CN113666879A - 一种树枝状激基复合物热活化延迟荧光材料及其应用 - Google Patents
一种树枝状激基复合物热活化延迟荧光材料及其应用 Download PDFInfo
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Abstract
本发明公开了一种树枝状激基复合物热活化延迟荧光材料,其涉及光电器件领域,其以苯胺及其衍生物为电子给体单元,以三嗪、二嗪、含砜基、磷氧基官能团单元及其衍生物为电子受体单元,其分子结构基于电子给体单元或电子受体单元为核,以电子受体单元和电子给体单元为枝而构成,其中电子受体单元和电子给体单元之间以烷基链连接;本发明还公开了一种旋转受限的树枝状激基复合物热活化延迟荧光材料和一种有机发光二极管及其制作方法;本发明可有效简化激基复合物发光器件的加工工艺并提高稳定性,通过控制电子给体和强电子受体单元的电子特性、能级特点,以控制激基复合物的发光颜色,最终获得单色光和白光发射,增加有机发光器件材料的选择性。
Description
技术领域
本发明涉及光电器件的技术领域,特别是涉及一种树枝状激基复合物热活化延迟荧光材料及其应用。
背景技术
经过多年的发展,有机电致发光器件已经实现产业化。目前,有机电致发光器件已在大尺寸电视、车载显示器、手机、电子手环等诸多电子设备中得到广泛应用,如OLED电视、折叠智能手机、智能手环等。当前市场上OLED中最关键的发光层采用的还是发展较为早且成熟的传统荧光材料和磷光材料,前者发光效率局限,后者制造成本昂贵,在一定程度上限制了其最大范围的商业化应用。因此,结合传统荧光材料与磷光材料的优点,利用热活化延迟荧光(TADF)、三线态-三线态湮灭(TTA)、杂化-局域电荷转移态(HLCT)等高激子利用率的发光机理开发低成本、高效和稳定的荧光材料具有重大意义。
近年来,激基复合物电荷转移态发光作为新的发光形态逐渐受到越来越多的关注。2007年,有人利用激基复合物和激基缔合物电荷转移态发光实现了高质量的白光发射,为实现高效、稳定有机发光二极管提供了一种简单、有效的途径。还有人在强电子给体材料m-MTDATA和受体材料t-Bu-PBD形成的激基复合物电荷转移态体系中发现,激基复合物电荷转移态的三线态激子可以有效实现反系间窜越。随后的专家对m-MTDATA:PBD体系的光物理特性进行了相关的研究,证明了激基复合物发光体系可具备普通TADF发光材料的特性。近年来,国内、外多个课题组的研究结果也表明了激基复合物发光体系可以实现高效的TADF发光,专家利用共混激基复合物体系实现最大外量子效率超过20%。因此,利用简单的激基复合物电荷转移态来实现TADF发光,发展新型高效荧光材料为实现高效率、低成本发光提供了一种简单、有效的方法。
综上所述,利用激基复合物的发光都是不同电子给体受体材料共混所形成,对于器件制备及共混薄膜稳定性要求较高,因此制约了激基复合物的利用。
发明内容
本发明的目的在于克服现有技术中的上述缺陷,提供了一种树枝状激基复合物热活化延迟荧光材料及其应用,其利用单分子树枝状激基复合物热活化延迟荧光材料可以解决器件制备工艺复杂和共混薄膜稳定性较差的问题,同时也可以实现激基复合物的高激子利用,这种简单易行的分子设计可使激基复合物更好的应用在有机发光器件上。
为实现上述目的,本发明提供了一种树枝状激基复合物热活化延迟荧光材料,其以苯胺及其衍生物等为电子给体单元,以三嗪、二嗪、含砜基、磷氧基官能团单元及其衍生物等为电子受体单元,其分子结构基于电子给体单元或电子受体单元为核,以电子受体单元和电子给体单元为枝而构成,其中电子受体单元和电子给体单元之间以烷基链连接。
优选的,其为如下结构中的任意一种:
上述各个结构式中,n为1~12。
优选的,所述电子给体单元为三苯胺,所述电子受体单元为三嗪。
本发明还提供了一种旋转受限的树枝状激基复合物热活化延迟荧光材料,其在上述技术方案所述的一种树枝状激基复合物热活化延迟荧光材料的基础上,进一步引入化学键或空间位阻单元而形成,以限制树枝状激基复合物材料分子内的自由旋转。
优选的,其为如下结构中的任意一种:
上述各个结构式中,n为1~12。
优选的,其在上述所述的一种树枝状激基复合物热活化延迟荧光材料的基础上,进一步引入甲基而形成。
本发明还提供了一种有机发光二极管,其以上述所述的树枝状激基复合物热活化延迟荧光材料、或以上述所述的旋转受限的树枝状激基复合物热活化延迟荧光材料作为发光层的有效成分。
优选的,其包括依次层叠设置的氧化铟锡层(ITO层)、参杂有聚苯乙烯磺酸的聚乙氧基噻吩膜(PEDOT:PSS层)、发光层、氟化铯(CsF)层和铝层,所述氧化铟锡层(ITO层)连接电源的一极,所述铝层连接电源的另一级。
本发明还提供了一种有机发光二极管的制作方法,其包括以下步骤:
S1、先将上述技术方案所述的树枝状激基复合物热活化延迟荧光材料、或将上述技术方案所述的旋转受限的树枝状激基复合物热活化延迟荧光材料溶解在有机溶剂中,得到混合溶液,
同时,在氧化铟锡(ITO)上涂一层参杂有聚苯乙烯磺酸的聚乙氧基噻吩膜(PEDOT:PSS),然后将参杂有聚苯乙烯磺酸的聚乙氧基噻吩膜在指定温度下加热;
S2、将步骤S1中得到的混合溶液旋涂在聚乙氧基噻吩膜(PEDOT:PSS)的表面,形成发光层;
S3、接着在发光层上依次蒸镀一层氟化铯(CsF)和金属铝。
优选的,步骤S1中所述的有机溶剂为对氯苯或对二甲苯。
与现有技术相比,本发明提供的树枝状激基复合物热活化延迟荧光材料的有益效果在于:
利用树枝状激基复合物结构明确、成膜性优异的特点构筑低成本、高效率的可印刷型热活化延迟荧光材料,利用树枝状激基复合物发光实现热活化延迟荧光发射,将强电子给体单元、强电子受体单元通过化学键连接,可以有效简化激基复合物发光器件的加工工艺并且提高其稳定性,通过控制强电子给体单元和强电子受体单元的电子特性、能级特点,以控制激基复合物的发光颜色,最终获得单色光以及白光发射,通过控制激基复合物的生成比例以实现对光谱的调控并优化发光器件的性能,增加有机发光器件材料的选择性。本发明提出的树枝状激基复合物热活化延迟荧光材料相对于传统的激基复合物材料而言,具有更好的发光效率以及器件的稳定性。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1a-1c分别为TPA-R、T2T-PhR和3TPA-C6-T2T的化学结构式。;
图2为TPA-R、T2T-PhR和3TPA-C6-T2T的光致发光(PL)光谱图;
图3为电子给体TPA-R薄膜的光致发光荧光衰减寿命图;
图4为强电子受体单元T2T-PhR薄膜的光致发光荧光衰减寿命图;
图5为TPA-R薄膜在不同气氛下的光致发光荧光衰减寿命图;
图6为树枝状激基复合物3TPA-C6-T2T-3M薄膜的光致发光荧光衰减寿命图;
图7为有机发光二极管的器件的结构图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,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作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。
本发明的目的在于利用树枝状激基复合物结构明确、成膜性优异的特点构筑低成本、高效率的可印刷型热活化延迟荧光材料。将电子给体单元、电子受体单元通过化学键连接,可以有效简化激基复合物发光器件的加工工艺并且提高其稳定性。通过控制电子给受体单元的电子特性、能级特点以控制激基复合物的发光颜色,最终获得单色光以及白光发射,增加有机发光器件材料的选择性。
本发明的另一个目的在于通过合适的分子设计,提高激基复合物三线态激子的利用。通过化学键及空间位阻单元的引入,降低树枝状激基复合物材料分子内的旋转,降低激子的非辐射跃迁,可以有效提高树枝状激基复合物热活化延迟荧光材料的激子利用率及发光效率。提供了一种限制激基复合物发光材料激子非辐射跃迁的设计理念和方法。
因此,本发明提供了一种树枝状激基复合物热活化延迟荧光材料及其在有机发光二极管与平板显示器中的应用。
本发明的目的通过以下技术方案实现:
一种树枝状激基复合物热活化延迟荧光材料,该激基复合物由强电子给体单元和强电子受体单元组成;其中该材料为如下结构中的任意一种:
式中,n为1-12。
进一步地,所述树枝状激基复合物热活化延迟荧光是利用强电子给体单元和强电子受体单元通过烷基链连接。以上所述的树枝状激基复合物热活化延迟荧光应用于有机发光二极管中的发光层,具体应用步骤为将单层激基复合物溶于有机溶剂中,然后利用旋涂或喷墨打印的溶液加工方法制备有机发光二极管的发光层。
进一步地,所述有机溶剂为氯苯或者对二甲苯。
一种旋转受限的树枝状激基复合物热活化延迟荧光材料,其利用化学键或者空间位阻单元限制分子内的自由旋转。该单分子激基复合物化学式下列任意一种:
式中,n为1~12。
以上所述的树枝状激基复合物热活化延迟荧光材料应用于有机发光二极管中的发光层。
本发明以苯胺及其衍生物等为强电子给体单元,以三嗪、二嗪、含砜基、磷氧基官能团单元及其衍生物等为强电子受体单元,其分子结构基于强电子给体单元或强电子受体单元为核,以强电子受体单元和强电子给体单元为枝而构成,其中强电子受体单元和强电子给体单元之间以烷基链连接。因为强电子给体单元、强电子受体单元分别具有高HOMO值和较低LUMO值,以实现单分子的激基复合物发射,通过调控强电子给体和强电子受体单元间烷基链的长短可以形成有效的激基复合物。通过电子给受体单元能级以及电子特性的调控,使得激基复合物的三线态激子可以有效实现反系间蹿越实现热活化延迟荧光发射。具体的发光过程如下:发光器件中电子和空穴分别从阴极和阳极注入,并传输到活性层。由于树枝状激基复合物的能级特点,大部分的电子会限制在低LUMO的电子受体单元上,而空穴则大部分限制在高HOMO能级的强电子给体单元上。因此,在激子发生跃迁时,由于激基复合物的形成,激子会存在电子从第LUMO单元回迁到高HOMO单元二辐射发光。由于激基复合物的发光能带受强电子给体单元的HOMO和强电子受体单元的LUMO所影响,因此激基复合物的光谱发射会出现明显的红移现象。通过调节树枝状分子强电子给体单元、强电子受体单元的电子特性,可以获得单色光或者激基复合物的白光发射。利用化学键或者空间位阻单元限制分子内的自由旋转,最终获得高效、稳定的树枝状激基复合物热活化延迟荧光材料。
本发明所设计的树枝状激基复合物热活化延迟荧光材料是设计具有合适HOMO/LUMO能级的强电子受体单元和强电子给体单元,利用这两种单元之间的相互作用形成一种新的低能量激发态,并通过能量的完全或者不完全转移实现对光谱的调控并实现单色光或者单分子白光的发射。
本树枝状激基复合物热活化延迟荧光材料具有如下优点:(1)涉及的器件采用溶液加工技术,制备工艺简单,制作成本低;(2)能利用树枝状激基复合物发光实现热活化延迟荧光发射;(3)能利用调节强电子给体单元和强电子受体单元的电子特性,控制激基复合物的生成比例以实现对光谱的调控并优化发光器件的性能;(4)能利用化学键及空间位阻基团限制分子自由旋转,有效限制激子的非辐射跃迁,实现更好的激基复合物发光性能,提供了一种制备高质量有机发光器件的方法;(5)相对于传统的激基复合物材料而言,具有更好的发光效率以及器件的稳定性。
实验例1:设计并合成了具有合适能级以及载流子传输特性的强电子给体、强电子受体单元作为形成激基复合物的材料(三苯胺TPA-R和三嗪T2T-PhR分别作为强电子给体单元、强电子受体单元),通过烷基链把强电子给体单元、强电子受体单元连接起来得到树枝状分子3TPA-C6-T2T。首先把强电子给体单元TPA-R、强电子受体单元T2T-PhR以及树枝状分子3TPA-C6-T2T溶解在对二甲苯中配成所需的溶液;强电子给体单元TPA-R(化学结构式如图1a所示)以非共轭烷基链与强电子受体单元T2T-PhR(化学结构式如图1b所示)连接得到树枝状激基复合物发光材料3TPA-C6-T2T(化学结构如图1b所示)。所选用的强电子给体单元、强电子受体单元均为蓝光发射,而树枝状激基复合物材料由于强电子给体单元、强电子受体单元发生相互作用时,会产生一种新的低能激发态即形成激基复合物,发射出有别于强电子给体单元、强电子受体单元的蓝光发射,实现明显红移的黄光发射(图2)。从强电子给体单元、强电子受体单元及树枝状激基复合物材料3TPA-C6-T2T的激子寿命图(图3、图4、图5)可以知道,3TPA-C6-T2T的激子寿命明显延长,证明3TPA-C6-T2T有效实现激基复合物发光。而且3TPA-C6-T2T的激子寿命(图6)在氮气氛围中表现的更长,这样说明了3TPA-C6-T2T中形成的激基复合物电荷转移态能有效实现热活化延迟荧光发射,有利于提高激基复合物的激子利用效率。
实验例2:通过在3TPA-C6-T2T的强电子受体单元上引入甲基得到空间限制型树枝状激基复合物发光材料3TPA-C6-T2T-3M(化学结构如图6所示)。测试两种不同激基复合物发光材料薄膜的荧光量子产率可知,3TPA-C6-T2T的荧光量子产率(PLQY)约为43.6%,而通过引入甲基限制分子振动的3TPA-C6-T2T-3M的(PLQY)约为52.1%。这也说明了位阻基团的引入可以有效提高树枝状激基复合物材料的发光性能。
实验例3:把上述树枝状激基复合物材料3TPA-C6-T2T和3TPA-C6-T2T-3M分别溶解在对二甲苯中制备溶液中,再将得到的溶液利用旋涂工艺制备有机发光二极管的发光层。其中有机发光二极管的器件结构如图7所示,为ITO/PEDOT:PSS(40nm)/发光层(100nm)/CsF(1.5nm)/Al(150nm)。有机发光二极管器件的制备:在预先处理好的氧化铟锡(ITO)玻璃上,制备有机发光器件,其方块电阻为10-20Ω。在ITO上旋涂参杂有聚苯乙烯磺酸的聚乙氧基噻吩(PEDOT:PSS)膜,厚度为40nm。PEDOT:PSS膜在120℃下加热处理20分钟。随后将树枝状激基复合物发光材料的对二甲苯溶液(1.5wt%)旋涂在PEDOT:PSS膜的表面,厚度约为80nm;最后在发光层上依次蒸镀一层氟化铯CsF(1.5nm)和150nm厚的金属Al层。表1为实验例1和实验例2中树枝状发光材料发光器件的效果参数。从器件数据可以知道,通过引入位阻基团可以有效提高激基复合物的光电性能。
表1树枝状激基复合物光电性能
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种树枝状激基复合物热活化延迟荧光材料,其特征在于,其以苯胺及其衍生物为电子给体单元,以三嗪、二嗪、含砜基、磷氧基官能团单元及其衍生物为电子受体单元,其分子结构基于电子给体单元或电子受体单元为核,以电子受体单元和电子给体单元为枝而构成,其中电子受体单元和电子给体单元之间以烷基链连接。
3.根据权利要求1所述的一种树枝状激基复合物热活化延迟荧光材料,其特征在于,所述电子给体单元为三苯胺,所述电子受体单元为三嗪。
4.一种旋转受限的树枝状激基复合物热活化延迟荧光材料,其特征在于,其在权利要求1-3任一项所述的一种树枝状激基复合物热活化延迟荧光材料的基础上,进一步在电子给受体单元上引入化学键或空间位阻单元而形成,以限制树枝状激基复合物材料分子内的自由旋转。
6.根据权利要求4所述的一种旋转受限的树枝状激基复合物热活化延迟荧光材料,其特征在于,在权利要求1-3任一项所述的一种树枝状激基复合物热活化延迟荧光材料的基础上,进一步引入甲基而形成。
7.一种有机发光二极管,其特征在于,其以权利要求1-3任一项所述的树枝状激基复合物热活化延迟荧光材料、或以权利要求4-6任一项所述的旋转受限的树枝状激基复合物热活化延迟荧光材料作为发光层的有效成分。
8.根据权利要求7所述的一种有机发光二极管,其特征在于,其包括依次层叠设置的氧化铟锡层(ITO层)、参杂有聚苯乙烯磺酸的聚乙氧基噻吩膜(PEDOT:PSS层)、发光层、氟化铯(CsF)层和铝层,所述氧化铟锡层(ITO层)连接电源的一极,所述铝层连接电源的另一级。
9.一种有机发光二极管的制作方法,其特征在于,其包括以下步骤:
S1、先将权利要求1-3任一项所述的树枝状激基复合物热活化延迟荧光材料、或将权利要求4-6任一项所述的旋转受限的树枝状激基复合物热活化延迟荧光材料溶解在有机溶剂中,得到混合溶液,
同时,在氧化铟锡(ITO)上涂一层参杂有聚苯乙烯磺酸的聚乙氧基噻吩膜(PEDOT:PSS),然后将参杂有聚苯乙烯磺酸的聚乙氧基噻吩膜在指定温度下加热;
S2、将步骤S1中得到的混合溶液旋涂在聚乙氧基噻吩膜(PEDOT:PSS)的表面,形成发光层;
S3、接着在发光层上依次蒸镀一层氟化铯(CsF)和金属铝。
10.根据权利要求9所述的一种有机发光二极管的制作方法,其特征在于,步骤S1中所述的有机溶剂为对氯苯或对二甲苯。
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