CN103715370B - 微胶囊的制备方法 - Google Patents
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Abstract
本发明提供一种微胶囊和包括该微胶囊的有机电致发光显示装置,属于显示技术领域,其可解决现有的有机电致发光显示装置的显示亮度低,使用寿命短的问题。本发明的有机电致发光显示装置包括以磷光发光材料为芯材的微胶囊,所述的微胶囊降低了磷光发光材料自我淬灭,隔绝了水、氧,使有机电致发光显示装置显示亮度得到提高和使用寿命得到延长。
Description
技术领域
本发明属于显示技术领域,具体涉及一种微胶囊的制备方法。
背景技术
自从邓青云教授发现有机分子发光现象以来,人们对有机电致发光器件的研究不断深入,由于有机电致发光(OLED)器件具有高效率,低功耗,高色域等优点。OLED按照发光材料进行分类,主要包括荧光发光材料和磷光发光材料,其中,由于磷光发光材料的内量子效率高而得到广泛的重视。
但是,磷光发光材料容易因为分子堆叠而产生三重态自我淬灭,特别是在高电流密度下,更容易因分子淬灭而造成磷光损失,从而降低了磷光OLED的亮度。
此外,虽然磷光OLED器件在实验室的研发技术已经比较成熟,但在应用中还存在一些问题,例如,磷光OLED器件使用寿命易受环境影响。众所周知,磷光OLED器件是一种对水分、氧气极其敏感的显示器件,特别是水分,如果环境中渗透进去水分,就容易在发光区域造成黑点,且黑点会随着时间而扩大,从而影响显示质量和显示寿命。目前主要通过对磷光OLED器件进行封装避免黑点的产生和扩大。封装技术主要包括金属盖和玻璃盖等盖板封装技术,及以Vitex Systems公司开发的Barix薄膜封装层为代表的薄膜封装技术。但这些现有技术存在易产生表面不平整(如金属盖板封装),产生微裂缝(如玻璃盖板封装),成本高、制作工艺复杂(如Barix薄膜封装技术)等缺点。
发明内容
本发明的目的是解决现有技术中有机电致发光显示装置的发光层中磷光发光材料易发生分子淬灭而影响亮度、易受水分和氧气的影响而产生黑点的问题,提供一种提高亮度,延长使用寿命的微胶囊的制备方法。
解决本发明技术问题所采用的技术方案是一种微胶囊,包括壁材和包裹在壁材内的芯材,所述的芯材为磷光发光材料。
优选的是,所述的微胶囊的粒径范围为0.5-200um。
优选的是,所述的磷光发光材料的粒径范围为0.1-20nm。
优选的是,所述的壁材为明胶、乙基纤维素、阿拉伯胶中的任意一种。
本发明还提供一种上述微胶囊的制备方法,以磷光发光材料为芯材,以明胶、乙基纤维素、阿拉伯胶中的任意一种作为壁材,通过凝聚法制备。
本发明还提供一种有机电致发光显示装置,包括发光材料层,所述的发光材料层包括上述的微胶囊。
优选的是,还包括位于所述发光材料层一侧的依次设置的电子传输层、电子注入层、阴极层;和位于另一侧的依次设置的空穴传输层、空穴注入层、阳极层。
优选的是,还包括位于所述阴极层远离发光材料层一侧的用于封装的薄膜层。
优选的是,在于,所述的薄膜层采用铝基复合物,其分子结构式如下:
本发明通过对磷光发光材料进行微胶囊化,使得微胶囊之间磷光发光材料不互相接触,且每个微胶囊内的磷光发光材料相对较少,从而有效减少因为磷光发光材料的分子堆叠而造成的磷光淬灭几率,避免了因为磷光淬灭而造成的磷光损失,提高了磷光OLED显示装置的显示亮度。此外,由于磷光发光材料包裹在微胶囊内,有效减少了环境侵入的水分,氧气等与磷光发光材料发生化学反应而降低磷光发光材料的寿命,能有效提高磷光OLED显示装置的寿命。
附图说明
图1为本发明实施例1提供的微胶囊的截面示意图。
图2为本发明实施例2提供的有机电致发光显示装置截面示意图。
其中:
1.微胶囊;2.磷光发光材料;3.衬底基板;4.阳极层;5.空穴注入层;6.空穴传输层;7.发光材料层;8.电子传输层;9.电子注入层;10.阴极层;11.薄膜层。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案,下面结合附图和具体实施方式对本发明作进一步详细描述。
实施例1
如图1所示,本实施例提供一种微胶囊,包括壁材和芯材,所述的芯材为磷光发光材料2。其中,所述的2磷光发光材料可以是绿光磷光材料Ir(ppy)3、蓝光磷光材料FCNIr、红光磷光材料Ir(pq)2acac等。其中,三者的分子结构式分别如下:
应当理解的是,现有技术磷光发光材料2都可以作为微胶囊1的芯材使用。
优选的,磷光发光材料2的粒径范围为0.1-20nm。当然,根据胶囊化的需要或应用情况的需要也可以将磷光发光材料2的粒径制作的更小或更大。
优选的,微胶囊1的粒径范围为0.5-200um。当然,根据胶囊化的需要或应用情况的需要也可以将微胶囊1的粒径制作的更小或更大。
优选的,所述的壁材为明胶、乙基纤维素、阿拉伯胶中的任意一种。上述的壁材适合采用凝聚法制备微胶囊1。
上述微胶囊1的制备方法,可以采用凝聚法制备,包括以下步骤:
将明胶用去离子水泡胀,在50℃水浴下溶解于正己烷中制备得到6%的明胶溶液。
将粒径范围为15nm的绿光磷光材料Ir(ppy)3粉末,加入明胶水溶液中,搅拌形成乳化分散体系,用10%醋酸溶液调节体系的pH为3.5(3.5-3.8均可),保持分散体系温度为50℃,然后向分散体系缓缓加入20%浓度的硫酸钠溶液。
降低分散体系的温度至15℃,在绿光磷光材料Ir(ppy)3粉末芯材料上形成微胶囊1,粒径范围为20nm。
应当理解的是,也可以采用现有技术中其它的方法制备微胶囊1,例如,界面聚合法,相应地,壁材也可以采用其它材料。由于微胶囊技术已经非常成熟,不再一一赘述以磷光发光材料为壁材,采用现有技术中其它微胶囊技术制备微胶囊的步骤。
实施例2
如图2所示,本实施例提供一种有机电致发光显示装置(OLED)。OLED显示装置可以是采用顶发射型结构的磷光白光OLED显示装置,包括衬底基板3,阳极层4,空穴注入层5,空穴传输层6,发光材料层7,电子传输层8,电子注入层9,阴极层10以及用于封装的薄膜层11。
所述的发光材料层7使用上述微胶囊化的磷光发光材料2。
作为介绍,本实施例提供一种上述的有机电致发光显示装置的制备方法,包括以下步骤:
制备阳极:在衬底基板上的沉积阳极层4,所述的阳极层4使用高功函的材料氧化铟锡(ITO),也可以使用透明的碳纳米管(CNTs)等材料。其中,衬底基板1,其材质优选的为玻璃,也可以为塑料等透明材料;ITO可以使用真空磁控溅射方法在玻璃衬底上沉积ITO薄膜,真空磁控溅射方法为现有技术范畴,在此不再一一赘述。
制备空穴注入层:在ITO阳极层2上使用真空热蒸发法沉积空穴注入层5,真空热蒸发法为现有技术范畴,在此不再一一赘述。空穴注入层5的材料为具有良好空穴注入能力的酞菁铜(CuPc),酞菁铜的分子结构式如下:
制备空穴传输层:在空穴注入层3上使用真空热蒸发法沉积空穴传输层6,空穴传输层6的材料为具有良好的空穴传输能力的TCTA,其分子结构式如下:
制备发光层:在空穴传输层4上使用真空热蒸发法沉积发光材料层7,发光材料层7包括主发光层和辅发光层,其中,主发光层为微胶囊化的绿光磷光材料Ir(ppy)3与微胶囊化的红光磷光材料Ir(pq)2acac共掺杂TCTA、TAZ的混合式主发光层;辅发光层为微胶囊化的蓝光磷光材料FCNIr掺杂mCP形成;其中,TAZ、mCP的分子结构式如下:
根据色度学原理,其中红,绿,蓝三色发光材料掺杂于同一发光层中将会通过混色而产生白光。
制备电子传输层:在发光材料层7上采用真空热蒸发法沉积电子传输层8;电子传输层8的材料为具有良好的电子传输能力的喹啉铝(Alq3),其分子结构式如下:
制备电子注入层:在电子传输层8上采用真空热蒸发法沉积电子注入层9,电子注入层9的材料为具有良好的电子注入能力的氟化锂(LiF)等低功函材料。
制备阴极层:在电子注入层9上利用真空热蒸发法沉积低电阻的Mg/Al阴极层10。其中在阴极层10和阳极层4之间通过外接电路加上电压。利用所阴极注入电子,阳极注入空穴,所形成的电子和空穴在发光层相遇而产生激子,从而激发发光材料发光。
薄膜封装:制作完磷光OLED器件后,通过在磷光OLED显示装置上形成封装薄膜层11。在先将含有铝基复合物的烃类溶液快速蒸发,在真空环境中以液体形式凝聚在衬底上,并将此薄膜烘干,从而使整个磷光OLED结构完全密封和平整化。其中,铝基复合物的分子结构式如下:
可以理解的是,封装薄膜层11也可以采用以及其他的可以阻隔水、氧的有机物。
本发明提供的微胶囊,由于磷光发光材料包裹在微胶囊中,使各微胶囊之间的磷光发光材料不容易相互接触,同时微胶囊内的磷光发光材料分散分布,降低了磷光发光材料的分子相互接触产生的分子堆叠,从而引发磷光自我淬灭的几率,提高了磷光发光效率,提高了其显示亮度。
同时,由于磷光发光材料包裹于微胶囊中,可以有效减少水、氧与磷光发光材料的化学反应,从而避免在发光区域产生黑点等不良,从而提高了显示质量和显示寿命。
综上所述,本发明提供的微胶囊可以提高磷光有机电致发光显示装置的显示亮度,延长磷光有机电致发光显示装置的使用寿命。
可以理解的是,以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式,然而本发明并不局限于此。对于本领域内的普通技术人员而言,在不脱离本发明的精神和实质的情况下,可以做出各种变型和改进,这些变型和改进也视为本发明的保护范围。
Claims (1)
1.一种微胶囊的制备方法,其特征在于,微胶囊,包括壁材和包裹在壁材内的芯材;
所述制备方法包括:
以磷光发光材料为芯材,以明胶作为壁材,通过凝聚法制备;
所述凝聚法包括:
将明胶用去离子水泡胀,在50℃水浴下溶解于正己烷中制备得到6%的明胶溶液;
将粒径范围为15nm的绿光磷光材料Ir(ppy)3粉末,加入所述明胶溶液中,搅拌形成乳化分散体系,用10%醋酸溶液调节所述乳化分散体系的pH为3.5,保持所述乳化分散体系温度为50℃,然后向所述乳化分散体系缓缓加入20%浓度的硫酸钠溶液;
降低所述乳化分散体系的温度至15℃,在所述绿光磷光材料Ir(ppy)3粉末芯材料上形成所述微胶囊。
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US14/415,818 US20150364710A1 (en) | 2013-12-26 | 2014-04-25 | Light emitting microcapsule, method of preparing the same and oled display device comprising the same |
PCT/CN2014/076231 WO2015096324A1 (zh) | 2013-12-26 | 2014-04-25 | 发光微胶囊、及其制备方法和包括该发光微胶囊的有机电致发光显示装置 |
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US10696899B2 (en) | 2017-05-09 | 2020-06-30 | International Business Machines Corporation | Light emitting shell in multi-compartment microcapsules |
US10900908B2 (en) | 2017-05-24 | 2021-01-26 | International Business Machines Corporation | Chemiluminescence for tamper event detection |
US10357921B2 (en) | 2017-05-24 | 2019-07-23 | International Business Machines Corporation | Light generating microcapsules for photo-curing |
US10662299B2 (en) | 2017-06-09 | 2020-05-26 | International Business Machines Corporation | Heat generating microcapsules for self-healing polymer applications |
US10392452B2 (en) | 2017-06-23 | 2019-08-27 | International Business Machines Corporation | Light generating microcapsules for self-healing polymer applications |
CN108565361B (zh) * | 2018-05-25 | 2023-07-07 | Oppo广东移动通信有限公司 | Oled胶囊结构、oled发光层及相关方法、显示面板和电子设备 |
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