技术领域Technical Field
本发明属于有机光电致发光材料技术领域，更具体的说是涉及一种发光辅助材料及其制备方法和有机电致发光器件。The invention belongs to the technical field of organic photo-electroluminescent materials, and more specifically relates to a luminescent auxiliary material and a preparation method thereof and an organic electroluminescent device.
背景技术Background Art
有机电致发光(OLED)为自发光显示元件的一种类型，显示器具有高亮度、高分辨率、宽视角、低能耗、高响应速度的优势。一般而言，有机电致发光是指，利用有机物质使电能转变为光能的现象。利用有机发光现象的有机发光元件通常具有包含阳极和阴极以及位于它们之间的有机物层的结构。例如空穴注入层(HIL)、空穴传输层(HTL)、发光层、电子传输层(ETL)和电子注入层(EIL)。Organic electroluminescence (OLED) is a type of self-luminous display element, and the display has the advantages of high brightness, high resolution, wide viewing angle, low energy consumption, and high response speed. Generally speaking, organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic light-emitting elements using the organic light-emitting phenomenon generally have a structure including an anode and a cathode and an organic layer located between them. For example, a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL).
为了解决寿命和效率问题，通常会在空穴输送层和发光层之间加入发光辅助层(多层空穴输送层)。发光辅助层主要起到辅助空穴传输层的作用，因此有时也称为第二空穴传输层。发光辅助层能够使阳极转移的空穴平稳地移动到发光层，并且可以阻挡从阴极转移的电子，以将电子限制在发光层内，减少空穴传输层与发光层之间的势垒，降低有机电致发光器件的驱动电压，进一步增加空穴的利用率，从而改善器件的发光效率和寿命。In order to solve the problems of lifespan and efficiency, a luminescent auxiliary layer (multi-layer hole transport layer) is usually added between the hole transport layer and the light-emitting layer. The luminescent auxiliary layer mainly plays the role of assisting the hole transport layer, so it is sometimes also called the second hole transport layer. The luminescent auxiliary layer can enable the holes transferred from the anode to move smoothly to the light-emitting layer, and can block the electrons transferred from the cathode to confine the electrons in the light-emitting layer, reduce the potential barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, and further increase the utilization rate of holes, thereby improving the luminous efficiency and life of the device.
但是现有能够形成发光辅助层且具有优异器件性能的材料较少。特别是，OLED的寿命和发光效率提升不明显，因此开发更高性能的有机功能材料，满足面板制造企业的要求，显得尤为重要。However, there are few materials that can form a light-emitting auxiliary layer and have excellent device performance. In particular, the lifespan and luminous efficiency of OLEDs have not been significantly improved, so it is particularly important to develop higher-performance organic functional materials to meet the requirements of panel manufacturers.
因此，如何研发一种高发光效率，长寿命，改善驱动电压的发光辅助材料及其制备方法和有机电致发光器件是本领域技术人员亟需解决的技术问题。Therefore, how to develop a luminescent auxiliary material with high luminous efficiency, long life and improved driving voltage and a preparation method thereof and an organic electroluminescent device is a technical problem that technical personnel in this field urgently need to solve.
发明内容Summary of the invention
有鉴于此，本发明提供了一种发光辅助材料及其制备方法和有机电致发光器件。In view of this, the present invention provides a luminescence auxiliary material and a preparation method thereof, and an organic electroluminescent device.
为了实现上述目的，本发明采用如下技术方案：在二苯并呋喃的1,4位分别连接三芳胺和9-苯基-9H-咔唑，其中9-苯基-9H-咔唑上的苯环与二苯并呋喃以邻位的取代方式连接。得到的化合物作为发光辅助层材料，能够使有机电致发光器件在保持效率，驱动电压不受影响的情况下，寿命得到大幅度提升。In order to achieve the above object, the present invention adopts the following technical scheme: triarylamine and 9-phenyl-9H-carbazole are connected to the 1 and 4 positions of dibenzofuran, respectively, wherein the benzene ring on 9-phenyl-9H-carbazole is connected to dibenzofuran in an ortho-substituted manner. The obtained compound is used as a light-emitting auxiliary layer material, which can significantly improve the life of the organic electroluminescent device while maintaining efficiency and unaffecting the driving voltage.
上述发光辅助材料的结构通式如式I或式II所示：The general structural formula of the above-mentioned luminescent auxiliary material is shown in Formula I or Formula II:
其中，in,
Ar1，Ar2各自独立的选自如下所示基团：Ar1 and Ar2 are each independently selected from the following groups:
*表示基团连接位置。*Indicates the position where the group is attached.
取代位置定义如下：The substitution positions are defined as follows:
进一步，上述发光辅助材料选自下述结构式所示化合物中的任一种：Furthermore, the above-mentioned luminescence auxiliary material is selected from any one of the compounds represented by the following structural formulas:
本发明还提供一种上述发光辅助材料的制备方法，包括以下步骤：The present invention also provides a method for preparing the above-mentioned luminescence auxiliary material, comprising the following steps:
(1)N2保护下，将反应物A-I、反应物B-I、钯催化剂和碱加入到甲苯、乙醇和水的混合溶剂中，升温反应，冷却至室温，加入H2O，待固体析出完毕后过滤，将滤饼烘干，用管柱色谱法纯化剩余物质，滤液用旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体C-I；(1) UnderN2 protection, reactant AI, reactant BI, palladium catalyst and base are added to a mixed solvent of toluene, ethanol and water, the temperature is raised for reaction, cooled to room temperature,H2O is added, and after solid precipitation is complete, the solid is filtered, the filter cake is dried, and the remaining substance is purified by column chromatography. The filtrate is used to remove the solvent by a rotary evaporator, and the obtained solid is dried to obtain intermediate CI;
(2)N2保护下，在反应容器中加入中间体C-I和反应物D-I溶于二甲苯之后，加入钯催化剂、膦配体和碱；添加后使反应温度缓慢升温，并且搅拌混合物；使用硅藻土趁热抽滤，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，用管柱色谱法纯化剩余物质，得到式I所示化合物；(2) UnderN2 protection, add intermediate CI and reactant DI to a reaction vessel and dissolve them in xylene, then add palladium catalyst, phosphine ligand and base; after the addition, slowly increase the reaction temperature and stir the mixture; use diatomaceous earth to filter while hot, cool the filtrate to room temperature, then add distilled water to the filtrate for washing, retain the organic phase after separation, and extract the aqueous phase with ethyl acetate; then use magnesium sulfate to dry the combined organic layer, and purify the remaining substance by column chromatography to obtain the compound of formula I;
式I合成路线：Formula I synthetic route:
R’为或R' is or
或，包括以下步骤：or, comprising the following steps:
①N2保护下，将反应物A-II、反应物B-II、钯催化剂和碱加入到甲苯、乙醇和水的混合溶剂中，升温反应，冷却至室温，加入H2O，待固体析出完毕后过滤，将滤饼烘干，用管柱色谱法纯化剩余物质，滤液用旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体C-II；① UnderN2 protection, reactant A-II, reactant B-II, palladium catalyst and base are added to a mixed solvent of toluene, ethanol and water, the temperature is raised for reaction, cooled to room temperature,H2O is added, and after solid precipitation is completed, it is filtered, the filter cake is dried, and the remaining substance is purified by column chromatography. The filtrate is used to remove the solvent by a rotary evaporator, and the obtained solid is dried to obtain intermediate C-II;
②N2保护下，在反应容器中加入中间体C-II和反应物D-II溶于二甲苯之后，加入钯催化剂、膦配体和碱；添加后使反应温度缓慢升温，并且搅拌混合物；使用硅藻土趁热抽滤，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，用管柱色谱法纯化剩余物质，得到式II所示化合物；② Under N2 protection, add intermediate C-II and reactant D-II to a reaction vessel and dissolve them in xylene, then add palladium catalyst, phosphine ligand and base; after adding, slowly increase the reaction temperature and stir the mixture; use diatomaceous earth to filter while hot, cool the filtrate to room temperature, then add distilled water to the filtrate for washing, retain the organic phase after separation, and extract the aqueous phase with ethyl acetate; then use magnesium sulfate to dry the combined organic layer, and purify the remaining substance by column chromatography to obtain the compound shown in formula II;
式II合成路线：Formula II synthetic route:
R’为或R' is or
进一步，步骤(1)中，上述反应物A-I、反应物B-I、钯催化剂和碱的摩尔比为1.0:(1-1.2):(0.01-0.02):(2.0-2.3)；Further, in step (1), the molar ratio of the reactant A-I, the reactant B-I, the palladium catalyst and the base is 1.0:(1-1.2):(0.01-0.02):(2.0-2.3);
步骤(2)中，上述中间体C-I、反应物D-I、钯催化剂、膦配体和碱的摩尔比为1.0:(1.1-1.3):(0.01-0.05):(0.02-0.15):(2.0-2.4)；In step (2), the molar ratio of the intermediate C-I, the reactant D-I, the palladium catalyst, the phosphine ligand and the base is 1.0:(1.1-1.3):(0.01-0.05):(0.02-0.15):(2.0-2.4);
步骤①中，上述反应物A-II、反应物B-II、钯催化剂和碱的摩尔比为1.0:(1-1.2):(0.01-0.02):(2.0-2.3)；In step ①, the molar ratio of the reactant A-II, the reactant B-II, the palladium catalyst and the base is 1.0:(1-1.2):(0.01-0.02):(2.0-2.3);
步骤②中，上述中间体C-II、反应物D-II、钯催化剂、膦配体和碱的摩尔比为1.0:(1.1-1.3):(0.01-0.05):(0.02-0.15):(2.0-2.4)。In step ②, the molar ratio of the intermediate C-II, reactant D-II, palladium catalyst, phosphine ligand and base is 1.0:(1.1-1.3):(0.01-0.05):(0.02-0.15):(2.0-2.4).
进一步，上述甲苯、乙醇和水的混合溶剂中，甲苯、乙醇和水的体积比为(2-4):1:1。Furthermore, in the above-mentioned mixed solvent of toluene, ethanol and water, the volume ratio of toluene, ethanol and water is (2-4):1:1.
进一步，步骤(1)中，上述升温至80-100℃，反应8-12h；步骤(2)中，上述添加后使反应温度缓慢升温到130-140℃，并且搅拌混合物8-12h；步骤①中，上述升温至80-100℃，反应8-12h；步骤②中，上述添加后使反应温度缓慢升温到130-140℃，并且搅拌混合物8-12h。Further, in step (1), the temperature is raised to 80-100°C and the reaction is carried out for 8-12 hours; in step (2), after the addition, the reaction temperature is slowly raised to 130-140°C, and the mixture is stirred for 8-12 hours; in step ①, the temperature is raised to 80-100°C and the reaction is carried out for 8-12 hours; in step ②, after the addition, the reaction temperature is slowly raised to 130-140°C, and the mixture is stirred for 8-12 hours.
进一步，上述钯催化剂为Pd2(dba)3、Pd(PPh3)4、PdCl2、PdCl2(dppf)、Pd(OAc)2、Pd(PPh3)2Cl2或NiCl2(dppf)中的一种或几种；Further, the palladium catalyst is one or more of Pd2 (dba)3 , Pd(PPh3 )4 , PdCl2 , PdCl2 (dppf), Pd(OAc)2 , Pd(PPh3 )2 Cl2 or NiCl2 (dppf);
上述膦配体为P(t-Bu)3、X-phos、PET3、PMe3、PPh3、KPPh2或P(t-Bu)2Cl中的一种或几种；The phosphine ligand is one or more of P(t-Bu)3 , X-phos, PET3 , PMe3 , PPh3 , KPPh2 or P(t-Bu)2 Cl;
上述碱为K2CO3、K3PO4、Na2CO3、CsF、Cs2CO3或t-BuONa中的一种或几种。The above-mentioned base is one or more of K2 CO3 , K3 PO4 , Na2 CO3 , CsF, Cs2 CO3 or t-BuONa.
本发明还提供一种有机电致发光器件，包括上述发光辅助材料或上述方法制备的发光辅助材料。The present invention also provides an organic electroluminescent device, comprising the above-mentioned auxiliary luminescent material or the auxiliary luminescent material prepared by the above-mentioned method.
进一步，上述有机电致发光器件包括空穴注入层、空穴传输层、电子阻挡层、发光辅助层、发光层、空穴阻挡层、电子传输层、电子注入层或盖帽层中的一层或几层的组合，上述发光辅助层包括上述发光辅助材料或上述方法制备的发光辅助材料。Furthermore, the above-mentioned organic electroluminescent device includes a hole injection layer, a hole transport layer, an electron blocking layer, a luminescence auxiliary layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer or a capping layer, or a combination of several layers, and the above-mentioned luminescence auxiliary layer includes the above-mentioned luminescence auxiliary material or the luminescence auxiliary material prepared by the above-mentioned method.
进一步，上述有机电致发光器件利用真空蒸镀法或利用溶液涂布法来形成有机物层，上述溶液涂布法为旋涂法、浸涂法、刮涂法、喷墨印刷法、丝网印刷法、喷雾法或辊涂法。Furthermore, the organic electroluminescent device forms the organic layer by vacuum evaporation or solution coating, and the solution coating method is spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying or roller coating.
进一步，上述有机电致发光器件包括顶部发光型、底部发光型或双向发光型。Furthermore, the organic electroluminescent device includes a top emission type, a bottom emission type or a bidirectional emission type.
本发明的有益效果：本发明在二苯并呋喃的1,4位分别连接三芳胺和9-苯基-9H-咔唑，其中9-苯基-9H-咔唑上的苯环与二苯并呋喃以邻位的取代方式连接。得到的化合物作为发光辅助层材料，能够使有机电致发光器件在保持效率，驱动电压不受影响的情况下，寿命得到大幅度提升。Beneficial effects of the present invention: The present invention connects triarylamine and 9-phenyl-9H-carbazole at the 1 and 4 positions of dibenzofuran, respectively, wherein the benzene ring on 9-phenyl-9H-carbazole is connected to dibenzofuran in an ortho-substituted manner. The obtained compound is used as a light-emitting auxiliary layer material, which can significantly improve the life of an organic electroluminescent device while maintaining efficiency and not affecting the driving voltage.
二苯并呋喃具有高三线态能级，作为蓝光发光辅助层材料与蓝光发光层之间的HOMO/LUMO能级更加适合。三芳胺具有优异的空穴传输性能，本发明将三芳胺类材料用作发光输辅助层，起到提高迁移率的作用。9-苯基-9H-咔唑上的苯环与二苯并呋喃邻位折叠使空间结构更加扭曲，根据扭曲的两个平面，结晶度可能由于分子间相互作用的减少而降低。因此，化合物的熔点降低，从而使得能够减少沉积中的堵塞，一方面使化合物的沉积温度降低，另一方面，可以减少化合物在过高的沉积温度下的分解。即，在有机电致发光装置的制备过程中，热稳定性得到增加，大幅度延长器件寿命。Dibenzofuran has a high triplet energy level, and is more suitable as the HOMO/LUMO energy level between the blue light emitting auxiliary layer material and the blue light emitting layer. Triarylamine has excellent hole transport performance. The present invention uses triarylamine materials as a light emitting auxiliary layer to improve mobility. The benzene ring on 9-phenyl-9H-carbazole and the ortho-folding of dibenzofuran make the spatial structure more distorted. According to the two distorted planes, the crystallinity may be reduced due to the reduction of intermolecular interactions. Therefore, the melting point of the compound is reduced, so that the blockage in the deposition can be reduced, the deposition temperature of the compound is reduced on the one hand, and the decomposition of the compound at an excessively high deposition temperature can be reduced on the other hand. That is, in the preparation process of the organic electroluminescent device, thermal stability is increased, and the device life is greatly extended.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为中间体C-22的核磁共振氢谱图。Figure 1 is the H NMR spectrum of intermediate C-22.
图2为化合物22的核磁共振氢谱图。FIG2 is a hydrogen nuclear magnetic resonance spectrum of compound 22.
图3为化合物67和对比化合物1-3的三维结构。FIG3 is the three-dimensional structure of compound 67 and comparative compounds 1-3.
具体实施方式DETAILED DESCRIPTION
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
本发明进行的一系列钯催化偶联反应，一方面利用Br的活性大于Cl这一差异，另一方面通过控制反应条件控制反应位点，并且用管柱色谱法或过硅胶漏斗纯化反应，去除副产物，得到目标化合物。参考公知常识如下：The present invention conducts a series of palladium-catalyzed coupling reactions, which utilize the difference that the activity of Br is greater than that of Cl, and control the reaction site by controlling the reaction conditions, and purify the reaction by column chromatography or silica gel funnel to remove by-products to obtain the target compound. Reference to the common knowledge is as follows:
《过渡金属有机化学》(原著第六版)，罗伯特·H·克拉布特里(RobertH.Crabtree)，出版社：上海华东理工大学出版社，出版时间：2017-09-00，ISBN:978-7-5628-5111-0，第388页。"Transition Metal Organic Chemistry" (Original Sixth Edition), Robert H. Crabtree, Publisher: Shanghai East China University of Science and Technology Press, Publication Date: 2017-09-00, ISBN: 978-7-5628-5111-0, page 388.
《有机化学与光电材料实验教程》，陈润锋，出版社:东南大学出版社，出版时间:2019-11-00，ISBN:9787564184230，第174页。"Organic Chemistry and Optoelectronic Materials Experimental Tutorial", Chen Runfeng, Publisher: Southeast University Press, Publication Date: 2019-11-00, ISBN: 9787564184230, Page 174.
实施例1：化合物22的合成Example 1: Synthesis of Compound 22
CAS：反应物B-22：2183475-72-9CAS: Reactant B-22: 2183475-72-9
N2保护下，将反应物A-22(50mmol)、反应物B-22(60mmol)、四(三苯基膦)钯(0.5mmol)和碳酸钾(110mmol)分别加入到甲苯、乙醇、水(150mL:50mL:50mL)的混合溶剂中，升温至90℃，反应10h，冷却至室温，加入H2O，待固体析出完毕后过滤，将滤饼烘干，用管柱色谱法纯化剩余物质，滤液用旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体C-22。(17.54g，产率：76％，理论值：443.93，测试值MS(ESI，m/Z):[M+H]+＝444.14)。UnderN2 protection, reactant A-22 (50 mmol), reactant B-22 (60 mmol), tetrakis(triphenylphosphine)palladium (0.5 mmol) and potassium carbonate (110 mmol) were added to a mixed solvent of toluene, ethanol and water (150 mL:50 mL:50 mL), respectively, and the temperature was raised to 90°C, reacted for 10 h, cooled to room temperature, andH2O was added. After solid precipitation was completed, the mixture was filtered, the filter cake was dried, and the remaining substance was purified by column chromatography. The filtrate was used to remove the solvent by a rotary evaporator, and the obtained solid was dried to obtain intermediate C-22 (17.54 g, yield: 76%, theoretical value: 443.93, test value MS (ESI, m/Z): [M+H]+ = 444.14).
中间体C-22的核磁共振氢谱如图1所示：The nuclear magnetic resonance hydrogen spectrum of intermediate C-22 is shown in Figure 1:
N2保护下，在反应容器中加入中间体C-22(35mmol)和反应物D-22(38.5mmol)溶于二甲苯(200mL)之后，加入Pd(OAc)2(0.7mmol)、X-Phos(1.4mmol)、t-BuONa(77mmol)；添加后使反应温度缓慢升温到135℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，用管柱色谱法纯化剩余物质，得到化合物22。(20.92g，产率：82％，理论值：728.90，测试值MS(ESI，m/Z):[M+H]+＝729.16)。UnderN2 protection, intermediate C-22 (35 mmol) and reactant D-22 (38.5 mmol) were added to the reaction vessel and dissolved in xylene (200 mL), and then Pd(OAc)2 (0.7 mmol), X-Phos (1.4 mmol), and t-BuONa (77 mmol) were added; after the addition, the reaction temperature was slowly raised to 135°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot suction filtration, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then dried with magnesium sulfate, and the remaining substance was purified by column chromatography to obtain compound 22 (20.92 g, yield: 82%, theoretical value: 728.90, test value MS (ESI, m/Z): [M+H]+ = 729.16).
化合物22的核磁共振氢谱如图2所示：The H NMR spectrum of compound 22 is shown in Figure 2:
表征：Characterization:
HPLC纯度：＞99.7％。HPLC purity: >99.7%.
元素分析：Elemental Analysis:
理论值：C,88.98；H,4.98；N,3.84；O,2.19Theoretical value: C, 88.98; H, 4.98; N, 3.84; O, 2.19
测试值：C,88.83；H,5.12；N,3.92；O,2.23Test values: C, 88.83; H, 5.12; N, 3.92; O, 2.23
实施例2：化合物59的合成Example 2: Synthesis of Compound 59
中间体C-22与中间体C-59反应路线一致；The reaction routes of intermediate C-22 and intermediate C-59 are consistent;
N2保护下，在反应容器中加入中间体C-59(35mmol)和反应物D-59(38.5mmol)溶于二甲苯(200mL)之后，加入Pd(OAc)2(0.7mmol)、X-Phos(1.4mmol)、t-BuONa(77mmol)；添加后使反应温度缓慢升温到130℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，用管柱色谱法纯化剩余物质，得到化合物59。(20.82g，产率：75％，理论值：792.94，测试值MS(ESI，m/Z):[M+H]+＝793.12)。UnderN2 protection, intermediate C-59 (35 mmol) and reactant D-59 (38.5 mmol) were added to the reaction vessel and dissolved in xylene (200 mL), and then Pd(OAc)2 (0.7 mmol), X-Phos (1.4 mmol), and t-BuONa (77 mmol) were added; after the addition, the reaction temperature was slowly raised to 130°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot suction filtration, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then dried with magnesium sulfate, and the remaining substance was purified by column chromatography to obtain compound 59 (20.82 g, yield: 75%, theoretical value: 792.94, test value MS (ESI, m/Z): [M+H]+ = 793.12).
表征：Characterization:
HPLC纯度：＞99.8％。HPLC purity: >99.8%.
元素分析：Elemental Analysis:
理论值：C,87.86；H,4.58；N,3.53；O,4.04Theoretical value: C, 87.86; H, 4.58; N, 3.53; O, 4.04
测试值：C,87.55；H,4.77；N,3.65；O,4.11Test values: C, 87.55; H, 4.77; N, 3.65; O, 4.11
实施例3：化合物95的合成Example 3: Synthesis of Compound 95
CAS：反应物B-95：2252237-87-7CAS: Reactant B-95: 2252237-87-7
N2保护下，将反应物A-95(50mmol)、反应物B-95(60mmol)、四(三苯基膦)钯(0.5mmol)和碳酸钾(110mmol)分别加入到甲苯、乙醇、水(150mL:50mL:50mL)的混合溶剂中，升温至95℃，反应10h，冷却至室温，加入H2O，待固体析出完毕后过滤，将滤饼烘干，用管柱色谱法纯化剩余物质，滤液用旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体C-95。(17.32g，产率：78％，理论值：443.93，测试值MS(ESI，m/Z):[M+H]+＝444.23)。UnderN2 protection, reactant A-95 (50 mmol), reactant B-95 (60 mmol), tetrakis(triphenylphosphine)palladium (0.5 mmol) and potassium carbonate (110 mmol) were added to a mixed solvent of toluene, ethanol and water (150 mL:50 mL:50 mL), respectively, heated to 95°C, reacted for 10 h, cooled to room temperature, addedH2O , filtered after solid precipitation, dried the filter cake, purified the remaining substance by column chromatography, removed the solvent from the filtrate by a rotary evaporator, and dried the obtained solid to obtain intermediate C-95 (17.32 g, yield: 78%, theoretical value: 443.93, test value MS (ESI, m/Z): [M+H]+ = 444.23).
N2保护下，在反应容器中加入中间体C-95(35mmol)和反应物D-95(38.5mmol)溶于二甲苯(200mL)之后，加入Pd(OAc)2(0.7mmol)、X-Phos(1.4mmol)、t-BuONa(77mmol)；添加后使反应温度缓慢升温到135℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，用管柱色谱法纯化剩余物质，得到化合物95。(23.45g，产率：86％，理论值：778.96，测试值MS(ESI，m/Z):[M+H]+＝779.21)。UnderN2 protection, intermediate C-95 (35 mmol) and reactant D-95 (38.5 mmol) were added to the reaction vessel and dissolved in xylene (200 mL), and then Pd(OAc)2 (0.7 mmol), X-Phos (1.4 mmol), and t-BuONa (77 mmol) were added; after the addition, the reaction temperature was slowly raised to 135°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot suction filtration, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then dried with magnesium sulfate, and the remaining substance was purified by column chromatography to obtain compound 95 (23.45 g, yield: 86%, theoretical value: 778.96, test value MS (ESI, m/Z): [M+H]+ = 779.21).
表征：Characterization:
HPLC纯度：＞99.8％。HPLC purity: >99.8%.
元素分析：Elemental Analysis:
理论值：C,89.43；H,4.92；N,3.60；O,2.05Theoretical value: C, 89.43; H, 4.92; N, 3.60; O, 2.05
测试值：C,89.21；H,5.09；N,3.64；O,2.13Test values: C, 89.21; H, 5.09; N, 3.64; O, 2.13
实施例4：化合物97的合成Example 4: Synthesis of Compound 97
中间体C-97与中间体C-95反应路线一致；The reaction route of intermediate C-97 is consistent with that of intermediate C-95;
N2保护下，在反应容器中加入中间体C-97(35mmol)和反应物D-97(38.5mmol)溶于二甲苯(200mL)之后，加入Pd(OAc)2(0.7mmol)、X-Phos(1.4mmol)、t-BuONa(77mmol)；添加后使反应温度缓慢升温到135℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，用管柱色谱法纯化剩余物质，得到化合物97。(22.55g，产率：80％，理论值：804.99，测试值MS(ESI，m/Z):[M+H]+＝805.32)。UnderN2 protection, intermediate C-97 (35 mmol) and reactant D-97 (38.5 mmol) were added to the reaction vessel and dissolved in xylene (200 mL), and then Pd(OAc)2 (0.7 mmol), X-Phos (1.4 mmol), and t-BuONa (77 mmol) were added; after the addition, the reaction temperature was slowly raised to 135°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot suction filtration, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then dried with magnesium sulfate, and the remaining substance was purified by column chromatography to obtain compound 97 (22.55 g, yield: 80%, theoretical value: 804.99, test value MS (ESI, m/Z): [M+H]+ = 805.32).
表征：Characterization:
HPLC纯度：＞99.8％。HPLC purity: >99.8%.
元素分析：Elemental Analysis:
理论值：C,89.52；H,5.01；N,3.48；O,1.99Theoretical value: C, 89.52; H, 5.01; N, 3.48; O, 1.99
测试值：C,89.37；H,5.13；N,3.52；O,2.04Test values: C, 89.37; H, 5.13; N, 3.52; O, 2.04
实施例5-53Example 5-53
参照实施例1至4的合成方法完成对如下化合物的合成，其分子式和质谱如下表1所示。The following compounds were synthesized by referring to the synthesis methods of Examples 1 to 4. Their molecular formulas and mass spectra are shown in Table 1 below.
表1分子式和质谱Table 1 Molecular formula and mass spectrum
另外，需要说明，本发明其他化合物参照上述所列举的实施例的合成方法即可获得，所以在此不再一一例举。In addition, it should be noted that other compounds of the present invention can be obtained by referring to the synthesis methods of the above-mentioned embodiments, so they are not listed one by one here.
本发明提供了一种有机电致发光器件，具有包含空穴注入层、空穴传输层、电子阻挡层、发光辅助层、发光层、空穴阻挡层、电子传输层、电子注入层、盖帽层等作为有机物层的结构。但是，有机发光元件的结构并不限于此，可以包含数量更少或更多的有机层。The present invention provides an organic electroluminescent device having a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, etc. as organic layers. However, the structure of the organic light-emitting element is not limited thereto, and may include fewer or more organic layers.
根据本说明书的一个实施方式，本发明制备的式I所示化合物作为发光辅助层材料。According to one embodiment of the present specification, the compound represented by formula I prepared by the present invention is used as a light-emitting auxiliary layer material.
关于上述式I所表示的化合物，在制造有机发光元件时，利用真空蒸镀法，或利用+溶液涂布法来形成有机物层。其中，所谓溶液涂布法是指，旋涂法、浸涂法、刮涂法、喷墨印刷法、丝网印刷法、喷雾法、辊涂法等，但并非仅限于此。When manufacturing an organic light-emitting element, the compound represented by the above formula I is subjected to vacuum evaporation or solution coating to form an organic layer. The solution coating method refers to, but is not limited to, spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roller coating, etc.
本发明的有机发光元件根据所使用的材料，为顶部发光型、底部发光型或双向发光型。The organic light emitting element of the present invention may be a top emission type, a bottom emission type or a bi-directional emission type depending on the materials used.
本发明所述的器件可以用于有机发光器件，包括但不限于平板显示器，计算机监视器，一种医用监护仪，一种电视机，广告牌，一种用于内部或外部照明和/或信号的灯，平视显示器，全透明或部分透明的显示器，柔性显示器，一种激光打印机，一种电话机，一种手机，片剂，一个相簿，个人数字助理(PDA)，一种可穿戴装置，一种笔记本电脑，一种数码相机，摄像机，取景器，微型显示器，三维显示器，虚拟现实或增强现实显示器，车辆，包括平铺在一起的多个显示器的视频墙，剧场或场馆屏幕，光疗装置和标志。The devices described in the present invention can be used in organic light-emitting devices, including but not limited to flat panel displays, computer monitors, a medical monitor, a television, a billboard, a light for interior or exterior lighting and/or signaling, a head-up display, a fully transparent or partially transparent display, a flexible display, a laser printer, a telephone, a mobile phone, a tablet, a photo album, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay, a three-dimensional display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or venue screen, a light therapy device and a sign.
作为阳极物质，通常为了使空穴能够顺利地向有机物层注入，选择功函数大的物质。作为本发明中可使用的阳极物质的具体例，有钒、铬、铜、锌、金等金属或它们的合金；氧化锌、氧化铟、氧化铟锡(ITO)、氧化铟锌(IZO)等金属氧化物；ZnO:A1或SnO2:Sb等金属与氧化物的组合；聚吡咯及聚苯胺等导电性高分子等。As the anode material, a material with a large work function is usually selected in order to smoothly inject holes into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2 :Sb; conductive polymers such as polypyrrole and polyaniline, etc.
空穴注入层采用有利地在低电压下接收来自阳极的空穴的材料，并且空穴注入材料的最高占据分子轨道(HOMO)在阳极材料的功函数与周围有机材料层的HOMO之间。空穴注入材料的具体实例包括金属卟啉、低聚噻吩、基于芳基胺的有机材料、基于六腈六氮杂苯并菲的有机材料、基于喹吖啶酮的有机材料、基于苝的有机材料、蒽醌、以及基于聚苯胺和基于聚噻吩的导电聚合物等，但不限于此，并且还包含能够进行p掺杂的另外的化合物。The hole injection layer is made of a material that is advantageously capable of receiving holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrins, oligothiophenes, organic materials based on arylamines, organic materials based on hexanitrile hexaazatriphenylene, organic materials based on quinacridone, organic materials based on perylene, anthraquinone, and conductive polymers based on polyaniline and polythiophene, etc., but are not limited thereto, and also include other compounds capable of p-doping.
空穴传输材料是能够接收来自阳极或空穴注入层的空穴并将空穴传输至发光层的材料，并且具有高空穴迁移率的材料。空穴传输材料，选自芳基胺系衍生物、导电性高分子、以及同时存在共轭部分和非共轭部分的嵌段共聚物等。The hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and has a high hole mobility. The hole transport material is selected from aromatic amine derivatives, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.
空穴输送层和发光层之间加入发光辅助层(多层空穴输送层)。发光辅助层主要起到辅助空穴传输层的作用，因此有时也称为第二空穴传输层。发光辅助层使得从阳极转移的空穴能够平稳地移动到发光层，并且可以阻挡从阴极转移的电子，以将电子限制在发光层内，减少空穴传输层与发光层之间的势垒，降低有机电致发光器件的驱动电压，进一步增加空穴的利用率，从而改善器件的发光效率和寿命。A luminescent auxiliary layer (multi-layer hole transport layer) is added between the hole transport layer and the light-emitting layer. The luminescent auxiliary layer mainly assists the hole transport layer, so it is sometimes also called the second hole transport layer. The luminescent auxiliary layer enables the holes transferred from the anode to move smoothly to the light-emitting layer, and can block the electrons transferred from the cathode to confine the electrons in the light-emitting layer, reduce the potential barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, and further increase the utilization rate of holes, thereby improving the luminous efficiency and life of the device.
电子阻挡层设置在空穴传输层与发光层之间。作为电子阻挡层，可以使用本领域中已知的材料，例如基于芳基胺的有机材料。The electron blocking layer is disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, materials known in the art, such as arylamine-based organic materials, may be used.
发光层的发光物质，是能够分别接收来自空穴传输层和电子传输层的空穴和电子并使其结合而发出可见光区域的光的物质，选择对于荧光或磷光的量子效率高的物质。The light-emitting material of the light-emitting layer is a material that can receive holes and electrons from the hole transport layer and the electron transport layer, respectively, and combine them to emit light in the visible light region. A material with high quantum efficiency for fluorescence or phosphorescence is selected.
发光层包含主体材料和掺杂剂材料。The light-emitting layer includes a host material and a dopant material.
主体材料和掺杂材料的质量比为90-99.5:0.5-10。The mass ratio of the main material to the doping material is 90-99.5:0.5-10.
主体材料有芳香族稠环衍生物或含杂环化合物等。具体而言，作为芳香族稠环衍生物，有蒽衍生物、芘衍生物、萘衍生物、并五苯衍生物、菲化合物、荧蒽化合物等，作为含杂环化合物，有咔唑衍生物、二苯并呋喃衍生物、嘧啶衍生物。The host material includes aromatic fused ring derivatives or heterocyclic compounds, etc. Specifically, as aromatic fused ring derivatives, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, pyrimidine derivatives.
本发明掺杂剂材料包括荧光掺杂和磷光掺杂。选自芳香族胺衍生物、苯乙烯基胺化合物、硼配合物、荧蒽化合物、金属配合物。The dopant material of the present invention includes fluorescent doping and phosphorescent doping, and is selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
空穴阻挡层可以设置在电子传输层与发光层之间，并且可以使用本领域中已知的材料，例如基于三嗪的化合物。The hole blocking layer may be disposed between the electron transport layer and the light emitting layer, and a material known in the art, such as a triazine-based compound, may be used.
电子传输层可以起到促进电子传输的作用。电子传输材料是有利地接收来自阴极的电子并将电子传输至发光层的材料，选择具有高电子迁移率的材料。电子传输层包括电子缓冲层、空穴阻挡层、电子传输层。The electron transport layer can promote electron transport. The electron transport material is a material that advantageously receives electrons from the cathode and transports the electrons to the light-emitting layer. A material with high electron mobility is selected. The electron transport layer includes an electron buffer layer, a hole blocking layer, and an electron transport layer.
电子注入层可以起到促进电子注入的作用。具有传输电子的能力，防止发光层中产生的激子迁移至空穴注入层。电子注入层的材料包括噁唑、噁二唑、三唑、咪唑、苝四羧酸、亚芴基甲烷、蒽酮以及它们的衍生物、镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、镱等金属或它们的合金，金属配合物或含氮5元环衍生物等，但并不限于此。The electron injection layer can promote electron injection. It has the ability to transfer electrons and prevent the excitons generated in the light-emitting layer from migrating to the hole injection layer. The materials of the electron injection layer include oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenyl methane, anthrone and their derivatives, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium and other metals or their alloys, metal complexes or nitrogen-containing 5-membered ring derivatives, etc., but are not limited thereto.
阴极选择具有小功函数的材料使得电子顺利注入有机材料层，该层的层厚度为0.5-5nm。阴极物质，通常为了使电子容易地向有机物层注入，选择为功函数小的物质。作为阴极物质的具体例，有镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡及铅等金属或它们的合金：LiF/A1或LiO2/A1，Mg/Ag等多层结构物质等。The cathode material is selected to have a small work function so that electrons can be smoothly injected into the organic material layer, and the layer thickness of the layer is 0.5-5nm. The cathode material is usually selected to have a small work function in order to facilitate the injection of electrons into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or their alloys: LiF/Al or LiO2/Al, Mg/Ag and other multilayer structure materials.
除本文所公开的发光辅助层中包含式I，OLED器件中对于其他层材料使用现有的空穴注入材料、空穴输送材料、空穴传输辅助材料，掺杂剂材料、空穴阻挡层材料、电子传输层材料和电子注入材料。In addition to the light-emitting auxiliary layer disclosed herein comprising Formula I, the OLED device uses existing hole injection materials, hole transport materials, hole transport auxiliary materials, dopant materials, hole blocking layer materials, electron transport layer materials and electron injection materials for other layer materials.
以下结合具体实施例对本发明提供的一种有机电致发光组合物和有机电致发光器件进行具体说明。The organic electroluminescent composition and the organic electroluminescent device provided by the present invention are described in detail below with reference to specific embodiments.
[应用例1]有机电致发光器件制备：[Application Example 1] Preparation of organic electroluminescent devices:
a、ITO阳极：将涂层厚度为150nm的ITO(氧化铟锡)-Ag-ITO(氧化铟锡)玻璃基板在蒸馏水中清洗2次，超声波洗涤30min，再用蒸馏水反复清洗2次，超声波洗涤10min，洗涤结束后，用真空烘箱220℃烘烤2小时，烘烤结束后降温即可使用。以该基板为阳极，使用蒸镀机进行蒸镀器件工艺，在其上依次蒸镀其它功能层。a. ITO anode: Wash the ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150nm in distilled water twice, ultrasonically wash for 30 minutes, and then repeatedly wash it with distilled water twice, ultrasonically wash for 10 minutes. After washing, bake it in a vacuum oven at 220℃ for 2 hours. After baking, cool it down and it can be used. Use this substrate as the anode, use an evaporation machine to carry out the evaporation device process, and evaporate other functional layers on it in sequence.
b、HIL(空穴注入层)：以的蒸镀速率，真空蒸镀空穴注入层材料HT和P-dopant，其化学式如下所示。所述HT和P-dopant的蒸镀速率比为97：3，厚度为10nm；b. HIL (hole injection layer): The hole injection layer materials HT and P-dopant are vacuum evaporated at a deposition rate of 97:3, and the thickness is 10 nm;
c、HTL(空穴传输层)：以的蒸镀速率，在空穴注入层上面真空蒸镀120nm的HT作为空穴传输层；c. HTL (hole transport layer): At a deposition rate of 100%, 120 nm of HT was vacuum-deposited on the hole injection layer as a hole transport layer.
d、Prime(发光辅助层)：以的蒸镀速率，在空穴传输层上面真空蒸镀10nm的本发明化合物1作为发光辅助层；d. Prime (luminous auxiliary layer): The evaporation rate is 10 nm, and the compound 1 of the present invention is vacuum evaporated on the hole transport layer as a light-emitting auxiliary layer;
e、EML(发光层)：然后在上述发光辅助层上，以的蒸镀速率，真空蒸镀厚度为25nm的主体材料(Host)和掺杂材料(Dopant)作为发光层，其Host和Dopant的化学式如下所示。其中Host和Dopant的蒸镀速率比为97：3。e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, The host material (Host) and dopant material (Dopant) with a thickness of 25nm are vacuum-deposited as the light-emitting layer. The chemical formulas of Host and Dopant are shown below. The evaporation rate ratio of Host to Dopant is 97:3.
f、HB(空穴阻挡层)：以的蒸镀速率，真空蒸镀厚度为5.0nm的空穴阻挡层。f. HB (hole blocking layer): The hole blocking layer with a thickness of 5.0 nm was vacuum deposited at a deposition rate of .
g、ETL(电子传输层)：以的蒸镀速率，真空蒸镀厚度为35nm的ET和Liq作为电子传输层。其中ET和Liq的蒸镀速率比为50：50。g. ETL (Electron Transport Layer): ET and Liq were vacuum-deposited at a deposition rate of 35 nm as an electron transport layer, where the deposition rate ratio of ET to Liq was 50:50.
h、EIL(电子注入层)：以的蒸镀速率，蒸镀Yb膜层1.0nm，形成电子注入层。h. EIL (electron injection layer): At a evaporation rate of , a 1.0 nm Yb film layer was evaporated to form an electron injection layer.
i、阴极：以的蒸镀速率比，蒸镀镁和银18nm，其蒸镀速率比为1:9，得到OLED器件。i. Cathode: The evaporation rate ratio is 1:9, and magnesium and silver are evaporated at 18nm, and the evaporation rate ratio is 1:9 to obtain an OLED device.
j、光取出层：以的蒸镀速率，在阴极上真空蒸镀厚度为70nm的CPL，作为光取出层。j. Light extraction layer: At a evaporation rate of , CPL with a thickness of 70nm was vacuum-deposited on the cathode as a light extraction layer.
k、将蒸镀完成的基板进行封装。首先采用涂胶设备将清洗后盖板用UV胶进行涂覆工艺，然后将涂覆完成的盖板移至压合工段，将蒸镀完成的基板置于盖板上端，最后将基板和盖板在贴合设备作用下进行贴合，同时完成对UV胶光照固化。k. Package the substrate after evaporation. First, use the glue coating equipment to coat the cleaned cover with UV glue, then move the coated cover to the pressing section, place the evaporation-deposited substrate on the upper end of the cover, and finally bond the substrate and cover with the bonding equipment, and complete the light curing of the UV glue.
器件结构：Device structure:
ITO/Ag/ITO/HT:P-dopant(10nm,3％)/HT(120nm)/prime(式I)(10nm)/Host:DopantITO/Ag/ITO/HT:P-dopant(10nm,3%)/HT(120nm)/prime(Formula I)(10nm)/Host:Dopant
(25nm,3％)/HB(5nm)/ET:Liq(35nm,50％)/Yb(1nm)/Mg:Ag(18nm,1:9)/CPL(70nm)。(25nm, 3%)/HB (5nm)/ET:Liq (35nm, 50%)/Yb (1nm)/Mg:Ag (18nm, 1:9)/CPL (70nm).
应用例2-53Application Example 2-53
按照上述有机电致发光器件的制备方法制备应用例2-53的有机电致发光器件，区别在于将应用例1中的化合物1分别替换为对应的化合物，形成发光辅助层。The organic electroluminescent devices of Application Examples 2-53 were prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a corresponding compound to form a light-emitting auxiliary layer.
对比例1Comparative Example 1
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物1，其中对比化合物1的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 1, wherein the structural formula of the comparative compound 1 is as follows:
对比例2Comparative Example 2
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物2，其中对比化合物2的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 2, wherein the structural formula of the comparative compound 2 is as follows:
对比例3Comparative Example 3
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物3，其中对比化合物3的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 3, wherein the structural formula of the comparative compound 3 is as follows:
对比例4Comparative Example 4
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物4，其中对比化合物4的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 4, wherein the structural formula of the comparative compound 4 is as follows:
对比例5Comparative Example 5
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物5，其中对比化合物5的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 5, wherein the structural formula of the comparative compound 5 is as follows:
对比例6Comparative Example 6
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物6，其中对比化合物6的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 6, wherein the structural formula of the comparative compound 6 is as follows:
对比例7Comparative Example 7
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物7，其中对比化合物7的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 7, wherein the structural formula of the comparative compound 7 is as follows:
对比例8Comparative Example 8
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物8，其中对比化合物8的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 8, wherein the structural formula of the comparative compound 8 is as follows:
对比例9Comparative Example 9
按照上述有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物1替换为对比化合物9，其中对比化合物9的结构式如下：An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 9, wherein the structural formula of the comparative compound 9 is as follows:
在1000(nits)亮度下对上述器件实施例1-53以及器件对比例1-9得到的有机电致发光器件的驱动电压、发光效率、BI值以及寿命进行表征，测试结果如下表2：The driving voltage, luminous efficiency, BI value and life of the organic electroluminescent devices obtained from the above device embodiments 1-53 and device comparative examples 1-9 were characterized at a brightness of 1000 (nits). The test results are shown in Table 2 below:
表2发光特性测试结果(亮度值为1000nits)Table 2 Luminous characteristics test results (brightness value is 1000nits)
本领域技术人员可知，发光辅助层的能级与发光层、空穴传输层匹配，针对不同的发光层，所需要调整的目标值不同。对于不同颜色的发光层，差别较大。即便同样蓝光，针对不同的主体、掺杂剂材料，亦有显著差别。Those skilled in the art will know that the energy level of the light-emitting auxiliary layer matches the light-emitting layer and the hole transport layer. Different target values need to be adjusted for different light-emitting layers. There are large differences for light-emitting layers of different colors. Even for the same blue light, there are significant differences for different host and dopant materials.
蓝光有机电致发光器件受微腔效应的影响，发光效率受色度影响较大，因此引入BI值作为蓝光发光材料效率的依据，BI＝发光效率/CIEy。且在本领域中，蓝光器件寿命短的问题一直是本领域技术人员急需解决的问题之一。Blue light organic electroluminescent devices are affected by the microcavity effect, and the luminous efficiency is greatly affected by the chromaticity. Therefore, the BI value is introduced as the basis for the efficiency of blue light emitting materials, BI = luminous efficiency / CIEy. In this field, the short life of blue light devices has always been one of the problems that technicians in this field need to solve urgently.
从表2可以看出，使用本发明实施例提供的蓝光发光辅助材料制备的有机电致发光器件应用例1～53与对比例1～9提供的现有的有机电致发光器件相比较而言，本发明实施例的发光辅助材料寿命普遍在200-250h，对比化合物在150h，展现出了超长的器件寿命的同时改善驱动电压和效率的技术效果。It can be seen from Table 2 that, compared with the existing organic electroluminescent devices provided by comparative examples 1 to 9, the organic electroluminescent device application examples 1 to 53 prepared using the blue light luminescent auxiliary materials provided by the embodiments of the present invention have a lifespan of 200-250 hours, while the comparative compound has a lifespan of 150 hours, demonstrating the technical effect of improving driving voltage and efficiency while providing an ultra-long device lifespan.
其中，本发明实施例提供的化合物67与对比化合物1-3相比，本发明采用的9-苯基-9H-咔唑上的苯基与二苯并呋喃以邻位的取代方式连接。邻位折叠构成的化合物的空间结构扭曲，而对比化合物1(苯环上的对位)，对比化合物2(苯环上的间位)构成的化合物空间扭曲程度低，根据扭曲的两个平面，结晶度可能由于分子间相互作用的减少而降低。因此，化合物的熔点降低，从而使得能够减少沉积中的堵塞，一方面使化合物的沉积温度降低，另一方面，可以减少化合物在过高的沉积温度下的分解。即，在有机电致发光装置的制备过程中，热稳定性得到增加。图3示出了本发明的有机电致发光化合物67和对比化合物1-3的三维结构。化合物67的空间结构呈现高度折叠状态，扭曲程度大。化合物67器件寿命达到201h，对比化合物1-3在150h左右，寿命增加30％，同时驱动电压得到改善。Among them, the compound 67 provided by the embodiment of the present invention is compared with the comparative compound 1-3, and the phenyl group on the 9-phenyl-9H-carbazole used in the present invention is connected to the dibenzofuran in an ortho-substituted manner. The spatial structure of the compound formed by ortho-folding is distorted, while the spatial distortion degree of the compound formed by the comparative compound 1 (para position on the benzene ring) and the comparative compound 2 (meta position on the benzene ring) is low. According to the two distorted planes, the crystallinity may be reduced due to the reduction of intermolecular interactions. Therefore, the melting point of the compound is reduced, so that the blockage in the deposition can be reduced, on the one hand, the deposition temperature of the compound is reduced, and on the other hand, the decomposition of the compound at an excessively high deposition temperature can be reduced. That is, in the preparation process of the organic electroluminescent device, the thermal stability is increased. Figure 3 shows the three-dimensional structure of the organic electroluminescent compound 67 of the present invention and the comparative compound 1-3. The spatial structure of compound 67 is highly folded and has a large degree of distortion. The device life of compound 67 reaches 201h, while that of comparative compound 1-3 is about 150h, and the life is increased by 30%, while the driving voltage is improved.
在本发明化合物1与对比化合物5，对比化合物6之间，邻位折叠导致的化合物的空间结构更加扭曲，大幅度延长器件寿命。化合物1寿命为247h，相比于对比化合物5，对比化合物6，寿命延长约100h，提升约68％。The spatial structure of the compound caused by ortho-folding is more distorted between the present compound 1 and the comparative compound 5 and the comparative compound 6, which greatly prolongs the device life. The life of compound 1 is 247 hours, which is about 100 hours longer than that of comparative compound 5 and comparative compound 6, an increase of about 68%.
对器件数据的结果分析，本发明化合物中，二苯并呋喃上1位连接9-苯基-9H-咔唑上的苯基，得到的寿命效果更加显著，普遍在230-250h；二苯并呋喃上4位连接9-苯基-9H-咔唑上的苯基，寿命在200上下，得到提高的同时，驱动电压降低约0.1V。The results of device data analysis show that in the compounds of the present invention, the lifespan effect is more significant when the 1-position on dibenzofuran is connected to the phenyl group on 9-phenyl-9H-carbazole, which is generally 230-250h; the lifespan is around 200 when the 4-position on dibenzofuran is connected to the phenyl group on 9-phenyl-9H-carbazole, which is improved while the driving voltage is reduced by about 0.1V.
可见，本发明范围内，尽管存在相似物质，但是9-苯基-9H-咔唑上的苯基取代的位置，直接影响化合物空间扭曲程度，影响在其有机电致发光中的器件性能。本发明式I的化合物在二苯并呋喃的1,4位分别连接三芳胺和9-苯基-9H-咔唑，其中9-苯基-9H-咔唑上的苯环与二苯并呋喃以邻位的取代方式连接。得到的化合物作为发光辅助层材料，能够使有机电致发光器件在保持效率，驱动电压不受影响的情况下，寿命得到大幅度提升。It can be seen that within the scope of the present invention, although similar substances exist, the position of the phenyl substitution on 9-phenyl-9H-carbazole directly affects the degree of spatial distortion of the compound and affects the device performance in its organic electroluminescence. The compound of formula I of the present invention is connected to triarylamine and 9-phenyl-9H-carbazole at the 1 and 4 positions of dibenzofuran, respectively, wherein the benzene ring on 9-phenyl-9H-carbazole is connected to dibenzofuran in an ortho-substituted manner. The obtained compound is used as a luminescent auxiliary layer material, which can greatly improve the life of the organic electroluminescent device while maintaining efficiency and the driving voltage is not affected.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the protection scope of the invention.
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| KR102436480B1 (en)* | 2019-09-25 | 2022-08-25 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
| CN113121515B (en)* | 2019-12-30 | 2023-11-28 | 江苏三月科技股份有限公司 | Compound with dibenzo five-membered heterocycle as core and application thereof |
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| CN116063293A (en) | 2023-05-05 |
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