CN112646570B - 一种基于钙钛矿量子点的防蓝光材料以及防蓝光复合膜及含有其的显示器件 - Google Patents
一种基于钙钛矿量子点的防蓝光材料以及防蓝光复合膜及含有其的显示器件 Download PDFInfo
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Abstract
本申请公开了一种防蓝光材料,包括基质和钙钛矿量子点;所述钙钛矿量子点将波长小于455nm的蓝光转化为波长不低于460nm的蓝光。以及一种基于钙钛矿量子点的防蓝光复合膜。利用钙钛矿量子点材料的斯托克斯位移小、发光效率高的优点,尽可能多地将对人眼有害的415‑455波段的蓝光转换成460‑480nm波段的蓝光。相比于传统的单吸收或者过滤型的防蓝光膜(问题在于过滤掉的蓝光浪费,白平衡变化较大,明显感觉显示的画面偏红),本方案可以将有害波段的蓝光高效率地转换为显示器件或人眼所需的蓝光,一方面避免了能量损失,另一方面可以更好地保证显示器件的白平衡在附加防蓝光膜后不发生剧烈地变化。
Description
技术领域
本申请涉及一种基于钙钛矿量子点的防蓝光涂层以及防蓝光复合膜,属于防蓝光材料领域。
背景技术
近年来,随着科学技术的发展,显示技术也在发生着翻天覆地的变化,显示器件从一开始的CRT发展到现在主流的LCD显示器与OLED显示器,可以说,显示无处不在,从智能手表、手机、平板电脑到家用电视,每个人每天面对显示屏幕的时间在不断增加。对此,显示器件导致的蓝光危害现象收到越来越多人的关注,特别是针对青少年群体,蓝光的对视网膜的危害成为了社会关注的问题。现在市面上存在的各种防蓝光的薄膜,大多是通过将一部分的有害蓝光过滤掉,不难发现,单纯地将蓝光过滤掉,会造成显示画面的色彩偏差,正常在画面在贴了防蓝光的薄膜后会发生偏红的现象。根据研究调查发现,东方人和西方人的眼球结构存在微小的区别,造成了东方人的眼睛对暖色的灯光会产生不适应的现象。因此,亟需寻找一种既能够将减少有害蓝光,又能够很好地维持显示器件白平衡的防蓝光技术手段。
发明内容
根据本申请的一个方面,提供了一种防蓝光材料,该材料利用钙钛矿量子点将对人眼有害的短波长蓝光转化为对人眼无害或者低伤害的长波长蓝光,同时避免蓝光损失,保证显示器件的白平衡不发生剧烈变化。
所述的防蓝光材料,其特征在于,包括基质和钙钛矿量子点;所述钙钛矿量子点将波长小于455nm的蓝光转化为波长不低于460nm的蓝光。
可选地,所述钙钛矿量子点将波长415~455nm的蓝光转化为波长位于460~480nm之间的蓝光。
可选地,所述钙钛矿量子点分散在所述基质中;或者
所述钙钛矿量子点涂覆在所述基质的表面。
可选地,所述防蓝光材料为防蓝光膜或防蓝光涂层。
可选地,所述基质为透明的基质。
可选地,所述基质的材料为高分子树脂。
可选地,所述基质的材料选自聚偏氟乙烯、聚甲基丙烯酸甲酯、聚醋酸乙烯酯、醋酸纤维素、聚砜、聚酰胺、聚酰亚胺、聚碳酸酯、聚苯乙烯、聚氯乙烯、聚乙烯醇、透明ABS塑料、聚丙烯腈中的至少一种
可选地,所述钙钛矿量子点包括选自具有式I所示的结构式的量子点中至少一种;
APbX3式I
其中,A选自Cs+、CH3NH3 +中的至少一种;X选自Cl-、Br-、I-中的至少一种。
可选地,X为Cl-、Br-的混合,其中Cl-、Br-的摩尔比为(1~10):1。X 为Cl-、I-的混合,其中Cl-、I-的摩尔比为(1~20):1。X中Cl-与Br-、Cl-与 I-的摩尔比调整,可以实现钙钛矿量子点的吸收光谱与发射光谱的调节。
可选地,所述钙钛矿量子点的发光效率不低于80%。
可选地,所述基质与钙钛矿量子点的质量比为(5~50):1。
可选地,所述防蓝光涂层的厚度为0.001~1mm。
可选地,所述防蓝光膜的厚度为0.05~2mm。
根据本申请的另一个方面,提供一种所述的防蓝光材料的制备方法。该方法操作简单,可控性高,适于规模化生产。
所述的防蓝光材料的制备方法,其特征在于,所述的防蓝光材料的制备方法选自方法一、方法二;
方法一:
所述的防蓝光材料的制备方法包括以下步骤:
将含有钙钛矿量子点前驱体、基质的材料的溶液,成型,干燥,得到所述防蓝光膜;
方法二:
将含有钙钛矿前驱体的溶液涂覆在所述基质的表面,干燥,得到所述防蓝光涂层。
可选地,所述钙钛矿量子点前驱体包括AX和PbX2;
其中,A选自Cs+、CH3NH3 +中的至少一种;X独立地选自Cl-、Br-、 I-中的至少一种。
可选地,AX和PbX2的摩尔比为(0.8~1):(0.8~1)。
可选地,所述含有钙钛矿量子点前驱体、基质的材料的溶液中 (AX+PbX2)与基质的材料的质量比为1:(5~50)。
可选地,所述含有钙钛矿量子点前驱体、基质的材料的溶液中 (AX+PbX2)与溶剂的质量比为1:(5~20)。
可选地,所述溶剂选自DMF(N,N-二甲基甲酰胺)、DMSO(二甲基亚砜)、TMP(磷酸三甲酯)、TEP(磷酸三乙酯)、NMP(N-甲基吡咯烷酮)、DMAc(二甲基乙酰胺)中的至少之一。
可选地,所述成型的方法包括:涂覆、刮涂、静电纺丝、浸渍法、提拉法、旋涂法、喷涂法、喷墨打印法。
可选地,所述干燥的条件包括:真空加热干燥、鼓风加热干燥、溶剂自然挥发,加热温度为30~150℃之间。
根据本申请的另一个方面,提供一种防蓝光复合膜。该复合膜不仅能够将有害的短波长蓝光转化为无害的或者低伤害的长波长蓝光,而且能够维持显示的白平衡。
所述防蓝光复合膜,其特征在于,包括阻隔膜层;和
所述的防蓝光材料或根据所述的制备方法制备的防蓝光材料;
所述阻隔膜层叠在所述基于钙钛矿量子点的防蓝光材料上。
可选地,所述阻隔膜层至少为两层;
所述阻隔膜层分别层叠在所述基于钙钛矿量子点的防蓝光材料的上下两个表面上。
可选地,所述的防蓝光复合膜,从上到下依次为:阻隔膜层、基于钙钛矿量子点的防蓝光材料、阻隔膜层。
可选地,所述阻隔膜层的总厚度为15um~500um。所述阻隔膜层的厚度调控对红光、绿光的透过率;防蓝光材料转换蓝光,补充了白光需要的蓝光成分,结合透过率的调整,维持白平衡。
可选地,所述阻隔层膜的材料选自聚偏二氯乙烯薄膜、乙烯-乙烯醇共聚物薄膜、间二甲基胺和已二酸缩聚物薄膜、氧化物镀覆薄膜。
可选地,所述阻隔膜层对红光的透过率为80%~95%;所述阻隔膜层对绿光的透过率为80%~95%。
根据本申请的另一个方面,提供任一项显示器件,包含所述的防蓝光涂层、根据所述的制备方法制备的防蓝光涂层、任一项所述的防蓝光涂层。
本申请能产生的有益效果包括:
1)本申请所提供的防蓝光材料,利用蓝光钙钛矿量子点材料的斯托克斯位移小、发光效率高的优点,尽可能多地将对人眼有害的415-455波段的蓝光转换成460-480nm波段的蓝光。
2)本申请所提供的防蓝光材料制备方法。该方法操作简单,可控性高,适于规模化生产。
3)本申请所提供的防蓝光复合膜,相比于传统的单吸收或者过滤型的防蓝光膜(问题在于过滤掉的蓝光浪费,白平衡变化较大,明显感觉显示的画面偏红),本方案可以将有害波段的蓝光高效率地转换为显示器件或人眼所需的蓝光,一方面避免了能量损失,另一方面可以更好地保证显示器件的白平衡在附加防蓝光膜后不发生剧烈地变化。测试结果表明,显示器件的原始白点坐标为(0.269,0.318),在加了防蓝光膜后,白点色坐标可以通过对绿光和红光波段透过率的微调,将白点色坐标调整到 (0.261,0.321)。
附图说明
图1为本申请基于钙钛矿量子点的防蓝光结构示意图。
图2为本申请CH3NH3PbCl3的钙钛矿量子点的吸收与发射光谱。
图3为本申请中的显示器件在白平衡下测得的光谱。
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料均通过商业途径购买。
本申请的实施例中分析方法如下:
利用FLSP920荧光光谱仪进行荧光发射光谱分析。
本申请提供一种基于钙钛矿量子点的防蓝光涂层,涂层包括透明基质与钙钛矿量子点,透明基质的作用作为钙钛矿量子点的载体,钙钛矿量子点可以均匀分散在透明基质中,也可以涂覆在透明基质的表面。本发明所采用的蓝光钙钛矿量子点具有斯托克斯位移小、发光效率高的特点,可以将有害的蓝光部分(415-455nm)尽可能的吸收并转化为显示器件中所必须的蓝光(460-480nm),在降低蓝光危害实现健康显示的同时尽可能地减少色度变化和亮度损失。
本申请中基于钙钛矿量子点的防蓝光结构示意图,在该器件结构中,从下到上依次为:阻隔膜层、钙钛矿量子点防蓝光层、阻隔膜层。在钙钛矿量子点防蓝光层两侧加上阻隔膜层,一方面可以提高钙钛矿量子点防蓝光层的稳定性,另一方面可以根据阻隔膜的厚度对薄膜的透光率进行微调,而透过率的微调可以对显示器件的白平衡进行微调。在钙钛矿量子点防蓝光层中,包括两个部分,透明树脂基质以及钙钛矿量子点,所述透明树脂基质材料为PAN、PVDF等透明材料,该树脂材料可以溶解于DMF极性溶剂中,所述钙钛矿量子点材料的化学通式为APbX3,其中A为Cs离子或者CH3NH3离子,X为Cl、I或Br,通过X中Cl、I与Br的摩尔比例调整,可以实现钙钛矿量子点的吸收光谱与发射光谱的调节。
实施例1基于钙钛矿量子点的防蓝光材料的制备
方法一:
将钙钛矿前驱体有机胺盐CH3NH3Cl(0.3375g,5mmol)、钙钛矿前驱体金属盐PbCl2(1.3906g,5mmol)、基质聚丙烯腈(PAN,35g)加入 200mL DMF中,得到均匀的溶液,取部分所述溶液置于成型模具中,80℃下干燥2小时得到厚度为1mm的基于钙钛矿量子点CH3NH3PbCl3的防蓝光膜,记为F-1。
方法二:
将钙钛矿前驱体有机胺盐CH3NH3Cl(0.135g,2mmol)、钙钛矿前驱体金属盐PbCl2(0.6953g,2.5mol)、基质聚丙烯腈(PVDF,10g)加入 300mL DMF中,得到均匀的溶液,取部分所述溶液通过喷涂的方式涂覆于已经成型的基质聚甲基丙烯酸甲酯(PMMA)表面,60℃下干燥1小时得到厚度为0.05mm的基于钙钛矿量子点CH3NH3PbCl3的防蓝光涂层,记为F-2。
实施例2基于钙钛矿量子点的防蓝光材料的制备
方法一:
将钙钛矿前驱体有机铵盐CH3NH3Cl(0.3375g,5mmol)、钙钛矿前驱体金属盐PbBr2(1.468g,4mol)、基质聚丙烯腈(PAN,20g)加入200mL DMF中,得到均匀的溶液,取部分所述溶液置于成型模具中,90℃下干燥2小时得到厚度为0.5mm的基于钙钛矿量子点CH3NH3PbCl2Br的防蓝光膜,记为F-3。
方法二:
将钙钛矿前驱体有机铵盐CH3NH3Cl(0.3375g,5mmol)、钙钛矿前驱体金属盐PbBr2(1.468g,4mol)、基质聚丙烯腈(PAN,10g)加入500mL DMF中,得到均匀的溶液,取部分,将所述溶液涂覆于已经成型的基质聚丙烯腈(PAN)光滑平整表面,100℃下干燥0.5小时得到厚度为0.01mm 的基于钙钛矿量子点CH3NH3PbCl2Br的防蓝光涂层,记为F-4。
实施例3基于钙钛矿量子点的防蓝光材料的制备
方法一:
将钙钛矿前驱体有机铵盐CH3NH3Br(0.448g,4mmol)、钙钛矿前驱体金属盐PbBr2(1.835g,5mmol)、基质聚丙烯腈(PAN,10g)加入200 mLDMSO中,得到均匀的溶液,将所述溶液置于成型模具中,120℃下干燥1小时得到厚度为0.2mm的基于钙钛矿量子点CH3NH3PbBr3的防蓝光膜,记为F-5。
方法二:
将钙钛矿前驱体有机铵盐CH3NH3Cl(0.224g,2mmol)、钙钛矿前驱体金属盐PbBr2(0.9175g,2.5mmol)、基质聚丙烯腈(PAN,10g)加入 200mLDMF中,得到均匀的溶液,取部分所述溶液涂覆于已经成型的基质PET表面,40℃下干燥3小时得到厚度为0.001mm的基于钙钛矿量子点CH3NH3PbBr3的防蓝光涂层,记为F-6。
实施例4基于钙钛矿量子点的防蓝光材料的制备
方法一:
将钙钛矿前驱体金属盐CsCl(0.8418g,5mmol)、钙钛矿前驱体金属盐PbCl2(1.3906g,5mmol)、基质聚丙烯腈(PAN,25g)加入250mLDMF 中,得到均匀的溶液,取部分所述溶液置于成型模具中,90℃下干燥2小时得到厚度为0.8mm的基于钙钛矿量子点的防蓝光膜,记为F-7。
方法二:
将钙钛矿前驱体金属盐CsCl(0.4209g,2.5mmol)、钙钛矿前驱体金属盐PbCl2(0.6953g,2.5mmol)、基质聚丙烯腈(PAN,5g)加入300mLDMF 中,得到均匀的溶液,将所述溶液涂覆于PET基膜表面,65℃下干燥3 小时得到厚度为0.06mm的基于钙钛矿量子点的防蓝光涂层,记为F-8。
实施例5基于钙钛矿量子点的防蓝光复合膜的制备
基于钙钛矿量子点的防蓝光复合膜包括:阻隔膜层;和
基于钙钛矿量子点的防蓝光材料;所述阻隔膜层叠在所述基于钙钛矿量子点的防蓝光材料上。
如图1基于钙钛矿量子点的防蓝光结构示意图所示,在该器件结构中,从下到上依次为:阻隔膜层、钙钛矿量子点防蓝光层、阻隔膜层。在F-1 的上下表面分别涂覆一层胶黏剂,然后将阻隔膜层分别层叠到上下表面上,得到M-1,阻隔膜层的总厚度(两侧之和)为100μm。按照该操作,得到M-3、M-5、M-7。
在F-2涂覆钙钛矿量子点防蓝光层的表面上涂覆一层胶黏剂,然后将阻隔膜层层叠到该表面上,得到M-2,阻隔膜层的厚度为400μm。按照该操作,得到M-4、M-6、M-8。
图1为本发明中基于钙钛矿量子点的防蓝光结构示意图,在该器件结构中,从下到上依次为:阻隔膜层、钙钛矿量子点防蓝光层、阻隔膜层。在钙钛矿量子点防蓝光层两侧加上阻隔膜层,一方面可以提高钙钛矿量子点防蓝光层的稳定性,另一方面可以根据阻隔膜的厚度对薄膜的透光率进行微调,而透过率的微调可以对显示器件的白平衡进行微调。
实施例6性能测试
6.1基于钙钛矿量子点的防蓝光涂层F-1~F-8的吸收与发射光谱测试
对实施例1~4中制备的基于钙钛矿量子点的防蓝光材料F-1~F-8进行吸收与发射光谱测试。典型的吸收与发射光谱图如图2所示,对应样品F-1。 CH3NH3PbCl3的钙钛矿量子点的吸收与发射光谱,钙钛矿量子点的吸收位置与发射峰之间的位移较小,称为斯托克斯位移小,同时该组分的钙钛矿量子点的PLQY为80%以上,可以保证将415-455nm的有害蓝光吸收后,高效率地转换到460-480nm波段。从而对显示器件中所需的蓝光组分进行一定地补充,没有办法校正回来的白平衡,再通过调节防蓝光膜中对绿光、红光的透过率进行微调。
6.2基于钙钛矿量子点的防蓝光复合膜M-1~M-8的显示性能测试
对实施例5制备的基于钙钛矿量子点的防蓝光复合膜M-1~M-8进行显示性能测试。
典型的测试结果如图3所示,对应防蓝光复合膜M-1色坐标为 (0.269,0.318),加上钙钛矿量子点防蓝光膜后,将455nn之前的蓝光吸收,部分转换到了475nm附近,再通过两侧阻隔膜的总厚度控制到100μm,将薄膜的整体透过率调整至92%,此时得到的显示器件的色坐标为 (0.261,0.321)。在实际制备工艺中,可以对蓝光钙钛矿量子点的吸收、阻隔膜的透过率进行调整,从而获得最佳的显示效果。
实施例7基于钙钛矿量子点的防蓝光复合膜在显示器件中的应用
将本发明中制备的M-1防蓝光复合膜切割成55英寸,并在其中一侧印刷上双面粘胶,并贴附到现有某品牌的55英寸液晶电视显示屏上,从而达到防蓝光的效果。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (14)
1.一种防蓝光复合膜,其特征在于,包括:阻隔膜层和防蓝光材料;
所述阻隔膜层叠在所述防蓝光材料上;
所述阻隔膜层对红光的透过率为80%~95%;所述阻隔膜层对绿光的透过率为80%~95%;
所述防蓝光材料包括基质和钙钛矿量子点;所述钙钛矿量子点将波长小于455nm的蓝光转化为波长不低于460nm的蓝光;
所述钙钛矿量子点包括选自具有式I所示的结构式的量子点中至少一种;
APbX3式I
其中,A选自Cs+、CH3NH3 +中的至少一种;X选自Cl-、Br-、I-中的至少一种;
所述基质与钙钛矿量子点的质量比为(5~50):1。
2.根据权利要求1所述的防蓝光复合膜,其特征在于,所述钙钛矿量子点分散在所述基质中;或者
所述钙钛矿量子点涂覆在所述基质的表面。
3.根据权利要求1所述的防蓝光复合膜,其特征在于,所述防蓝光材料为防蓝光涂层或防蓝光膜。
4.根据权利要求1所述的防蓝光复合膜,其特征在于,所述基质为透明的基质。
5.根据权利要求1所述的防蓝光复合膜,其特征在于,所述基质的材料为高分子树脂。
6.根据权利要求1所述的防蓝光复合膜,其特征在于,所述基质的材料选自聚丙烯腈、聚偏氟乙烯、聚甲基丙烯酸甲酯、聚醋酸乙烯酯、醋酸纤维素、聚砜、聚酰胺、聚酰亚胺、聚碳酸酯、聚苯乙烯、聚氯乙烯、聚乙烯醇、透明ABS塑料、聚丙烯腈中的至少一种。
7.根据权利要求3所述的防蓝光复合膜,其特征在于,
所述防蓝光涂层的厚度为0.001~1mm。
8.根据权利要求3所述的防蓝光复合膜,其特征在于,
所述防蓝光膜的厚度为0.05~2mm。
9.根据权利要求1所述的防蓝光复合膜,其特征在于,所述的防蓝光材料的制备方法选自方法一、方法二;
方法一:
所述的防蓝光涂层的制备方法包括以下步骤:
将含有钙钛矿量子点前驱体、基质的材料的溶液,成型,干燥,得到所述防蓝光膜;
方法二:
将含有钙钛矿前驱体的溶液涂覆在所述基质的表面,干燥,得到所述防蓝光涂层。
10.根据权利要求1所述的防蓝光复合膜,其特征在于,所述阻隔膜层至少为两层;
所述阻隔膜层分别层叠在所述防蓝光材料的上下两个表面上。
11.根据权利要求10所述的防蓝光复合膜,其特征在于,从上到下依次为:阻隔膜层、基于钙钛矿量子点的防蓝光材料、阻隔膜层。
12.根据权利要求1所述的防蓝光复合膜,其特征在于,所述阻隔膜层的总厚度为15um~500um。
13.根据权利要求1所述的防蓝光复合膜,其特征在于,所述阻隔层膜的材料选自聚偏二氯乙烯薄膜、乙烯-乙烯醇共聚物薄膜、间二甲基胺和已二酸缩聚物薄膜、氧化物镀覆薄膜中的至少一种。
14.一种显示器件,其特征在于,包含权利要求1至13任一项所述的防蓝光复合膜。
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