CN108752320B - 一种基于四苯基碳的oled主体材料及其在制备oled器件中的应用 - Google Patents
一种基于四苯基碳的oled主体材料及其在制备oled器件中的应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 10
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- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
本发明提供了一种基于四苯基碳的OLED主体材料及其在OLED器件中的应用，所述主体材料的化合物结构式为
其中，R1、R2、R3和R4四个取代基中，有n个为相同的给电子基团，4‑n个为相同的吸电子基团，0≤n≤4；本发明提供的基于四苯基碳的OLED主体材料可用于溶液法制备OLED器件。本发明提供的基于四苯基碳的OLED主体材料具有可控的HOMO和LUMO能级，可实现载流子从电极或载流子传输层低能垒或无能垒注入发光层；具有大于3.0eV的单线态及三线态能级，可实现有效的防止激子从发光材料反传到主体材料而使器件性能降低，可提高OLED器件效率；具有可调控的空穴和电子传输速率，可实现发光层中电子和空穴传输的平衡，扩展激子复合区域和发光区域以减小OLED器件效率的滚降。
Description
技术领域
本发明属于光电材料技术领域，具体涉及一种基于四苯基碳的OLED主体材料及其在制备OLED器件中的应用。
背景技术
有机发光二极管(OLED)由于具有成本低廉、材料多样且易于大面积制备等特点，是发展平板显示、固态照明等多个领域的核心部件，因而得到了学术界和商业界的广泛关注。为满足实际应用的要求，追求“高效率、低成本”的OLED材料及器件制备技术一直是科研工作者研究的焦点。众所周知，对于有机电致发光材料，无论是最初发现的有机荧光材料，还是应用最广泛的有机磷光材料或者是近年发展起来的热活化延迟荧光(TADF)材料，都存在发光聚集淬灭的现象。为了克服这一现象，将各类型有机电致发光材料掺杂到主体材料中形成主客体混合的发光层是目前制备OLED的常规做法。因此，开发OLED主体材料具有和发展有机电致发光材料相同的重要性，并得到越来越多的科研工作者的关注。
主体材料对OLED器件中电荷的注入/传输、激子的形成/复合、及能量传递等过程都具有重要的影响。因此，通常要求主体材料必须同时具备三个条件：(1)具有恰当的HOMO和LUMO能级，以方便载流子从相应的电极或载流子传输层注入到发光层中；(2)具有比有机电致发光材料更高的单线态能级间隙及三线态能级，以防止有机电致发光材料上形成的激子反传而降低器件效率；(3)要有匹配的空穴和电子传输能力，以扩大发光层中载流子复合的区域并降低器件的效率滚降。然而，从目前发展的OLED主体材料来看，要同时具备上述三个条件是比较困难的，特别是对于蓝光OLED主体材料而言，要求其具有更高的单线态及三线态能级。
发明内容
针对现有技术存在的上述不足，本发明的目的是提供一种基于四苯基碳的OLED主体材料，解决现有OLED主体材料不能同时具备较宽的能带间隙、可调控的HOMO和LUMO能级以及匹配的空穴和电子传输能力的问题。
本发明还提供了该基于四苯基碳的OLED主体材料在溶液法制备OLED器件中的应用。
本发明还提供了一种包括该基于四苯基碳的OLED主体材料的OLED器件。
为实现上述目的，本发明采用如下技术方案：
一种基于四苯基碳的OLED主体材料，所述主体材料的化合物结构式为：
其中，R1、R2、R3和R4四个取代基中，有n个为相同的给电子基团，4-n个为相同的吸电子基团，0≤n≤4。
由于四苯基碳具有较宽的能带间隙，本发明将其作为设计主体材料的核心部分可以有效提高主体材料的能带间隙。同时，在四苯基碳的四个苯基上可以接入不同的给电子和吸电子基团，从而调控主体材料的HOMO和LUMO能级及调控其对电子和空穴的传输能力。因此，本发明提供的基于四苯基碳的主体材料具有非常强的可调节性，有利于开发“高效率、低成本”的主体材料。
作为优选，所述给电子基团包括给电子体芳基，且给电子体芳基中为咔唑基、三苯胺基、二苯胺基、吖啶基、吩恶嗪基或吩噻嗪基。
作为优选，所述给电子基团为
相较于其他给电子基团，这几类给电子基团具有更加适中的最高占据轨道(5.1–5.5eV)，其与常用的空穴注入材料PEDOT:PSS的能级差更小，利用其设计的主体材料更有利于空穴注入到发光层中。
作为优选，所述吸电子基团包括吸电子体芳基，且吸电子体芳基中为恶二唑基、三嗪基、二苯基砜基、-P＝O基、苯并咪唑基、嘧啶基、吲哚基、氰基或卤素。
作为优选，所述所述吸电子基团为
此类吸电子基团，具有较为合适的最低空轨道能级(2.0–2.4eV)，这与常用的阴极Ca/Al的能级匹配更好，更有利于电子的注入。
本发明提供的
由带有烷基的给电子基团和四苯基碳构成，此类材料主要适用于利用溶液法制备OLED发光层，其中包含四个给电子基团，可以实现高效的空穴传输能力；
由四个三苯基磷氧吸电子基团和四苯基碳构成，此材料继承了三苯基磷氧和四苯基碳具有较高三线态能级的优点，其更有利于应用到有机磷光OLED器件的发光层中，可以有效的阻碍三线态激子的反传，从而提高在高亮度下器件的效率；
同时具有给电子和吸电子基团，其具有较为平衡的空穴和电子传输能力，可以有效的提高发光层中载流子传输的平衡并拓宽发光区域，提高OLED器件的发光效率。
本发明提供的基于四苯基碳的OLED主体材料可用于溶液法制备OLED器件。
相比现有技术，本发明具有如下有益效果：
本发明提供的基于四苯基碳的OLED主体材料具有可控的HOMO和LUMO能级，可实现载流子从电极或载流子传输层低能垒或无能垒注入发光层；具有大于3.0eV的单线态及三线态能级，可实现有效的防止激子从发光材料反传到主体材料而使器件性能降低，从而有效提高OLED器件效率；具有可调控的空穴和电子传输速率，可实现发光层中电子和空穴传输的平衡，扩展激子复合区域和发光区域以减小OLED器件效率的滚降。同时，本发明提高的主体材料具备较高的分子量，可实现溶液法加工的要求。本发明基于四苯基碳的OLED主体材料可用于制备红光、绿光和蓝光的各类发光材料的主体材料，并实现“高效率、低成本”OLED器件的制备。
附图说明
图1为本发明实施例4制备的OLED器件的结构示意图。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明。
实施例1
结构式为
的第一目标化合物的合成：
将正丁基锂正己烷溶液(6.6mL，10.5mmol)滴加到含有1,4-二溴苯(2.36g,10mmol)THF(20mL)溶液中，在-78℃和惰性气体氩气保护下反应1h。然后，将四氯化碳(1.05mL，5mmol)加入到反应溶液中并保持以上条件反应2h，之后缓慢加热到室温27℃并搅拌反应12h。最后，加入30mL水中断反应并利用氯仿进行萃取。得到的有机层通过柱层析提纯得到中间产物TBrBen(2.15g,产率68.5％)。通过质谱仪对中间产物鉴定分析，其结果为：质谱(EI)：m/z C25H16Br4理论值：635.79；实测值：635(M)+。
将Cz(2.5g,8.9mmol)、中间产物TBrBen(1.4g,2.2mmol)、CuI(0.19g,1.0mmol)和K3PO4(1.69g,8mmol)加入到100mL甲苯中，在氩气保护和回流的条件下反应48小时。除去溶剂后残余物用二氯甲烷(3×100mL)萃取三次，合并有机相并用无水硫酸镁干燥，浓缩得到的剩余物以二氯甲烷:正己烷(7:3)作为洗脱剂采用柱层析方法提纯得到产物TCzC(2.31g,产率59.3％)。通过质谱仪对中间产物鉴定分析，其结果为：质谱(MALDI-TOF)：m/zC105H112N4理论值：1429.89；实测值：1429(M)+。
本实施例中，第一目标化合物的合成路线为：
实施例2
结构式为
的第二目标化合物的合成：
本实施例中，中间产物TbrBen的合成方法与实施例1相同(具体合成过程省略)。
将Cz(2.5g,8.9mmol)、中间产物TBrBen(2.8g,4.5mmol)、CuI(0.19g,1.0mmol)和K3PO4(1.69g,8.0mmol)加入到100mL甲苯中，在氩气保护和回流的条件下反应24小时。除去溶剂后残余物用二氯甲烷(3×100mL)萃取三次，合并有机相并用无水硫酸镁干燥，浓缩得到的剩余物以二氯甲烷:正己烷(7:3)作为洗脱剂采用柱层析方法提纯得到产物DCzCBr(2.7g,产率50.3％)。通过质谱仪对中间产物鉴定分析，其结果为：质谱(MALDI-TOF)：m/zC65H64Br2N2理论值：1032.34；实测值：1032(M)+。
将DCzCBr(2.0g,1.9mmol)、正丁基锂(6.6mL，10.5mmol，1.6M正己烷溶液)加入到30mL的-78℃的THF溶液中，搅拌反应3h。然后在氩气保护条件下加入CDP(0.8g,3.8mmol)，将反应溶液缓慢升温到室温27℃反应1h，之后利用甲醇(10mL)终止反应并利用二氯甲烷对反应溶液进行萃取。有机相用无水硫酸镁干燥，浓缩得到的剩余物以二氯甲烷:正己烷(7:3)作为洗脱剂采用柱层析方法提纯得到固体产物DCzCTp。将DCzCTp(1.5g)、二氯甲烷(20mL)和双氧水(5mL)混合并搅拌12h，之后将有机层利用二氯甲烷:正己烷(7:3)作为洗脱剂采用柱层析方法提纯得到产物DCzCTpo，通过质谱仪对中间产物鉴定分析，其结果为：质谱质谱(MALDI-TOF)：m/z C89H84N2O2P2理论值：1274.60；实测值：1274(M)+。
本实施例中，第二目标化合物的合成路线为：
关于实施例1和实施例2中采用TBrBen分别合成TCzC和DCzCBr的反应，由于TbrBen的四个Br都有可能被取代，因而会生成不同的取代产物，最后需要采用柱层析法将各种取代产物分离并表征，之后根据需要选择不同的取代产物即可。其中可通过控制反应时间以调控个取代产物的产率，比如DCzCBr反应时间比TCzC的短，在较短的反应时间内产物中大部分是DCzCBr，TCzC只有很少一部分。
实施例3
将蓝光有机电致发光材料FIrpic掺杂到第二目标化合物DCzCTpo的二氯甲苯溶液中(DczCTpo的质量分数为8％)，配置成总质量浓度(溶质包括FIrpic和DCzCTpo)为15mg/mL的溶液。如图1所示，取20μL溶液滴加到氧化铟锡玻璃基底上，在台式匀胶机(KW-4A型)制备有机发光层薄膜，转速为1000r/min，旋涂时间为30s。得到的有机薄膜经测量厚度约为50nm。
实施例4
本实施例提供的一种OLED器件Q如图1所示，其包括依次相连的氧化铟锡玻璃(ITO)Q1、空穴注入层Q2、发光层Q3、电子注入层Q4以及金属阴极Q5。其中，发光层Q3的制备方法与实施例3制备有机薄膜的方法相同。
本实施例中OLED器件Q的制备方法为：
ITO玻璃Q1的表面依次利用去离子水、丙酮和无水乙醇进行超声清洗，并利用紫外光臭氧处理使其表面亲水。接着，利用匀胶机以3000r/s的转速悬涂聚3,4-乙撑二氧噻吩，悬涂时间为30秒，之后在120℃干燥箱中退火处理10分钟，形成空穴注入层Q2。
将蓝光有机电致发光材料FIrpic掺杂到第二目标化合物DCzCTpo的二氯甲苯溶液中(质量分数8％)，配置成总质量浓度(包括FIrpic和DCzCTpo)为15mg/mL的溶液。按实施例3中的旋涂方法在空穴传输层Q2的远离Q1的表面上制备发光层，之后，在充满氮气的手套箱中100℃条件下退火处理10分钟形成发光层Q3。
真空条件下，利用化学气相蒸镀法在发光层Q3的远离空穴注入层Q2的表面蒸镀2,7-双(二苯基氧膦基)-9,9’-螺双[芴]形成电子注入层Q4。
真空条件下，利用化学气相蒸镀法在电子注入层Q4的远离发光层Q3的表面先后蒸镀钙金属层Q5和铝金属层Q6，形成金属阴极Qa。
本实施例制备的OLED器件，经测试表现出优异的发光性能：电流效率达到52.7cd/A，功能效率达到41.0lm/W，外量子效率突破20％，达到20.5％。其比当前基于FIrpic磷光材料的常规器件性能更好，可见本发明基于四苯基碳的OLED主体材料更适合应用于OLED器件的制备。
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。
Claims (2)
1.一种基于四苯基碳的OLED主体材料，其特征在于，所述主体材料的化合物为DCzCTpo，其结构式为：
所述基于四苯基碳的OLED主体材料的制备方法为：
1)将正丁基锂正己烷溶液6.6mL，10.5mmol滴加到含有1,4-二溴苯2.36g,10mmol THF20mL溶液中，在-78℃和惰性气体氩气保护下反应1h；然后，将四氯化碳1.05mL，5mmol加入到反应溶液中并保持以上条件反应2h，之后缓慢加热到室温27℃并搅拌反应12h；最后，加入30mL水中断反应并利用氯仿进行萃取，得到的有机层通过柱层析提纯得到中间产物TBrBen；
2)将Cz 2.5g,8.9mmol、中间产物TBrBen 2.8g,4.5mmol、CuI 0.19g,1.0mmol和K3PO41.69g,8.0mmol加入到100mL甲苯中，在氩气保护和回流的条件下反应24小时，除去溶剂后残余物用二氯甲烷萃取三次，合并有机相并用无水硫酸镁干燥，浓缩得到的剩余物以二氯甲烷：正己烷7:3作为洗脱剂采用柱层析方法提纯得到产物DCzCBr；
3)将DCzCBr 2.0g,1.9mmol、正丁基锂6.6mL，10.5mmol，1.6M正己烷溶液加入到30mL的-78℃的THF溶液中，搅拌反应3h；然后在氩气保护条件下加入CDP 0.8g,3.8mmol，将反应溶液缓慢升温到室温27℃反应1h，之后利用甲醇10mL终止反应并利用二氯甲烷对反应溶液进行萃取；有机相用无水硫酸镁干燥，浓缩得到的剩余物以二氯甲烷:正己烷7：3作为洗脱剂采用柱层析方法提纯得到固体产物DCzCTpo 。
2.权利要求1所述的基于四苯基碳的OLED主体材料在溶液法制备OLED器件中的应用。
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