時，反應完成後加入10%氫氯酸，再以水及乙酸乙酯進行萃取，將得到之有機層濃縮後，使用管柱層析予以純化，得黃色固體(產率77%)。
(化合物4的合成)
在250毫升的雙頸瓶中加入30毫升甲苯、12毫升水、0.5克(0.4毫莫耳)Pd(pph3 )4 、3.3克(24毫莫耳)碳酸鉀、1.5克(12.3毫莫耳)苯基硼酸、2克(4.7毫莫耳)3-(3,6-二溴-9氫-咔唑-9-基)苯甲腈、20毫升(1毫莫耳)Pt Bu3 及磁石，氮氣下迴流並攪拌24小時，反應完成後，以二氯甲烷與水萃取，將得到之有機層再一次濃縮得固體，使用管柱層析予以純化，得白色固體3-(3,6-二苯基-9氫-咔唑-9-基)苯甲腈(3-(3,6-Diphenyl-9H-carbazol-9-yl)benzonitrile)(產率69.8%)。
在一個250毫升雙頸瓶，加入60毫升二甲基甲醯胺、450毫克(1.07毫莫耳)3-(3,6-二苯基-9氫-咔唑-9-基)苯甲腈、208.71毫克(3.21毫莫耳)疊氮化鈉、171.73毫克(3.21毫莫耳)氯化銨及磁石，在氮氣下恆溫100℃反應38小時，反應完成後，加入10毫升10%氫氯酸後過濾，並以乙酸乙酯 及水萃取，有機層抽乾得淡橘色固體3,6-二苯基-9-(3-2氫-四唑-5-基-苯基)-9氫-咔唑(3,6-Diphenyl-9-(3-2H-tetraazol-5-yl-phenyl)-9H-carbazole)(產率85%)。
在一個250毫升單頸瓶，加入100毫升丙酮(acetone)、486毫克(1.05毫莫耳)3,6-二苯基-9-(3-2氫-四唑-5-基-苯基)-9氫-咔唑、149毫克(1.05毫莫耳)甲基碘(Methyl iodide,CH3 I)、145.1毫克(1.05毫莫耳)碳酸鉀及磁石，迴流反應18小時後過濾，以管柱純化，得白色固體(產率38%)。
(化合物5的合成)
在一個50毫升單頸瓶，加入15毫升甲苯、500毫克(1.17毫莫耳)3-(3,6-二溴-9氫-咔唑-9-基)苯甲腈、154毫克(0.785毫莫耳)二苯基乙酮(2-Phenylacetophenone)、0.05毫升(0.94毫莫耳)濃硫酸及磁石，迴流反應24小時後過濾，以乙酸乙酯及水萃取後，減壓濃縮得白色固體3,6-二溴-9-3-(4,5- 二苯基-1,3-噁唑-2-基)苯基-9氫-咔唑(3,6-Dibromo-9-3-(4,5-diphenyl-1,3-oxazol-2-yl)-phenyl-9H-carbazole)(產率77.8%)。
在50毫升的雙頸瓶中，加入15毫升甲苯、1.9毫升水、10.9毫克(0.009毫莫耳)Pd(pph3 )4 、533毫克(3.8毫莫耳)碳酸鉀、82毫克(0.67毫莫耳)苯基硼酸、454毫克(0.73毫莫耳)3,6-二溴-9-3-(4,5-二苯基-1,3-噁唑-2-基)苯基-9氫-咔唑、0.4毫升(0.02毫莫耳)Pt Bu3 及磁石，氮氣下迴流並攪拌24小時，反應完成後，以二氯甲烷與水萃取，將得到之有機層再一次濃縮得固體，使用管柱層析予以純化，得白色固體(產率50%)。
(應用例)
底下提出數個不同之有機發光二極體裝置的應用實例，並進行元件性質測試該等測試結果能顯現本發明之材料具有發展性。測試結果列於表一。
元件一
陽極：一銦錫氧化物設置於玻璃基板上(厚度120nm)
電洞注入層：PEDOT(聚(3,4-亞乙二氧基噻吩)(Poly(3,4-ethylenedioxythiophene)),4000rpm)
電洞傳輸層、發光層及電子傳輸層：皆為化合物2(厚度100nm)
電子注入層：LiF(厚度0.3nm)
陰極：Al(厚度100nm)
元件二
陽極：一銦錫氧化物設置於玻璃基板上(厚度120nm)
電洞傳輸層：化合物2(厚度40nm)
發光層：客體材料叁(2-苯基吡啶)銥(Tris(2-phenylpyridine)iridium,Ir(ppy)3 )及主體材料化合物2(厚度30nm)
電洞阻擋層：2,9-二甲基-4,7-二苯基-1,10-鄰二氮雜菲(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline,BCP)(厚度10nm)
電子傳輸層：化合物2(厚度20nm)
電子注入層：LiF(厚度0.3nm)
陰極：Al(厚度100nm)
元件三
陽極：一銦錫氧化物設置於玻璃基板上(厚度120nm)
電洞注入層：PEDOT(4000rpm)
電洞傳輸層：N,N'-雙(萘-1-基)-N,N'-雙(苯基)聯苯胺(N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine,NPB)(厚度40nm)
發光層：化合物3(厚度30nm)
電子傳輸層：叁(8-羥基喹啉)鋁(Tris(8-hydroxyquinolinato)aluminum,Alq3 )(厚度30nm)
電子注入層：LiF(厚度0.3nm)
陰極：Al(厚度100nm)
元件四
陽極：一銦錫氧化物設置於玻璃基板上(厚度120nm)
電洞傳輸層：NPB(厚度40nm)
發光層：客體材料Ir(ppy)3 及主體材料化合物2(厚度30nm)
電洞阻擋層：BCP(厚度10nm)
電子傳輸層：Alq3 (厚度20nm)
電子注入層：LiF(厚度0.3nm)
陰極：Al(厚度100nm)
(產業利用性)
本發明之新穎咔唑衍生物，可單獨作為有機發光二極體之電洞傳輸層、發光層之主體或客體、或電子傳輸層使用，亦可同時作為電洞傳輸層、電子傳輸層及發光層使用，有效減化元件製作流程。此等材料可以被用來做為具備指示元件用、電子照相機、發光光源、顯示器、記錄光源、讀寫光源、信號板、光學聯絡裝置或照明等之發光裝置。
10‧‧‧陰極
20‧‧‧電子注入層(EIL)
30‧‧‧電子傳輸層(ETL)
40‧‧‧發光層(EML)
50‧‧‧電洞傳輸層(HTL)
60‧‧‧陽極
70‧‧‧基板
第1圖為有機發光二極體裝置之結構示意圖。
10．．．陰極
20．．．電子注入層(EIL)
30．．．電子傳輸層(ETL)
40．．．發光層(EML)
50．．．電洞傳輸層(HTL)
60．．．陽極
70．．．基板

Claims (7)

  1. 一種咔唑衍生物，具有以下述之式(1)所表示之構造： 式(1)中，R1 ~R10 分別選自於氫、C6~20 芳香基、C6~20 氟化芳香基、C4~20 雜環芳香基；X1 ~X2 係選自下式(2)~(4)所表示之任一結構， 其中，R11 ~R33 分別選自於氫、C6~20 芳香基、C6~20 氟化芳香基、C4~20 雜環芳香基；X3 係選自下式(5)~(7)所表示之任一結構， 其中，R34 ~R37 及R39 ~R48 分別選自於氫、C6~20 芳香基、C6~20 氟化芳香基、C4~20 雜環芳香基，以及R38 選自於氫、C1~4 烷基、C6~10 芳香基。
  2. 如申請專利範圍第1項之咔唑衍生物，其中，X1 、X2 選自於咔唑基，以及X3 選自於5-(4-第三丁基苯基)-1,3,4-噁二唑基，而具有以下化學式：
  3. 如申請專利範圍第1項之咔唑衍生物，其中，X1 、X2 選自於苯基，以及X3 選自於5-(4-第三丁基苯基)-1,3,4-噁二唑基，而具有以下化學式：
  4. 如申請專利範圍第1項之咔唑衍生物，其中，X1 、X2 選自於二苯基氨基，以及X3 選自於5-(4-第三丁基苯基)-1,3,4-噁二唑基，而具有以下化學式：
  5. 如申請專利範圍第1項之咔唑衍生物，其中，X1 、X2 選自於苯基，以及X3 選自於2-甲基-1氫-四唑-5-基，而具有以下化學式：
  6. 如申請專利範圍第1項之咔唑衍生物，其中，X1 、X2 選自於苯基，以及X3 選自於4,5-二苯基-1,3-噁唑-2-基，而具有以下化學式：
  7. 一種有機發光二極體裝置，其特徵為：在一對電極之間包含有申請專利範圍第1至6項中任一項之咔唑衍生物，該咔唑衍生物係使用作為該有機發光二極體裝置之電洞傳輸層、電子傳輸層、或發光層主體或客體材料。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080230747A1 (en) * 2007-03-20 2008-09-25 Semiconductor Energy Laboratory Co., Ltd. Oxadiazole derivative and light-emitting element, light-emitting device, and electronic device in which the oxadiazole derivative is used
US20090167162A1 (en) * 2007-12-28 2009-07-02 Universal Display Corporation Dibenzothiophene-containing materials in phosphorescent light emitting diodes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080230747A1 (en) * 2007-03-20 2008-09-25 Semiconductor Energy Laboratory Co., Ltd. Oxadiazole derivative and light-emitting element, light-emitting device, and electronic device in which the oxadiazole derivative is used
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