CN109273614A - 一种有机电致发光器件和显示装置 - Google Patents
一种有机电致发光器件和显示装置 Download PDFInfo
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- CN109273614A CN109273614A CN201811019655.8A CN201811019655A CN109273614A CN 109273614 A CN109273614 A CN 109273614A CN 201811019655 A CN201811019655 A CN 201811019655A CN 109273614 A CN109273614 A CN 109273614A
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 58
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- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 2
- -1 anilino- Chemical class 0.000 claims description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
本发明提供一种有机电致发光器件和显示装置,其中有机电致发光器件,包括发光层、空穴阻挡层和电子阻挡层,其中:发光层的材料包括主体材料;构成空穴阻挡层和电子阻挡层的材料均与主体材料相同。本发明提供的有机电致发光器件,使用同一款材料作为发光层的主体材料、空穴阻挡层和电子阻挡层,可以有效的降低器件中发光层主体与相邻的空穴阻挡层和电子阻挡层之间的能级势垒,降低器件开启电压,提高发光效率,同时还提高了器件的使用寿命。
Description
技术领域
本发明属于显示技术领域,具体涉及一种有机电致发光器件和显示装置。
背景技术
有机电致发光器件是在电子传输层和空穴传输层之间设有发光层,并进一步在其外侧设置阴极和阳极,通过外加电压向器件中注入电子和空穴并在发光层复合形成激子,通过荧光或磷光过程向外发射光子并失活的器件。由于其具有全固态、自发光、广视角、响应速度快、低驱动电压、低能耗等诸多特点,因此在显示和照明领域有着巨大的应用前景。
近年来,新一代的热活化延迟荧光(Thermally Activated DelayedFluorescence,TADF)材料被广泛应用于有机电致发光器件的发光材料中,TADF材料可以同时利用生成概率25%的单重态激子和75%的三重态激子从而获得高的发光效率。图1是TADF分子电致发光过程原理示意图,如图1所示,TADF由于其单线态(S1)与三线态(T1)的能级差(ΔEST)较小,三线态激子可以通过反向系间窜越(reverse intersystem crossing,RISC)回到单线态,形成单线态激子继而辐射发光,从而提高了激子的辐射发光效率。
但是在有机电致发光器件的发光层中使用TADF材料,往往存在器件发光效率低、寿命较低的情况。
发明内容
针对现有技术中的上述缺陷,本发明提供一种有机电致发光器件,能够提高有机电致发光器件的发光效率,并延长有机电致发光器件的寿命。
本发明还提供一种显示装置,由于包括有上述有机电致发光器件,因此也具有良好的性能。
为实现上述目的,本发明提供的有机电致发光器件,包括发光层、空穴阻挡层和电子阻挡层,其中:发光层的材料包括主体材料;构成空穴阻挡层和电子阻挡层的材料均与主体材料相同。
本发明采用发光层的主体材料作为与发光层分别相邻的空穴阻挡层和电子阻挡层,可以有效的拦截激子扩散到空穴阻挡层和电子阻挡层,从而提升有机电致发光器件的发光效率以及寿命。
同时,使用同一款材料作为发光层的主体材料、空穴阻挡层材料和电子阻挡层材料,还可以有效的降低有机电致发光器件中发光层与相邻的空穴阻挡层和电子阻挡层之间的能级势垒,降低有机电致发光器件的开启电压,提高发光效率。
并且,由于发光层的主体材料一般具有较好的双极传输性能,因此使用该主体材料作为空穴阻挡层和电子阻挡层,能够避免因材料迁移率较差而导致器件复合区域过窄,避免影响器件寿命。
本发明还提供一种显示装置,包括上述有机电致发光器件。该显示装置与上述有机电致发光器件相对于现有技术所具有的优势相同,在此不再赘述。
本发明提供的有机电致发光器件,发光层的主体材料与空穴阻挡层、电子阻挡层的材料使用相同的材料,能够有效的降低发光层与相邻的空穴阻挡层和电子阻挡层之间的能级势垒,降低器件开启电压,提高发光效率;同时,由于发光层主体材料三线态能级较高,使用其作为空穴阻挡层和电子阻挡层,还可以有效的拦截激子扩散,进一步提高器件的发光效率和使用寿命。
并且,由于发光层的主体材料与空穴阻挡层和电子阻挡层的材料使用相同的材料,所以在实际量产时,在同一个腔室即可完成发光层、空穴阻挡层和电子阻挡层的精细金属掩膜版蒸镀作业,从而能够较常规工艺省略两个真空蒸镀腔室,也提高了器件的生产制造效率。
本发明提供的显示器件,由于包括上述有机电致发光器件,因此也具有良好的性能。
附图说明
图1为TADF分子电致发光过程原理示意图;
图2为本发明一实施例中有机电致发光器件结构示意图;
图3为本发明另一实施例中有机电致发光器件结构示意图;
图4为本发明一实施例中电致发光过程能量转移原理示意图。
具体实施方式
本实施例提供的有机电致发光器件,包括发光层、空穴阻挡层和电子阻挡层,其中:发光层的材料包括主体材料;构成空穴阻挡层和电子阻挡层的材料均与主体材料相同。
如图2和图3所示,有机电致发光器件一般包括依次设置的阳极、空穴传输层(HTL)、发光层(EML)、电子传输层(ETL)和阴极,其中阳极与空穴传输层之间还可进一步设有空穴注入层(HIL)、阴极与电子传输层之间还可进一步设有电子注入层(EIL),电子阻挡层(EBL)设置在发光层与空穴传输层之间,空穴阻挡层(HBL)设置在发光层与电子传输层之间。
发光层的材料通常包括主体材料和客体材料,或者包括主体材料、敏化剂和客体材料。作为发光层的主体材料,其通常应该满足以下要求:1)具有高于客体材料的三线态能级,以有效防止能量从客体材料反转到主体材料上,造成能量损失;2)具有良好的传输性能,即具有较高的电荷和能量转移速率,使电荷有效的发生转移;3)拥有平衡电子和空穴传输的能力;4)具有稳定的性能。
本实施例中,由于主体材料的三线态能级较高、尤其是高于客体材料的三线态能级,因此,采用发光层的主体材料作为与发光层分别相邻的空穴阻挡层和电子阻挡层,可以有效的拦截激子扩散到空穴阻挡层和电子阻挡层,从而提升有机电致发光器件的发光效率以及寿命。
同时,使用同一款材料作为发光层的主体材料、空穴阻挡层材料和电子阻挡层材料,还可以有效的降低有机电致发光器件中发光层与相邻的空穴阻挡层和电子阻挡层之间的能级势垒,降低有机电致发光器件的开启电压,提高发光效率。
并且,如上所述,由于发光层的主体材料一般具有较好的双极传输性能,因此使用该主体材料作为空穴阻挡层和电子阻挡层,能够避免因材料迁移率较差而导致器件复合区域过窄,避免影响器件寿命。
进一步参考图2,发光层的材料具体包括主体材料(Host)和客体材料,其中客体材料包括至少一种热活化延迟荧光材料(TADF Emitter)。采用一种或多种TADF材料作为发光层的客体材料,或称为热活化延迟荧光染料,能够有效避免能级势垒及激基复合物的产生,降低有机电致发光器件的开启电压,提高器件的发光效率及寿命。
或者进一步参考图3,发光层的材料具体包括主体材料(Host)、敏化剂和客体材料,其中敏化剂为TADF材料,客体材料为传统荧光染料和/或传统磷光染料。以传统荧光染料(Fluorescent dyes)作为客体材料为例,其发光原理可参考图4,在该有机电致发光器件中,主体材料的能量传递给敏化剂(即TADF材料),然后TADF材料的三线态能量通过反向系间窜越(RISC)过程回到单线态,进而将能量传递给传统荧光染料,这样可以实现主体材料向客体材料分子完全的能量传递,尤其可以使荧光掺杂染料突破25%的内量子效率限制,进一步提高器件发光效率。
具体的,发光层主体材料的三线态能级应大于热活化延迟荧光材料的三线态能级,以实现主体材料与TADF材料之间能量的有效传递。在具体实施过程中,所用的主体材料的分子结构中含有咔唑基、苯胺基、芳环基、嘧啶基、三嗪基、硅烷基、磷氧基等中的至少一种基团。
优选的,主体材料尤其可以选择以下编号为TDH1至TDH24所代表的有机化合物,以确保有机电致发光器件具有更良好的发光效率和更长的寿命。
目前,在有机电致发光器件的发光层中使用TADF材料,往往存在器件发光效率较低、寿命较低的情况。导致这一情况出现的主要原因之一是发光层的激子扩散。由于TADF材料的单线态与三线态的能级差相对较小,使得TADF材料的发光层的三线态激子能级较高,容易产生激子扩散至其它功能层,与其它功能层的载流子发生碰撞而湮灭,最终使得有机电致发光器件的发光效率较低,对器件寿命也有所影响。而为了降低从三线态能级到单线态能级的势垒,目前一般倾向于选择具有较低单线态-三线态能级差的TADF材料,但又进一步影响了器件的发光效率及寿命。
而本实施例的技术方案,通过发光层的主体材料、空穴阻挡层和电子阻挡层使用同一款材料,可以有效的拦截激子扩散到与发光层相邻的空穴阻挡层和电子阻挡层,从而提升有机电致发光器件的发光效率以及寿命。
不难理解,本实施例的技术方案,对于具有较小的单线态-三线态能级差的热活化延迟荧光材料具有很好的效果。因此,本实施例中所使用的热活化延迟荧光材料可以是目前OLED器件中发光层中所常用的热活化延迟荧光材料,优选单线态-三线态能级差小于0.3eV的热活化延迟荧光材料。相较于发光层主体材料与电子阻挡层、空穴阻挡层的材料不完全一致或完全不一致的情况,采用本实施例的方案,OLED器件的发光效率和寿命都有明显的改善。
在具体实施过程中,所用的热活化延迟荧光材料优选以下编号为T-1至T-99所代表的化合物。
本发明中,所谓的“传统荧光染料”,指的是除TADF材料之外的其它可用于OLED器件发光层染料的荧光材料。在具体实施过程中,所选用的传统荧光染料包括但不限于以下编号为F-1至F-24所代表的化合物。
本发明中,所谓的“传统磷光染料”,指的是目前用于OLED器件发光层染料的磷光材料,不做特别限定。
具体的,对于热活化延迟荧光材料作为客体材料的情况,客体材料的掺杂浓度(即热活化延迟荧光组分占发光层材料的质量比)一般控制在0.1wt%-50wt%,优选5wt%-50wt%,以确保有机电致发光器件具有良好的发光效率和较长的寿命。
具体的,对于TADF材料作为发光层的敏化剂、传统荧光染料和/或传统磷光染料作为客体材料的情况,敏化剂的掺杂浓度一般控制在0.1wt%-50wt%,客体材料的掺杂浓度为0.1wt%-50wt%。合理控制二者的掺杂浓度,有利于进一步提高器件的发光效率和寿命,优选的,敏化剂的掺杂浓度为5wt%-50wt%,客体材料的掺杂浓度为0.1wt%-30wt%。
本实施例中,发光层的厚度一般控制在1-200nm。优选的,为进一步控制发光层复合区域,确保有机电致发光器件的发光效率和使用寿命,发光层的厚度一般为1-50nm。
具体的,电子阻挡层的厚度一般控制在1-500nm,为进一步提高有机电致发光器件的发光效率和寿命,电子阻挡层的厚度优选为1-50nm。
具体的,空穴阻挡层的厚度一般为1-200nm,为进一步提高有机电致发光器件的发光效率和寿命,空穴阻挡层的厚度优选为1-50nm。
本实施例还提供一种显示装置,包括上述有机电致发光器件。
该显示装置具体可以为OLED显示器等显示器件,以及包括该显示器件的电视、数码相机、手机、平板电脑等任何具有显示功能的产品或者部件。该显示装置与上述有机电致发光器件相对于现有技术所具有的优势相同,在此不再赘述。
下面将结合本发明实施例中的附图,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。
实施例1-7
实施例1-7分别提供一种有机电致发光器件,如图2所示,其器件结构依次包括ITO阳极、空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EML)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)和阴极。
其中,空穴注入层的材料为HATCN,一般总厚度为5-30nm,本实施例为10nm。空穴传输层的材料为OLED中HTL常用材料,本实施例为NPB,一般总厚度为5-500nm,本实施例为40nm。电子阻挡层的厚度一般为1-500nm,本实施例为5nm。发光层的主体材料(Host)与电子阻挡层、空穴阻挡层的材料一致,客体材料为TADF材料(TADF Emitter),掺杂浓度为0.1-50wt%;发光层的厚度一般为1-200nm,本实施例为30nm。空穴阻挡层的厚度一般为1-200nm,本实施例为5nm。电子传输层的材料为OLED中ETL常用材料,本实施例为TPBI,厚度一般为5-300nm,本实施例为30nm。电子注入层及阴极材料选择LiF(1nm)和金属铝(200nm)。
其中,NPB为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺,英文名称为N,N'-Bis-(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine。TPBI为1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯,英文名称为1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene。二者的化学结构式如下:
实施例1-7中所提供的有机电致发光器件中,发光层、电子阻挡层和空穴阻挡层材料的具体选择和掺杂浓度,以及相应有机电致发光器件的测试结果如表1。
表1
由表1的测试结果可知,当发光层的主体材料、空穴阻挡层材料和电子阻挡层的材料均保持一致时,OLED器件具有相对较高的发光效率和寿命。并且,随着发光层中TADF材料的掺杂浓度发生改变,OLED器件的发光效率和寿命也随之变化,当TADF材料的掺杂浓度为5wt%至50wt%的条件下,OLED器件具有相对最佳的发光效率和寿命。
特别是,当TADF材料的掺杂浓度为30wt%,实施例1的OLED器件在1000cd/m2亮度下的电流效率为17.9cd/A,寿命LT50为61h;实施例4的OLED器件在1000cd/m2亮度下的电流效率为15.8cd/A,寿命LT50为51h,性能更佳。
因此,本实施例所提供的技术方案,当发光层的主体材料、空穴阻挡层材料和电子阻挡层材料均一致,且发光层采用TADF材料作为客体材料时,OLED器件具有非常高的发光效率和寿命;并且,还可通过调节TADF材料的掺杂浓度,使OLED器件性能更佳。
对比例1-2
对比例1-2分别提供一种有机电致发光器件,其结构与实施例1-7相同,具体可参考图2;相应功能层的参数与实施例1-7基本一致,区别仅在于发光层的主体材料、空穴阻挡层和电子阻挡层所用材料并不完全一致,以及掺杂浓度有所区别。具体发光层、空穴阻挡层和电子阻挡层材料的选择、掺杂浓度以及相应OLED器件的测试结果如表1所示。
根据表1中对比例1与实施例1的对比情况可知,在发光层主体材料与电子阻挡层材料一致,但不同于空穴阻挡层材料的条件下,对比例1中的OLED器件在发光效率和寿命方面的表现明显不及实施例1中的OLED器件。
根据对比例2与实施例3的对比情况可知,在发光层主体材料与空穴阻挡层材料一致,但不同于电子阻挡层材料的条件下,对比例2中的OLED器件在发光效率和寿命方面的表现明显不及实施例3中的OLED器件。
以上对比结果进一步证实了,当发光层的主体材料与电子阻挡层、空穴阻挡层所用材料相一致时,OLED器件的发光效率和寿命有明显提升。
对比例3
本对比例提供一种有机电致发光器件,其结构与实施例1-7一致,具体可参考图2;相应功能层的参数与实施例2基本一致,区别仅在于:发光层的主体材料、空穴阻挡层和电子阻挡层均采用下述结构的化合物(编号为TDH25)。具体发光层、空穴阻挡层和电子阻挡层中材料的选择以及相应OLED器件的测试结果如表1所示。
由表1的对比结果可知,对比例2中主体材料未选择编号为TDH1至TDH24的化合物,OLED器件的发光效率和寿命虽然较对比例1-2有所提升,但仍旧明显低于实施例1-7中OLED器件的性能。
实施例8-10
实施例8-10分别提供一种有机电致发光器件,如图3所示,其器件结构依次包括ITO阳极、空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EML)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)和阴极。其中,发光层的主体材料(Host)、空穴阻挡层的材料和电子阻挡层的材料均相同,并使用TADF材料作为发光层的敏化剂、传统荧光染料作为发光层的客体材料(即Fluorescent dyes)。其它功能层所用的材料以及厚度均与实施例1-7一致,发光层的厚度为30nm,空穴阻挡层的厚度为5nm、电子阻挡层的厚度为5nm。
具体发光层、空穴阻挡层和电子阻挡层的材料选择、掺杂浓度以及相应实施例中OLED器件性能测试结果参见表2。
表2
由上述表2的测试结果可知,当发光层的主体材料、空穴阻挡层和电子阻挡层所用材料均完全一致时,OLED器件具有非常高的发光效率和寿命。并且,除了材料本身的因素以外,调整发光层中敏化剂和/或染料的掺杂浓度,OLED器件的发光效率和寿命也随之变化。相较而言,当TADF材料的掺杂浓度为5wt%至50wt%、尤其是10wt%至50wt%的条件下,且传统荧光染料的掺杂浓度为0.1wt%至30wt%、尤其是0.1wt%至10wt%的条件下,OLED器件具有相对最佳的发光效率和寿命。
特别是,当发光层中TADF的掺杂浓度为30wt%,且传统荧光染料的掺杂浓度为5wt%的条件下(实施例8),OLED器件在5000cd/m2亮度下的电流效率为80.7cd/A,寿命LT50在812h,性能最佳。
因此,本实施例所提供的技术方案,当发光层的主体材料、空穴阻挡层材料和电子阻挡层材料均保持一致,且发光层采用TADF材料作为敏化剂、传统荧光染料作为染料时,OLED器件具有非常高的发光效率和寿命;并且,还可通过调节TADF材料和传统荧光染料的掺杂浓度,使OLED器件性能达到更佳。
对比例4-5
对比例4-5分别提供一种有机电致发光器件,其器件结构与实施例8-10一致,具体可参考图3;相应功能层的参数与实施例8-10也基本一致,区别仅在于发光层的主体材料、电子阻挡层和空穴阻挡层所用材料不完全一致或者掺杂浓度不一致。具体材料的选择以及相应有机电致发光器件的测试结果如表2所示。
根据表2中对比例4与实施例8的对比情况可知,在发光层主体材料、空穴阻挡层和电子阻挡层所用材料不完全一致的条件下,对比例4中的OLED器件在发光效率和寿命方面的表现明显不及实施例8中的OLED器件。
根据对比例5与实施例10的对比情况可知,在发光层主体材料、电子阻挡层材料和电子阻挡层材料完全不一致的条件下,对比例5中的OLED器件在发光效率和寿命方面的表现明显不及实施例10中的OLED器件。
以上对比结果进一步证实了,当发光层的主体材料与电子阻挡层、空穴阻挡层所用材料完全一致时,OLED器件的发光效率和寿命有明显提升。
实施例11-14
实施例11-14分别提供一种有机电致发光器件,其结构与实施例1-7一致,具体可参考图2。实施例11-14中OLED器件各功能层所用材料及厚度均与实施例1基本一致,区别仅在于电子阻挡层及空穴阻挡层的厚度。
具体的,实施例11-14中,电子阻挡层及空穴阻挡层的厚度以及相应OLED器件的性能测试结果参见表3。
表3
由表3可知,当发光层的主体材料、电子阻挡层所用材料以及空穴阻挡层所用材料完全一致时,随着电子阻挡层厚度和/或空穴阻挡层厚度改变,有机电致发光器件的发光效率和寿命均有所改变。当电子阻挡层的厚度为1nm至50nm、空穴阻挡层的厚度为1nm至50nm的条件下,OLED器件的发光效率和寿命具有突出的表现。
进一步结合表1中实施例1的数据,当电子阻挡层和空穴阻挡层的厚度均为5nm时(即实施例1),OLED器件的发光效率和寿命都最佳。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
1.一种有机电致发光器件,其特征在于,包括发光层、空穴阻挡层和电子阻挡层,其中:所述发光层的材料包括主体材料;构成所述空穴阻挡层和电子阻挡层的材料均与所述主体材料相同。
2.根据权利要求1所述的有机电致发光器件,其特征在于,所述发光层的材料还包括客体材料,所述客体材料包括至少一种热活化延迟荧光材料。
3.根据权利要求1所述的有机电致发光器件,其特征在于,所述发光层的材料还包括敏化剂和客体材料,其中所述敏化剂为热活化延迟荧光材料,所述客体材料为传统荧光染料和/或传统磷光染料。
4.根据权利要求2或3所述的有机电致发光器件,其特征在于,所述主体材料的三线态能级大于所述热活化延迟荧光材料的三线态能级。
5.根据权利要求1-4任一项所述的有机电致发光器件,其特征在于,所述主体材料的分子结构中含有咔唑基、苯胺基、芳环基、嘧啶基、三嗪基、硅烷基和磷氧基中的至少一种基团。
6.根据权利要求5所述的有机电致发光器件,其特征在于,所述主体材料选自以下编号为TDH1至TDH24所代表的化合物之一:
7.根据权利要求2所述的有机电致发光器件,其特征在于,所述客体材料的掺杂浓度为0.1-50wt%。
8.根据权利要求3所述的有机电致发光器件,其特征在于,所述敏化剂的掺杂浓度为0.1-50wt%,所述客体材料的掺杂浓度为0.1-50wt%。
9.根据权利要求1-8任一项所述的有机电致发光器件,其特征在于,所述空穴阻挡层的厚度为1-200nm,和/或,所述电子阻挡层的厚度为1-500nm。
10.一种显示装置,其特征在于,包括权利要求1-9中任一项所述的有机电致发光器件。
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