TWI651318B - An organic electroluminescent device comprising a bipolar host material of a spiro [fluorene-9,2'-imidazole] group - Google Patents

An organic electroluminescent device comprising a bipolar host material of a spiro [fluorene-9,2'-imidazole] group Download PDF

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TWI651318B
TWI651318B TW106138222A TW106138222A TWI651318B TW I651318 B TWI651318 B TW I651318B TW 106138222 A TW106138222 A TW 106138222A TW 106138222 A TW106138222 A TW 106138222A TW I651318 B TWI651318 B TW I651318B
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electroluminescent device
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organic electroluminescent
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TW201823233A (en
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彭嘉歡
戴雷
蔡麗菲
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大陸商廣東阿格蕾雅光電材料有限公司
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

本發明涉及有機電致發光器件,包括陰極、陽極和有機層,所述有機 層為空穴阻擋層、電子傳輸層、發光層中的一層或多層,所述有機層具有式(I)所述結構的化合物,其中,R1-R3為示為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,氫,鹵素,C1-C4烷基。實驗表明,本發明的器件由於採用的雙極材料具有較高的玻璃化轉變溫度(Tg=158℃),雙極材料有利於載流子注入和傳輸平衡,因此發光效率高,使用壽命長。 The present invention relates to an organic electroluminescent device comprising a cathode, an anode and an organic layer, the organic layer being a hole blocking layer, an electron transporting layer, one or more layers in the light emitting layer, the organic layer having the formula (I) A compound of the formula wherein R 1 -R 3 are a C1-C4 alkyl or alkoxy substituted or unsubstituted acridinyl, phenothiazine, carbazolyl, diphenylamino, hydrogen, halogen, C1 -C4 alkyl. Experiments show that the device of the present invention has a high glass transition temperature (T g = 158 ° C) due to the bipolar material used, and the bipolar material is advantageous for carrier injection and transmission balance, thereby high luminous efficiency and long service life. .

Description

含有螺[芴-9,2’-咪唑]基團的雙極主體材料的有機電致發光器件 Organic electroluminescent device containing a bipolar host material of a spiro[芴-9,2'-imidazole] group

本發明涉及有機電致發光器件,具體涉及一種以螺[芴-9,2’-咪唑]為中心核的雙極主體材料製備的有機電致發光器件。 The present invention relates to an organic electroluminescent device, and in particular to an organic electroluminescent device prepared from a bipolar host material having a snail [芴-9, 2'-imidazole] as a central core.

有機發光二極體(OLED)具有相應速度快、耗能低、亮度高、視角廣、可彎曲、主動發光等特性,受到了科學界和產業界的高度重視。其在顯示、照明等方面的應用具有較大的潛力。電致螢光和電致磷光分別被稱為第一代和第二代OLED。基於螢光材料的OLED具有穩定性高的特點,但受限於量子統計學定律,在電啟動作用下,產生的單線態激子和三線態激子的比例為1:3,所以螢光材料電致發光內量子效率最大僅有25%。而磷光材料具有重原子的自旋軌道耦合作用,可以綜合利用單線態激子和三線態激子,理論的內量子效率可達100%,但是基於磷光的OLED具有明顯的效率滾降效應,在高亮度應用中有一定的阻礙。另外,磷光材料需用使用Pt,Ir等貴價金屬,因此磷光材料價格較高。而目前,OLED器件中客體材料主要應用磷光材料。 The organic light-emitting diode (OLED) has the characteristics of high speed, low energy consumption, high brightness, wide viewing angle, bendability and active illumination, and has been highly valued by the scientific community and the industry. Its application in display, lighting and other aspects has great potential. Electroluminescence and electrophosphorescence are referred to as first generation and second generation OLEDs, respectively. OLED based on fluorescent materials has high stability, but is limited by the law of quantum statistics. Under the action of electric start, the ratio of singlet excitons to triplet excitons is 1:3, so the fluorescent material The internal quantum efficiency of electroluminescence is only 25%. The phosphorescent material has a spin-orbit coupling effect of heavy atoms, which can comprehensively utilize singlet excitons and triplet excitons. The theoretical internal quantum efficiency can reach 100%, but the phosphorescent-based OLED has a significant efficiency roll-off effect. There are certain obstacles in high-brightness applications. In addition, phosphorescent materials require the use of expensive metals such as Pt, Ir, etc., so the price of phosphorescent materials is relatively high. At present, the guest materials in OLED devices mainly use phosphorescent materials.

磷光材料可以綜合利用單線態激子和三線態激子,實現100%的內量子效率。然而,由於過渡金屬配合物的激發態激子壽命相對過長,導致三 線態-三線態(T1-T1)在器件實際工作中淬滅。為了克服這個問題,研究者們常將磷光材料摻雜於有機主體材料中。因此,對於高效有機發光二極體,開發高性能的主體材料以及客體材料十分重要。 Phosphorescent materials can utilize singlet excitons and triplet excitons in combination to achieve 100% internal quantum efficiency. However, since the excited state exciton lifetime of the transition metal complex is relatively long, resulting in three The linear-triplet (T1-T1) is quenched in the actual operation of the device. To overcome this problem, researchers often dope phosphorescent materials into organic host materials. Therefore, for high-efficiency organic light-emitting diodes, it is important to develop high-performance host materials as well as guest materials.

目前,廣泛應用於磷光器件的主體材料為CBP(4,4’-二(9-咔唑基)聯苯),但是它要求的驅動電壓較高、玻璃化轉變溫度(Tg)低(Tg=62℃),易於結晶。另外,CBP是一種P型材料,空穴遷移率遠高於電子遷移率,不利於載流子注入和傳輸平衡,且發光效率低。 At present, the main material widely used in phosphorescent devices is CBP (4,4'-bis(9-carbazolyl)biphenyl), but it requires a higher driving voltage and a lower glass transition temperature (T g ) (T g = 62 ° C), easy to crystallize. In addition, CBP is a P-type material, the hole mobility is much higher than the electron mobility, which is not conducive to carrier injection and transmission balance, and the luminous efficiency is low.

針對現有主體(CBP)材料要求的驅動電壓較高、玻璃化轉變溫度易於結晶、載流子注入和傳輸不平衡等問題,本發明提供一種有機電致發光器件,其發光層主體材料為雙極性主體材料,該材料以螺[芴-9,2’-咪唑]作為強拉電子中心核,具有強給電子能力的二苯胺類、咔唑、吖啶等衍生物作為連接基團,形成D-A型、D-A-D型雙極性材料。 The present invention provides an organic electroluminescent device with a high driving voltage, a glass transition temperature, a crystallization, a carrier injection, and a transmission imbalance. The main body of the luminescent layer is bipolar. The host material, which uses spiro[芴-9,2'-imidazole] as the central core of the strong electrons, and has a strong electron donating ability such as diphenylamines, carbazoles, acridines and the like as a linking group to form a DA type. , DAD type bipolar material.

有機電致發光器件,包括陰極、陽極和有機層,所述有機層為空穴阻擋層、電子傳輸層、發光層中的一層或多層,所述有機層具有式(I)所述結構的化合物, An organic electroluminescent device comprising a cathode, an anode and an organic layer, the organic layer being a hole blocking layer, an electron transporting layer, one or more layers in the light emitting layer, the organic layer having a compound of the formula (I) ,

其中,R1、R2、R3表示為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,氫,鹵素,C1-C4的烷基,R1、R2、R3至少一個為C1-C4烷基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基。 Wherein R 1 , R 2 , R 3 are represented by C1-C4 alkyl or alkoxy substituted or unsubstituted acridinyl, phenothiazine, carbazolyl, diphenylamino, hydrogen, halogen, C1-C4 The alkyl group, at least one of R 1 , R 2 and R 3 is a C1-C4 alkyl-substituted or unsubstituted acridinyl group, a phenothiazine group, a carbazolyl group or a diphenylamino group.

優選:R1表示為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,R2、R3中至少一個為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,其餘為氫或C1-C4的烷基。 Preferably, R 1 represents a C1-C4 alkyl group or an alkoxy substituted or unsubstituted acridinyl group, a phenothiazine group, a carbazolyl group, a diphenylamino group, and at least one of R 2 and R 3 is a C1-C4 alkane. Alkyl or alkoxy substituted or unsubstituted acridinyl, phenothiazine, carbazolyl, diphenylamino, the balance being hydrogen or a C1-C4 alkyl group.

優選:R1、R3為C1-C4烷基或烷氧基取代或者未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基。 Preferably, R 1 and R 3 are a C1-C4 alkyl group or an alkoxy-substituted or unsubstituted acridinyl group, a phenothiazine group, an oxazolyl group, or a diphenylamino group.

優選:R1、R3相同。 Preferably, R 1 and R 3 are the same.

式(I)所述的化合物具有下列結構: The compound of formula (I) has the following structure:

所述式(I)所述的化合物為發光層的材料。 The compound of the formula (I) is a material of the light-emitting layer.

本發明的電子器件有機層的總厚度為1-1000nm,優選1-500nm,更優選5-300nm。 The organic layer of the electronic device of the present invention has a total thickness of from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 5 to 300 nm.

所述有機層可以通過蒸渡或旋塗形成薄膜。 The organic layer may be formed into a film by steaming or spin coating.

如上面提到,本發明的式(I)所述的化合物如下,但不限於所列舉的結構: As mentioned above, the compounds of formula (I) of the present invention are as follows, but are not limited to the structures listed:

上述雙極材料的製備方法,包括以下製備步驟:首先將鹵素取代芳基乙二酮與鹵素取代或未取代的9-芴酮在醋酸銨和乙酸條件下反應,得到鹵素取代的4’,5’-二芳基螺(芴-9,2’-咪唑),最後鹵素取代的4’,5’-二芳基螺(芴-9,2’-咪唑)與C1-C4烷基或烷氧基取代或未取代的吖啶、吩噻嗪基、咔唑基、二苯胺基通過鈀催化的Buchwald反應,得到所述的雙極性主體材料。 The preparation method of the above bipolar material comprises the following steps: firstly reacting a halogen-substituted arylethanedione with a halogen-substituted or unsubstituted 9-fluorenone under ammonium acetate and acetic acid to obtain a halogen-substituted 4',5. '-Diaryl spiro (芴-9,2'-imidazole), the last halogen-substituted 4',5'-diaryl spiro (芴-9,2'-imidazole) and C1-C4 alkyl or alkoxy The disubstituted or unsubstituted acridine, phenothiazine, carbazolyl, and diphenylamine groups are subjected to a palladium catalyzed Buchwald reaction to give the bipolar host material.

實驗表明,本發明的器件由於採用的雙極主體材料具有較高的玻璃化轉變溫度(Tg=158℃),雙極主體材料有利於載流子注入和傳輸平衡,因此發光效率高,使用壽命長。 Experiments show that the device of the present invention has a high glass transition temperature (T g = 158 ° C) due to the bipolar host material used, and the bipolar host material is advantageous for carrier injection and transmission balance, so the luminous efficiency is high, and the use is high. long life.

10‧‧‧玻璃基板 10‧‧‧ glass substrate

20‧‧‧陽極 20‧‧‧Anode

30‧‧‧空穴注入層 30‧‧‧ hole injection layer

40‧‧‧空穴傳輸層 40‧‧‧ hole transport layer

50‧‧‧發光層 50‧‧‧Lighting layer

60‧‧‧空穴阻擋層 60‧‧‧ hole blocking layer

70‧‧‧電子傳輸層 70‧‧‧Electronic transport layer

80‧‧‧電子注入層 80‧‧‧electron injection layer

90‧‧‧陰極 90‧‧‧ cathode

圖1為化合物2的DSC曲線;以及圖2為本發明的器件結構圖,其中10代表為玻璃基板,20代表為陽極,30代表為空穴注入層,40代表為空穴傳輸層,50代表發光層,60代表為空穴阻擋層,70代表為電子傳輸層,80代表為電子注入層,90代表為陰極。 1 is a DSC curve of Compound 2; and FIG. 2 is a structural view of the device of the present invention, wherein 10 represents a glass substrate, 20 represents an anode, 30 represents a hole injection layer, 40 represents a hole transport layer, and 50 represents a hole transport layer. The luminescent layer, 60 represents a hole blocking layer, 70 represents an electron transporting layer, 80 represents an electron injecting layer, and 90 represents a cathode.

下面結合實施例對本發明作進一步詳細的描述,但本發明的實施方式不限於此。 The present invention will be further described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto.

實施例1 Example 1 (1)4’-(4-溴苯基)-5’-苯基螺(芴-9,2’-咪唑)(c1)的合成 (1) Synthesis of 4'-(4-bromophenyl)-5'-phenylspiro(芴-9,2'-imidazole) (c1)

合成路線如下所示: The synthetic route is as follows:

具體合成步驟為:秤取1-(4-溴苯基)-2-苯基乙基-1,2-二酮(14.5g,50mmol)(a1)(通過Sonogashira偶聯反應,再氧化製備),9-芴酮(7.2g,40mmol)(b1),醋酸銨(19.2g,250mmol),150mL冰醋酸於250mL的圓底燒瓶中,升溫至回流反應攪拌16小 時。反應結束後,自然冷卻至室溫,倒入200mL純淨水中,析出黃色固體。砂芯漏斗抽濾,水洗。矽膠柱層析分離得到9.9g黃色固體。產率:55%。 The specific synthetic procedure is as follows: 1-(4-bromophenyl)-2-phenylethyl-1,2-dione (14.5 g, 50 mmol) (a1) (prepared by Sonogashira coupling reaction, reoxidation) , 9-fluorenone (7.2 g, 40 mmol) (b1), ammonium acetate (19.2 g, 250 mmol), 150 mL of glacial acetic acid in a 250 mL round bottom flask, warmed to reflux and stirred for 16 min. Time. After completion of the reaction, it was naturally cooled to room temperature, poured into 200 mL of purified water to precipitate a yellow solid. The core funnel was suction filtered and washed. Separation by gel column chromatography gave 9.9 g of a yellow solid. Yield: 55%.

(2)9,9-二甲基-10-[4-[4’-苯基螺(芴-9,2’-咪唑)-5’-基]苯基]-9,10-二氫吖啶(1)的合成 (2) 9,9-Dimethyl-10-[4-[4'-phenylspiro(芴-9,2'-imidazole)-5'-yl]phenyl]-9,10-dihydroanthracene Synthesis of pyridine (1)

其合成路線見圖1所示。 The synthetic route is shown in Figure 1.

具體合成步驟為:秤取4’-(4-溴苯基)-5’-苯基螺(芴-9,2’-咪唑)(0.9g,2mmol)(c1),9,9-二甲基-9,10-二氫吖啶(0.46g,2.2mmol)(d1),Pd2(dba)3(0.18g,0.2mmol),NaOtBu(0.39g,4mmol)於25mL三口燒瓶中,換氮氣三次。三叔丁基膦甲苯溶液(0.15g,0.42mmol)溶於10mL乾燥的甲苯中,注入到反應瓶中。升溫回流16小時。反應結束後,加入5%的亞硫酸氫鈉溶液,二氯甲烷萃取,合併有機層,無水硫酸鎂乾燥。砂芯漏斗過濾,旋乾溶劑,以正己烷:乙酸乙酯=10:1為洗脫劑,矽膠層析柱提純,分離得到1.03g黃色粉末固體。再用4mL二氯甲烷溶解,加入20mL甲醇,放置於5℃冰箱析晶,得到0.85g黃色晶體。產率:73%。產物鑒定資料如下: 1H NMR(400MHz,CDCl3)δ=8.02-7.94(m,J=8.3Hz,2 H),7.80(d,J=7.1Hz,2 H),7.83(d,J=7.8Hz,2 H),7.53(d,J=7.3Hz,1 H),7.51-7.37(m,8 H),7.30-7.22(m,2 H),7.05-6.90(m,6 H),6.37-6.31(m,J=8.1Hz,2 H).13C NMR(100MHz,CDCl3)δ=168.5,167.9,143.7,142.4,140.6,138.7,132.2,132.1,131.9,131.5,131.0,130.3,129.8,129.2,128.6,128.0,126.4,125.4,123.2,121.0,121.0,114.1,110.3,53.5,36.1,31.2ppm.Ms(ESI:Mz 577)(M+1) The specific synthetic steps are: weighing 4'-(4-bromophenyl)-5'-phenylspiro(芴-9,2'-imidazole) (0.9g, 2mmol) ( c1 ), 9,9-dimethyl Base-9,10-dihydroacridine (0.46 g, 2.2 mmol) ( d1 ), Pd 2 (dba) 3 (0.18 g, 0.2 mmol), NaOtBu (0.39 g, 4 mmol) in a 25 mL three-neck flask, with nitrogen three times. A solution of tri-tert-butylphosphine in toluene (0.15 g, 0.42 mmol) was dissolved in 10 mL of dry toluene and poured into a reaction flask. The temperature was refluxed for 16 hours. After the reaction was completed, a 5% solution of sodium hydrogensulfite was added, and the mixture was extracted with dichloromethane. The mixture was filtered through a celite funnel, and the solvent was evaporated to dryness eluting with hexane: ethyl acetate = 10:1 as eluent. Further, it was dissolved in 4 mL of dichloromethane, and 20 mL of methanol was added thereto, and the mixture was allowed to stand in a refrigerator at 5 ° C to obtain 0.85 g of a yellow crystal. Yield: 73%. The product identification data is as follows: 1 H NMR (400 MHz, CDCl 3 ) δ = 8.02 - 7.94 (m, J = 8.3 Hz, 2 H), 7.80 (d, J = 7.1 Hz, 2 H), 7.83 (d, J = 7.8 Hz, 2 H), 7.53 (d, J = 7.3 Hz, 1 H), 7.51-7.37 (m, 8 H), 7.30-7.22 (m, 2 H), 7.05-6.90 (m, 6 H), 6.37-6.31 (m, J = 8.1 Hz, 2 H). 13 C NMR (100 MHz, CDCl 3 ) δ = 168.5, 167.9, 143.7, 142.4, 140.6, 138.7, 132.2, 132.1, 131.9, 131.5, 131.0, 130.3, 129.8, 129.2, 128.6, 128.0, 126.4, 125.4, 123.2, 121.0, 121.0, 114.1, 110.3, 53.5, 36.1, 31.2 ppm. Ms (ESI: Mz 577) (M+1)

實施例2 Example 2 (1)2-溴-4’-(4-溴苯基)-5’-苯基螺(芴-9,2’-咪唑)(c2)的合成 (1) Synthesis of 2-bromo-4'-(4-bromophenyl)-5'-phenylspiro(芴-9,2'-imidazole) (c2)

合成路線如下所示: The synthetic route is as follows:

秤取1-(4-溴苯基)-2-苯基乙基-1,2-二酮(4.34g,15mmol)(a1)(通過Sonogashira偶聯反應,再氧化製備),2-溴-9-芴酮(3.89g,15mmol),醋酸銨(5.8g,75mmol),30mL冰醋酸於50mL的圓底燒瓶中,升溫至回流反應攪拌16小時。反應結束後,自然冷卻至室溫,倒入100mL純淨水中,析出黃色固體。砂芯漏斗抽濾,水洗。矽膠柱層析分離得到4.1g黃色固體。產率:52%。 Weigh 1-(4-bromophenyl)-2-phenylethyl-1,2-dione (4.34 g, 15 mmol) (a1) (prepared by Sonogashira coupling reaction, reoxidation), 2-bromo- 9-fluorenone (3.89 g, 15 mmol), ammonium acetate (5.8 g, 75 mmol), 30 mL of glacial acetic acid in a 50 mL round bottom flask, warmed to reflux and stirred for 16 hours. After completion of the reaction, it was naturally cooled to room temperature, poured into 100 mL of purified water to precipitate a yellow solid. The core funnel was suction filtered and washed. Separation by gel column chromatography gave 4.1 g of a yellow solid. Yield: 52%.

(2)10-(4-(2-(9,9-二甲基吖啶-10(9H)-基)-4’-苯基螺(芴-9,2’-咪唑)-5’-基]苯基]-9,9-二甲基-9,10-二氫吖啶(2)的合成 (2) 10-(4-(2-(9,9-Dimethylacridin-10(9H)-yl)-4'-phenylspiro(芴-9,2'-imidazole)-5'- Synthesis of phenyl]-9,9-dimethyl-9,10-dihydroacridine (2)

合成路線如下所示: The synthetic route is as follows:

具體合成步驟為:秤取2-溴-4’-(4-溴苯基)-5’-苯基螺(芴-9,2’-咪唑)(1g,1.9mmol)(c2),9,9-二甲基-9,10-二氫吖啶(0.79g,3.8mmol)(d1),Pd2(dba)3(0.18g,0.2mmol),NaOtBu(0.73g,7.6mmol)於25mL三口燒瓶中,換氮氣三次。三叔丁基膦甲苯溶液(0.12g,0.6mmol)溶於10mL乾燥的甲苯中,注入到反應瓶中。升溫回流16小時。反應結束後,加入5%的亞硫酸氫鈉溶液,二氯甲烷萃取,合併有機層,無水硫酸鎂乾燥。砂芯漏斗過濾,旋乾溶劑,以正己烷:乙酸乙酯=10:1為洗脫劑,矽膠層析柱提純,分離得到1.35g黃色粉末固體。再用4mL二氯甲烷溶解,加入20mL甲醇,放置於5℃冰箱析晶,得到1.1g黃色晶體。產率:73%。產物鑒定資料如下:1H NMR(400MHz,CDCl3)δ=8.08(d,J=7.9Hz,1 H),7.95-7.87(m,3 H),7.72(d,J=7.2Hz,2 H),7.56-7.48(m,2 H),7.48-7.41(m,7 H),7.38(d,J=8.3Hz,2 H),7.32(s,1 H),7.04-6.86(m,10 H),6.43-6.36(m,2 H),6.34-6.27(m,2 H),1.67(s,12 H)ppm.13C NMR(100MHz,CDCl3)δ=168.9,168.3,143.8,142.5,141.7,141.5,140.8,140.7,140.5,139.1,133.1,131.9,131.7,131.5,131.1,130.3,130.1,129.9,129.2,128.6,128.4,126.5,126.5,126.4,125.4,125.3,123.3,123.1,121.3,120.9,120.7,114.3,114.1,110.0,,53.5,36.0,36.0,31.6,31.2ppm.Ms(ESI:Mz 784)(M+1)。Tg=158℃。 The specific synthetic procedure is as follows: 2-bromo-4'-(4-bromophenyl)-5'-phenylspiro(芴-9,2'-imidazole) (1 g, 1.9 mmol) ( c2 ), 9, 9-Dimethyl-9,10-dihydroacridine (0.79 g, 3.8 mmol) ( d1 ), Pd 2 (dba) 3 (0.18 g, 0.2 mmol), NaOtBu (0.73 g, 7.6 mmol) in 25 mL three In the flask, change the nitrogen three times. A solution of tri-tert-butylphosphine in toluene (0.12 g, 0.6 mmol) was dissolved in 10 mL of dry toluene and poured into a reaction flask. The temperature was refluxed for 16 hours. After the reaction was completed, a 5% solution of sodium hydrogensulfite was added, and the mixture was extracted with dichloromethane. The mixture was filtered through a celite funnel, and the solvent was evaporated to dryness eluting with hexane: ethyl acetate = 10:1 as eluent. Further, it was dissolved in 4 mL of dichloromethane, and 20 mL of methanol was added thereto, and the mixture was allowed to stand in a refrigerator at 5 ° C to obtain 1.1 g of yellow crystals. Yield: 73%. The product identification data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ = 8.08 (d, J = 7.9 Hz, 1 H), 7.95-7.87 (m, 3 H), 7.72 (d, J = 7.2 Hz, 2 H ), 7.56-7.48 (m, 2 H), 7.48-7.41 (m, 7 H), 7.38 (d, J = 8.3 Hz, 2 H), 7.32 (s, 1 H), 7.04-6.86 (m, 10) H), 6.43-6.36 (m, 2 H), 6.34-6.27 (m, 2 H), 1.67 (s, 12 H) ppm. 13 C NMR (100 MHz, CDCl 3 ) δ = 168.9, 168.3, 143.8, 142.5 , 141.7, 141.5, 140.8, 140.7, 140.5, 139.1, 133.1, 131.9, 131.7, 131.5, 131.1, 130.3, 130.1, 129.9, 129.2, 128.6, 128.4, 126.5, 126.5, 126.4, 125.4, 125.3, 123.3, 123.1, 121.3 , 120.9, 120.7, 114.3, 114.1, 110.0, 53.5, 36.0, 36.0, 31.6, 31.2 ppm. Ms (ESI: Mz 784) (M+1). T g = 158 ° C.

實施例3 Example 3 玻璃化轉變溫度測試 Glass transition temperature test

氮氣保護下,以20℃/min的加熱和冷卻速率用示差掃描量熱法(DSC)測試化合物2的玻璃化轉變溫度。測得化合物2的玻璃化轉變溫度Tg為158℃(圖1)。而文獻所報導的CBP的玻璃化轉變溫度僅為62℃。 The glass transition temperature of Compound 2 was tested by differential scanning calorimetry (DSC) at a heating and cooling rate of 20 ° C/min under nitrogen atmosphere. The glass transition temperature T g of Compound 2 was measured to be 158 ° C ( FIG. 1 ). The glass transition temperature of CBP reported in the literature is only 62 °C.

可見,本發明中的化合物比常用主體材料CBP具有更高的玻璃化轉變溫度,本發明顯著提高了主體材料的熱穩定性。 It can be seen that the compound of the present invention has a higher glass transition temperature than the conventional host material CBP, and the present invention remarkably improves the thermal stability of the host material.

實施例4 Example 4 電致發光器件的製備 Preparation of electroluminescent device

器件結構為ITO/MoO3(10nm)/NPB(40nm)/化合物2:Ir(ppy):(7wt%,30nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/AL(100nm)(見圖2) The device structure is ITO/MoO 3 (10 nm) / NPB (40 nm) / compound 2 : Ir (ppy): (7 wt%, 30 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / AL (100 nm ) (see Figure 2)

器件製備方式描述如下: The device preparation method is described as follows:

首先,將透明導電ITO玻璃基板(包含10和20)按照以下步驟處理:預先用洗滌劑溶液、去離子水,乙醇,丙酮,去離子水洗淨,再經氧等離子處理30秒。 First, the transparent conductive ITO glass substrate (including 10 and 20) was treated as follows: previously washed with a detergent solution, deionized water, ethanol, acetone, deionized water, and then subjected to oxygen plasma treatment for 30 seconds.

然後,在ITO上蒸渡10nm厚的MoO3作為空穴注入層30。 Then, 10 nm thick MoO 3 was vapor-deposited on the ITO as the hole injection layer 30.

然後,在空穴注入層上蒸渡40nm厚的NPB作為空穴傳輸層40。 Then, a 40 nm-thick NPB was vapor-deposited on the hole injection layer as the hole transport layer 40.

然後,在空穴傳輸層上蒸渡30nm厚的化合物2:Ir(ppy):(7wt%)作為發光層50。 Then, a compound 2 of 2 nm thick: Ir(ppy): (7 wt%) was vapor-deposited on the hole transport layer as the light-emitting layer 50.

然後,在發光層上蒸渡10nm厚的BCP作為空穴阻擋層60。 Then, a BCP having a thickness of 10 nm was vapor-deposited on the light-emitting layer as the hole blocking layer 60.

然後,在空穴阻擋層上蒸渡30nm厚的Alq3作為電子傳輸層70。 Then, 30 nm thick Alq 3 was vapor-deposited on the hole blocking layer as the electron transport layer 70.

然後,在電子傳輸層上蒸渡1nm厚的Alq3作為電子注入層80。 Then, 1 nm thick Alq 3 was vaporized on the electron transport layer as the electron injection layer 80.

最後,在電子注入層上蒸渡100nm厚的鋁作為器件陰極90。 Finally, 100 nm thick aluminum was vaporized on the electron injecting layer as the device cathode 90.

所製備的器件在20mA/cm2的工作電流密度下,亮度5224cd/m2,電流效率為26.12cd/A,發射綠光CIEx為0.307,CIEy為0.620。 Devices prepared in operating current density 20mA / cm 2, the luminance of 5224cd / m 2, the current efficiency was 26.12cd / A, green light emission of CIEx 0.307, CIEy of 0.620.

比較例 Comparative example 電致發光器件的製備 Preparation of electroluminescent device

器件結構為ITO/MoO3(10nm)/NPB(40nm)/CBP:Ir(ppy):(7wt%,30nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/AL(100nm) The device structure is ITO/MoO 3 (10 nm) / NPB (40 nm) / CBP: Ir (ppy): (7 wt%, 30 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / AL (100 nm)

方法同實施例4,但使用常用市售化合物CBP作為主體材料,製作對比用電致發光有機半導體二極體器件。 The method was the same as in Example 4 except that a commonly used commercially available compound CBP was used as a host material to prepare a comparative electroluminescent organic semiconductor diode device.

所製備的器件在20mA/cm2的工作電流密度下,亮度3875cd/m2,電流效率為19.38cd/A,發射綠光CIEx為0.312,CIEy為0.620。 Devices prepared in operating current density 20mA / cm 2, the luminance of 3875cd / m 2, the current efficiency was 19.38cd / A, green light emission of CIEx 0.312, CIEy of 0.620.

通過對比實施例4和比較例的實驗結果可見,本發明中的雙極主體材料相比於廣泛使用的主體材料CBP,更利於載流子注入和傳輸平衡,使用本發明的有機材料製備的器件具有更好的電致發光性能,更符合高性能有機半導體器件對主體材料的要求。 By comparing the experimental results of Example 4 and the comparative example, it can be seen that the bipolar host material of the present invention is more advantageous for carrier injection and transport balance than the widely used host material CBP, and the device prepared using the organic material of the present invention. It has better electroluminescence properties and is more in line with the requirements of high performance organic semiconductor devices for host materials.

Claims (10)

一種有機電致發光器件,包括陰極、陽極和有機層,所述有機層為空穴阻擋層、電子傳輸層、發光層中的一層或多層,所述有機層為具有式(I)所述結構的化合物, 其中,R1、R2、R3表示為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,氫,鹵素,C1-C4的烷基,R1、R2、R3至少一個為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基。 An organic electroluminescent device comprising a cathode, an anode and an organic layer, the organic layer being a hole blocking layer, an electron transporting layer, one or more layers of the light emitting layer, the organic layer having the structure of the formula (I) compound of, Wherein R 1 , R 2 , R 3 are represented by C1-C4 alkyl or alkoxy substituted or unsubstituted acridinyl, phenothiazine, carbazolyl, diphenylamino, hydrogen, halogen, C1-C4 The alkyl group, at least one of R 1 , R 2 and R 3 is a C1-C4 alkyl group or an alkoxy-substituted or unsubstituted acridinyl group, a phenothiazine group, an oxazolyl group or a diphenylamino group. 如申請專利範圍第1項所述的有機電致發光器件,其中,R1表示為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,R2、R3中至少一個為C1-C4烷基或烷氧基取代或未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基,其餘為氫或烷基。 The organic electroluminescent device according to claim 1, wherein R 1 represents a C1-C4 alkyl group or an alkoxy substituted or unsubstituted acridinyl group, a phenothiazine group, a carbazolyl group, or a The anilino group, at least one of R 2 and R 3 is a C1-C4 alkyl group or an alkoxy-substituted or unsubstituted acridinyl group, a phenothiazine group, an oxazolyl group, a diphenylamino group, and the remainder is hydrogen or an alkyl group. 如申請專利範圍第2項所述的有機電致發光器件,其中,R1、R3為C1-C4烷基或烷氧基取代或者未取代的吖啶基、吩噻嗪基、咔唑基、二苯胺基。 The organic electroluminescent device according to claim 2, wherein R 1 and R 3 are a C1-C4 alkyl group or an alkoxy-substituted or unsubstituted acridinyl group, a phenothiazine group, or a carbazolyl group. Diphenylamine group. 如申請專利範圍第3項所述的有機電致發光器件,其中,R1、R3相同。 The organic electroluminescent device according to claim 3, wherein R 1 and R 3 are the same. 如申請專利範圍第1項所述的有機電致發光器件,其中,所述有機層具有下列結構化合物: The organic electroluminescent device according to claim 1, wherein the organic layer has the following structural compound: 如申請專利範圍第5項所述的有機電致發光器件,所述有機層具有下列結構化合物: The organic electroluminescent device according to claim 5, wherein the organic layer has the following structural compound: 如申請專利範圍第1項所述的有機電致發光器件,其中,所述式(I)所述的化合物為發光層的材料。 The organic electroluminescent device according to claim 1, wherein the compound of the formula (I) is a material of the light-emitting layer. 如申請專利範圍第1項所述的有機電致發光器件,其中,所述有機層的總厚度為1-1000nm。 The organic electroluminescent device according to claim 1, wherein the organic layer has a total thickness of from 1 to 1000 nm. 如申請專利範圍第1項所述的有機電致發光器件,其中,所述有機層的總厚度為1-500nm。 The organic electroluminescent device according to claim 1, wherein the organic layer has a total thickness of from 1 to 500 nm. 如申請專利範圍第1項所述的有機電致發光器件,其中,所述有機層通過蒸渡或旋塗形成薄膜。 The organic electroluminescent device according to claim 1, wherein the organic layer is formed into a thin film by evaporation or spin coating.
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Title
MAHMOODI et al.,"Photochromism of Several Synthesized 1,3-Diazabicyclo[3.1.0]hex-3-ene Derivatives.",J. Chem. Res., Synop. 2004, 6, 438-440
Siva Senthil Kumar Boominathan et al.," A sequential one-pot approach to 1,2,4,5-tetrasubstituted-2H-imidazole synthesis from disubstituted alkynes", New J. Chem., 29 June 2015.
Siva Senthil Kumar Boominathan et al.," A sequential one-pot approach to 1,2,4,5-tetrasubstituted-2H-imidazole synthesis from disubstituted alkynes", New J. Chem., 29 June 2015. MAHMOODI et al.,"Photochromism of Several Synthesized 1,3-Diazabicyclo[3.1.0]hex-3-ene Derivatives.",J. Chem. Res., Synop. 2004, 6, 438-440 *

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