CN114058365B - 一种钙钛矿纳米晶溶胶、色转换膜及其制备方法 - Google Patents
一种钙钛矿纳米晶溶胶、色转换膜及其制备方法 Download PDFInfo
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Abstract
本申请公开了一种钙钛矿纳米晶溶胶、色转换膜及其制备方法,该钙钛矿纳米晶溶胶由乙烯基硅氧烷、正硅酸酯、氨基硅氧烷复合包覆剂包覆的化学式为Cs(Pb1‑a,Zna)X3纳米晶、ZnX2、丙烯酸酯溶剂组成。采用ZnX2提供卤源,直接在丙烯酸酯封装基质中合成钙钛矿纳米晶,并且用复合包覆剂包覆在纳米晶体周围,形成稳定性极佳的溶胶;溶胶中加入交联剂和光引发剂后,涂布在基板上,采用紫外固化形成钙钛矿色转换膜。本发明提出的纳米晶溶胶以及色转换膜光、热稳定性高,其制备方法简单,易于操作,成本低,适合各种尺寸钙钛矿色转换膜的批量化制作等优点,在全彩显示中具有巨大潜力。
Description
技术领域
本发明涉及光电材料领域,尤其涉及一种钙钛矿溶胶和色转换膜及其制备方法。
背景技术
金属卤化物钙钛矿材料因其具有较高的光致发光量子产率(PLQY)和鲜艳的色彩等这些优异的光学性能而被广泛研究,相较其他领域的应用,钙钛矿材料在显示技术领域的应用稍晚,从2015年开始,相关的研究才逐渐兴起。这些材料的一个潜在应用是将它们结合蓝光LED或OLED用作颜色转换层(CCLs),此处的能量转移是经由钙钛矿色转换层后,蓝光需要完全转化成相对应的绿光或红光,进而达到全彩显示的目的。如中国发明专利公开号CN110854167A公开了一种显示面板及其制作方法,色转换层中的第一水氧阻挡层可以有效的将钙钛矿色转换功能层密封在像素开口中,避免钙钛矿材料与水分和氧气接触,从而提高了色转换层的稳定性。此方法只是单一从物理角度对色转换膜进行密封,稳定性并不能很好的保持。如中国发明专利公开号CN111016478A公开了一种钙钛矿色转换膜的制作方法,采用丝网印刷的方式将所述网板上的钙钛矿浆料图案化印刷在基板上并固化,相比于现有的光刻或喷墨打印制作工艺,极大的简化了钙钛矿色转换膜的制作流程,但此方法所用的钙钛矿浆料需要烘烤,这就要求原材料具有较好的稳定性。
目前制备的色转换micro-LED全彩显示器仍然采用常规的量子点材料作为光色转换层,基于钙钛矿的光色转换层目前仍未成功开发,与传统的量子点材料相比,钙钛矿材料的半峰宽较窄,因此其色转换效果与传统量子点色转换膜相当甚至更好,所以,开发钙钛矿光色转换层材料尤为重要。另外,钙钛矿需要有较高的耐光、耐湿热性能,其组成和制备工艺也需要优化,以提高其稳定性。如文献[Adv.Mater.Technol,2020.5(6):2000251]报道了一种采用蓝光micro-LEDs 背光源与CsPbBr3钙钛矿和CdSe量子点分别作为绿光和绿光色转换层的全彩显示样机,虽然显示器的色域较高,但红光色转换膜采用的是传统量子点材料。
在之前的工作里,如中国发明专利公开号CN108165259A,以丙烯酸酯单体为溶剂,在室温下用一种简便的原位合成法制备了CsPbBr3纳米晶,并引入3-氨基丙基三乙氧基硅烷(APTES)来提高纳米晶的稳定性。但仍存在以下问题: 1.APTES中-NH2基团与CsPbBr3纳米晶相连接,但是另一端的乙氧基随着水解缩合反应不断进行而形成与丙烯酸酯不相容的Si-O-Si和Si-OH,从而在长期储存时纳米晶发生沉降;2.包覆层薄且水解缩合不完全时使包覆层不致密,具有阴离子、水汽、氧气的出入孔道,造成不能阻止离子交换的缺陷,导致纳米晶稳定性不高。
发明内容
为解决钙钛矿溶胶中纳米晶长期储存发生沉降且不能阻止离子交换的缺陷以及色转换膜稳定性差,工艺复杂,不易于大规模批量生产的问题,本发明提出一种钙钛矿纳米晶溶胶、色转换膜及其制备方法,所述的钙钛矿纳米晶溶胶由乙烯基硅氧烷、正硅酸酯、氨基硅氧烷共同预水解得到的复合包覆剂包覆的化学式为Cs(Pb1-a,Zna)X3钙钛矿纳米晶、ZnX2、丙烯酸酯溶剂组成,其中:
X=Cl、Br、I,0≦a≦0.1;
Cs(Pb1-a,Zna)X3钙钛矿、复合包覆剂、ZnX2、丙烯酸酯溶剂的质量百分比分别为0.3~5%、1~5%、0~1%、89~98.7%;
所述的钙钛矿纳米晶色转换膜由质量百分比为20~80%的钙钛矿纳米晶溶胶、10~60%的丙烯酸酯交联剂、0.5~5%光引发剂、0~50%的丙烯酸酯齐聚物的混合胶涂布于基板上再经光固化制备得到,厚度为0.1~300um;
它们的制备方法包括如下步骤:(1)将乙烯基硅氧烷、正硅酸酯、氨基硅氧烷加入到丙烯酸酯溶剂中,搅拌0.5~24小时预水解后得到复合包覆剂溶胶;(2)将铯、铅的有机酸化物与丙烯酸酯溶剂混合后,加入有机卤化铵,再加入ZnX2; (3)加入复合包覆剂溶胶并搅拌0.5~10小时,即可得到钙钛矿纳米晶溶胶;(4) 将钙钛矿纳米晶溶胶、丙烯酸酯交联剂、光引发剂、丙烯酸酯齐聚物混合,涂布于基板上,使用紫外光照射后即可制得钙钛矿色转换膜。
所述的乙烯基硅氧烷化学式为R1CH2=CHR2Si(O-R3)3,氨基硅氧烷的化学式为NH2-R4-Si(O-R5)3,R1、R2、R3分别为不高于5、3和4个碳原子的烷基, R4和R5分别为不高于6和4个碳原子的烷基,正硅酸酯为正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯和正硅酸四丁酯中的一种及以上。氨基硅氧烷含有-NH2基团作为配体对纳米晶起保护稳定作用,又可水解成网络结构的-Si-O-基团在纳米晶最内层;正硅酸酯水解缩合后产生-Si-O-Si-交联网络结构,作为第二层与氨基硅氧烷水解的-Si-O-链接;乙烯基硅氧烷水解后含-Si-O-的一端与正硅酸酯水解的-Si-O-Si-链接,从而形成3层包覆层,另一端的含C=C的烷基链与丙烯酸酯溶剂具有良好的相溶性,使得包覆后的纳米晶能均匀分散在丙烯酸酯溶剂中,因此,氨基硅氧烷、乙烯基硅氧烷和正硅酸酯在丙烯酸酯中的溶解性是复合包覆剂的关键之一,氨基硅氧烷、乙烯基硅氧烷的烷基链太长,溶解性降低甚至不溶解,而正硅酸酯的烷氧基链太长会造成水解速度低,需要较长时间进行水解,使得效率下降。
所述的乙烯基硅氧烷、正硅酸酯、氨基硅氧烷的质量比为 2.5~3.5:0.5~1.5:1,超出此范围,溶胶放置容易产生沉淀,存储稳定性差。
所述的复合包覆剂溶胶中乙烯基硅氧烷、正硅酸酯、氨基硅氧烷的质量之和占溶胶总质量的20%~60%,太低,则复合包覆剂溶胶的用量大,使得最终的钙钛矿溶胶中纳米晶的含量降低,太高,则复合包覆剂见互相缩合成颗粒状,产生沉淀,无法进行包覆。
所述的复合包覆剂原料在丙烯酸酯溶剂中进行0.5~24h的预水解。若水解时间过短,复合包覆剂加入时未达到一定的水解度,则在加入纳米晶溶胶后水解形成网络结构所需时间较长,无法控制纳米晶尺寸。若水解时间过长,则复合包覆剂水解过度,直接形成SiO2溶胶,也无法在纳米晶周围形成包覆。
所述的铯、铅的有机酸化物中的有机酸为含碳原子大于等于2小于等于 20的有机酸,高于20,则不溶于丙烯酸酯溶剂中,低于2,则溶胶的稳定性差。
所述的有机卤化铵中的碳原子大于等于2小于等于20,小于2,反应太快,容易造成团聚沉淀,高于20,则不溶于丙烯酸酯溶剂中。
由于步骤1为预水解,因此,在步骤3中,加入复合包覆剂溶胶后需要搅拌0.5~10小时,以便复合包覆剂继续水解并包覆于纳米晶表面,从而阻止纳米晶团聚长大,时间太短,水解不充分,包覆层致密度低,不能阻挡离子交换,稳定性也下降;时间太长,则使包覆层水解过度或包覆层太厚,导致合成的纳米晶溶胶产生沉淀。
本发明的优点是:
1.采用三种包覆剂组成的复合包覆剂对红色纳米晶进行组合式包覆,相对于之前单一包覆剂,提高了纳米溶胶以及色转换膜的稳定性。
2.由于致密的三层包覆,阻止了不同发光波长溶胶之间的阴离子交换。可直接将两种溶胶混合而不会发生任何交换,一步制备混合色转换膜,制备工艺简单。
3.采用卤化锌原位合成不同颜色钙钛矿纳米晶溶胶,制备的色转换膜材料,具有好的柔韧性,其热稳定性和光稳定性都较高,在全彩显示中具有巨大潜力。
附图说明
附图1:实施例1纳米晶溶胶的高分辨透射电子显微镜镜照片;
附图2:实施例1色转换膜的发射及吸收光谱图;
附图3:实施例1色转换膜在紫外光照下发光强度随时间变化关系图;
附图4:实施例6色转换膜在紫外光照下发射光谱随时间变化图。
具体实施方式
实施例1
将1.65g乙烯基三乙氧基硅烷,0.55g正硅酸乙酯,0.438g三氨丙基三甲氧基硅烷滴入5ml的甲基丙烯酸异冰片酯溶剂中,密封持续搅拌水解6h,得到复合包覆剂溶胶。将0.0414g油酸铯、0.0489g油酸铅与5ml甲基丙烯酸异冰片酯溶剂混合后,加入含0.0547g四辛基溴化铵的10ml甲基丙烯酸异冰片酯中,再将含有0.0319g ZnI2的10ml甲基丙烯酸异冰片酯溶液加入上述混合溶液中,再加入 800ul复合包覆剂溶胶并搅拌5h,得到钙钛矿纳米晶溶胶。将1.4g钙钛矿纳米晶溶胶、0.6g环三羟甲基丙烷甲缩醛丙烯酸酯、0.056g 2-羟基-2-甲基-1-苯基-1-丙酮、0.1g聚氨酯丙烯酸酯树脂混合,涂布于基板上,用紫外光照射固化3min后,得到钙钛矿色转换膜。
实施例2
将1.375g乙烯基三乙氧基硅烷,0.275g正硅酸四丁酯,0.438g三氨丙基三甲氧基硅烷滴入5ml甲基丙烯酸异冰片酯和5ml甲基丙烯酸甲酯的混合溶剂中,密封持续搅拌水解0.5h,得到复合包覆剂溶胶。将0.0191g乙酸铯、0.0266g乙酸铅与5ml甲基丙烯酸异冰片酯溶剂混合后,加入含0.0547g四辛基溴化铵的20ml 甲基丙烯酸异冰片酯中,再将含有0.0319g ZnBr2的10ml甲基丙烯酸异冰片酯溶液加入上述混合溶液中,再加入800ul复合包覆剂溶胶并搅拌0.5h,得到钙钛矿纳米晶溶胶。将1.4g钙钛矿纳米晶溶胶、0.6g环三羟甲基丙烷甲缩醛丙烯酸酯、 0.056g 2-羟基-2-甲基-1-苯基-1-丙酮、0.1g聚氨酯丙烯酸酯树脂混合,涂布于基板上,用紫外光照射固化3min后,得到钙钛矿色转换膜。
实施例3
将1.925g乙烯基三叔丁氧基硅烷,0.825g正硅酸四丙酯,0.356g二乙氨基甲基三乙氧基硅烷滴入7ml的甲基丙烯酸异冰片酯溶剂中,密封持续搅拌水解24h,得到复合包覆剂溶胶。将0.0375g十五酸铯、0.0450g十五酸铅与3ml甲基丙烯酸异冰片酯和2ml甲基丙烯酸丁酯溶剂混合后,加入含0.0862g四甲基氯化铵的 5ml甲基丙烯酸异冰片酯中,再将含有0.0757g ZnBr2的5ml甲基丙烯酸异冰片酯溶液加入上述混合溶液中,再加入150ul复合包覆剂溶胶并搅拌10h,得到钙钛矿纳米晶溶胶。将1.4g钙钛矿纳米晶溶胶、0.6g环三羟甲基丙烷甲缩醛丙烯酸酯、0.056g 2-羟基-2-甲基-1-苯基-1-丙酮、0.1g聚氨酯丙烯酸酯树脂混合,涂布于基板上,用紫外光照射固化3min后,得到钙钛矿色转换膜。
实施例4
将1.65g乙烯基三乙氧基硅烷,0.55g正硅酸乙酯,0.438g三氨丙基三甲氧基硅烷滴入5ml的甲基丙烯酸异冰片酯溶剂中,密封持续搅拌水解18h,得到复合包覆剂溶胶。将0.0444g二十酸铯、0.0518g二十酸铅与5ml甲基丙烯酸异冰片酯溶剂混合后,加入含0.0547g四辛基溴化铵的10ml甲基丙烯酸异冰片酯中,再将含有0.0319g ZnCl2的10ml甲基丙烯酸异冰片酯溶液加入上述混合溶液中,再加入1.25ml复合包覆剂溶胶并搅拌4h,得到钙钛矿纳米晶溶胶。将1.8g钙钛矿纳米晶溶胶、0.2g二缩三丙二醇二丙烯酸酯、0.073g 2-羟基-2-甲基-1-苯基-1-丙酮、0.05g季戊四醇四丙烯酸酯混合,涂布于基板上,用紫外光照射固化10min 后,得到钙钛矿色转换膜。
实施例5
将1.50g乙烯基三乙酰氧基硅烷,0.45g正硅酸四甲酯,0.380g三N-(2-氨基乙基)-3- 氨基丙基三甲氧基硅烷滴入5ml的甲基丙烯酸异冰片酯溶剂中,密封持续搅拌水解6h,得到复合包覆剂溶胶。将0.0219g丁酸铯、0.0294g丁酸铅与5ml甲基丙烯酸异冰片酯溶剂混合后,加入含0.0547g四辛基溴化铵的10ml甲基丙烯酸异冰片酯中,再将含有0.052g ZnI2的10ml甲基丙烯酸异冰片酯溶液加入上述混合溶液中,再加入800ul复合包覆剂溶胶并搅拌4h,得到钙钛矿纳米晶溶胶。将 0.6g钙钛矿纳米晶溶胶、1.4g新戊二醇二丙烯酸酯、0.1g2-羟基-2-甲基-1-苯基-1- 丙酮、0.2g乙氧基化三羟甲基丙烷三丙烯酸酯混合,涂布于基板上,用紫外光照射固化1min后,得到钙钛矿色转换膜。
实施例6
取1.5g实施例1方法制备的纳米晶溶胶,依次加入0.5g新戊二醇二丙烯酸酯, 1g二缩三丙二醇二丙烯酸酯光交联剂,0.084g 2-羟基-2-甲基-1-苯基-1-丙酮,磁力搅拌3min;取1.5g实施例2制备的纳米晶溶胶溶胶,并加入上述相同物质,磁力搅拌3min。然后将两种溶胶混合,搅拌2min后涂布在基板上,紫外光固化 2min,得到混合色转换膜。
Claims (7)
1.一种钙钛矿色转换膜的制备方法,其特征在于,所述钙钛矿色转换膜由质量百分比为20~80%的钙钛矿纳米晶溶胶、10~60%的丙烯酸酯交联剂、0.5~5%光引发剂、0~50%的丙烯酸酯齐聚物的混合胶涂布于基板上再经光固化制备得到,厚度为0.1~300um;
所述钙钛矿纳米晶溶胶由乙烯基硅氧烷、正硅酸酯、氨基硅氧烷共同预水解得到的复合包覆剂包覆的化学式为Cs(Pb1-a,Zna)X3钙钛矿纳米晶、ZnX2、丙烯酸酯溶剂组成,其中:
X=Cl、Br、I,0≦a≦0.1;
所述Cs(Pb1-a,Zna)X3钙钛矿、复合包覆剂、ZnX2、丙烯酸酯溶剂的质量百分比分别为0.3~5%、1~5%、0~1%、89~98.7%,且ZnX2的质量百分比不为0;
所述钙钛矿色转换膜的制备方法包括如下步骤:(1)将乙烯基硅氧烷、正硅酸酯、氨基硅氧烷加入到丙烯酸酯溶剂中,搅拌0.5~24小时预水解后得到复合包覆剂溶胶;(2)将铯、铅的有机酸化物与丙烯酸酯溶剂混合后,加入有机卤化铵,再加入ZnX2;(3)加入复合包覆剂溶胶并搅拌0.5~10小时,即可得到钙钛矿纳米晶溶胶;(4)将钙钛矿纳米晶溶胶、丙烯酸酯交联剂、光引发剂、丙烯酸酯齐聚物混合,涂布于基板上,使用紫外光照射后即可制得钙钛矿色转换膜;
所述铯、铅的有机酸化物中的有机酸为含碳原子大于等于2小于等于20的有机酸;
所述有机卤化铵中的碳原子大于等于2小于等于20。
2.根据权利要求1所述的制备方法,其特征在于乙烯基硅氧烷、正硅酸酯、氨基硅氧烷的质量比为2.5~3.5:0.5~1.5:1。
3.根据权利要求1所述的制备方法,其特征在于复合包覆剂溶胶中乙烯基硅氧烷、正硅酸酯、氨基硅氧烷的质量之和占溶胶总质量的20%~60%。
4.根据权利要求1~3任一项所述的制备方法,其特征在于正硅酸酯为正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯和正硅酸四丁酯中的一种及以上。
5.根据权利要求1~3任一项所述的制备方法,其特征在于氨基硅氧烷为化学式为NH2-R4-Si(O-R5)3中的一种及以上,其中,R4和R5分别为不高于6和4个碳原子的烷基。
6.根据权利要求1所述的制备方法,其特征在于钙钛矿纳米晶表面包覆的复合包覆剂层的厚度为5~200nm。
7.一种如权利要求1~6任一项所述的制备方法制备得到的钙钛矿色转换膜。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106634961A (zh) * | 2016-12-19 | 2017-05-10 | 中央民族大学 | 一种有机无机杂化钙钛矿量子点及其制备方法 |
CN107446572A (zh) * | 2017-09-01 | 2017-12-08 | 中国科学院长春光学精密机械与物理研究所 | 合成二氧化硅包覆有机‑无机钙钛矿结构量子点的方法及其合成的量子点的应用 |
CN108165259A (zh) * | 2017-12-26 | 2018-06-15 | 华东理工大学 | 一种钙钛矿量子点溶胶的制备方法 |
CN108441211A (zh) * | 2018-05-03 | 2018-08-24 | 中央民族大学 | 一种基于有机无机杂化钙钛矿量子点的荧光材料及其制备方法 |
CN108728077A (zh) * | 2018-05-08 | 2018-11-02 | 天津理工大学 | 合成二氧化硅包覆无机钙钛矿量子点的制备方法 |
CN109837084A (zh) * | 2019-03-22 | 2019-06-04 | 苏州大学 | 钙钛矿复合材料及其制备方法 |
CN112540508A (zh) * | 2020-12-04 | 2021-03-23 | 厦门大学 | 一种波长转换胶膜材料及其制备方法 |
CN112680213A (zh) * | 2020-12-24 | 2021-04-20 | 温州大学 | 一种正硅酸乙酯包覆的钙钛矿纳米晶的制备方法 |
CN112961675A (zh) * | 2021-01-31 | 2021-06-15 | 福建工程学院 | 溶胶-凝胶钝化提高钙钛量子点稳定性的方法 |
KR20210123030A (ko) * | 2020-04-02 | 2021-10-13 | 고려대학교 산학협력단 | 실리카 코팅된 페로브스카이트 나노입자의 제조 방법, 이로부터 제조된 나노입자의 박막 제조 방법 및 이의 패턴 형성 방법 |
-
2021
- 2021-12-03 CN CN202111467725.8A patent/CN114058365B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106634961A (zh) * | 2016-12-19 | 2017-05-10 | 中央民族大学 | 一种有机无机杂化钙钛矿量子点及其制备方法 |
CN107446572A (zh) * | 2017-09-01 | 2017-12-08 | 中国科学院长春光学精密机械与物理研究所 | 合成二氧化硅包覆有机‑无机钙钛矿结构量子点的方法及其合成的量子点的应用 |
CN108165259A (zh) * | 2017-12-26 | 2018-06-15 | 华东理工大学 | 一种钙钛矿量子点溶胶的制备方法 |
CN108441211A (zh) * | 2018-05-03 | 2018-08-24 | 中央民族大学 | 一种基于有机无机杂化钙钛矿量子点的荧光材料及其制备方法 |
CN108728077A (zh) * | 2018-05-08 | 2018-11-02 | 天津理工大学 | 合成二氧化硅包覆无机钙钛矿量子点的制备方法 |
CN109837084A (zh) * | 2019-03-22 | 2019-06-04 | 苏州大学 | 钙钛矿复合材料及其制备方法 |
KR20210123030A (ko) * | 2020-04-02 | 2021-10-13 | 고려대학교 산학협력단 | 실리카 코팅된 페로브스카이트 나노입자의 제조 방법, 이로부터 제조된 나노입자의 박막 제조 방법 및 이의 패턴 형성 방법 |
CN112540508A (zh) * | 2020-12-04 | 2021-03-23 | 厦门大学 | 一种波长转换胶膜材料及其制备方法 |
CN112680213A (zh) * | 2020-12-24 | 2021-04-20 | 温州大学 | 一种正硅酸乙酯包覆的钙钛矿纳米晶的制备方法 |
CN112961675A (zh) * | 2021-01-31 | 2021-06-15 | 福建工程学院 | 溶胶-凝胶钝化提高钙钛量子点稳定性的方法 |
Non-Patent Citations (7)
Title |
---|
All-inorganic CsPbBr3 perovskite quantum dots embedded in dual-mesoporous silica with moisture resistance for two-photon-pumped plasmonic nanoLasers;Yu Chen等;《Nanoscale》;20180314;第10卷(第14期);第6704-6711页 * |
CsPbX3纳米晶稳定性的研究进展;杨丹丹等;《无机材料学报》;20201031;第35卷(第10期);第1088-1098页 * |
Room Temperature In-Situ Synthesis of Inorganic Lead Halide Perovskite Nanocrystals Sol Using Ultraviolet Polymerized Acrylic Monomers as Solvent and Their Composites with High Stability;Ludan Zhu等;《Appl. Sci.》;20200511;第10卷(第9期);第1-11页 * |
Room-Temperature in Situ Synthesis of Highly Efficient CsPbBr3/SiO2 Sol in Entirely Ethanol Solvent by Constructing Amine-Functionalized Silica Micelles;Jun Cheng等;《Langmuir》;20200318;第36卷(第13期);第3565-3572页 * |
The synthesis and characterisation of the highly stable perovskite nano crystals and their application to ink-jet printed colour conversion layers;Sol Choi等;《Journal of Industrial and Engineering Chemistry》;20200215;第85卷;第226-239页 * |
发光铅卤钙钛矿纳米晶稳定性的研究进展;樊钦华等;《物理学报》;20201231;第69卷(第11期);第1-11页 * |
金属离子掺杂提高全无机钙钛矿纳米晶发光性质的研究进展;于鹏等;《物理学报》;20201231;第69卷(第18期);第1-11页 * |
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