CN114242923A - 一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法 - Google Patents
一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法 Download PDFInfo
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Abstract
本发明属于电致发光器件的技术领域,公开了一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法。所述方法:在ITO基板上依次制备电子传输层、磷化铟量子点发光层、界面修饰层、空穴传输层、空穴注入层及金属阳极;所述界面修饰层为硫醇类化合物界面修饰层;所述硫醇类化合物包括含有硫醇基团的烷烃或芳香族化合物。本发明采用硫醇类化合物对磷化铟量子点发光层进行界面修饰,钝化其薄膜表面缺陷,增强其稳定性,有利于提升磷化铟量子点器件的电流效率和亮度,推动磷化铟量子点器件在下一代显示和照明领域的应用。
Description
技术领域
本发明属于磷化铟量子点光电器件领域,具体涉及一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法。
背景技术
1983年Brus等人发现并报道了CdS纳米晶具有尺寸依赖的荧光性质,揭开了量子点研究的序幕。此后,量子点得到广泛的关注并应用在多个领域,例如生物标记,发光二极管,太阳能电池等。在光电显示领域,由早期的阴极射线管(cathode-ray tube,CRT)到液晶平板显示(liquid-crystal display,LCD),再到如今的有机发光显示(organic lightemitting diode,OLED),显示技术都趋向于厚度越来越薄、重量越来越轻和清晰度越来越高的方向发展。对于现今主流的OLED而言,有机发光材料往往比无机材料具有更差的稳定性,这导致OLED产品通常很难有长的使用寿命。而量子点是一种具有优良稳定性的无机半导体纳米粒子,其光学和电学性质与粒子的大小和化学组成密切相关。因此,胶体量子点因具有宽的光谱可调性、非常窄的半峰全宽(full width at half maxima,FWHM)、高的色纯度和可溶液加工等优异特性,而成为下一代光电显示材料中很有前途的候选者。在众多研究的量子点材料中,镉基量子点发展最为迅速。然而,镉基量子点中的重金属镉会导致严重的慢性疾病和癌症,对人体和环境都有很大的危害,这极大地限制了其大规模商业化应用。因此,大力发展环境友好型的无镉发光量子点具有重大意义。
相对于镉基量子点,InP量子点具有更大的激子波尔半径(量子限域效应更强)、宽的光谱可调性(可以覆盖可见光至近红外范围)以及更大的本征吸收系数等优越特征,从而成为极为突出的镉基量子点替代材料。但是,InP量子点也存在一些固有缺陷,比如电子束缚能力差、量子产率较低以及材料稳定性相对较差等,极大的限制了InP量子点在光电显示的应用。
本发明采用硫醇类化合物界面修饰磷化铟量子点,钝化其薄膜表面缺陷,增强其稳定性,有利于提升磷化铟量子点器件的电流效率和亮度,推动磷化铟量子点器件在下一代显示和照明领域的应用。
发明内容
为了克服现有技术的缺点和不足,本发明的目的在于提供一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法。针对现有的磷化铟量子点稳定性问题,本发明采用了硫醇类化合物对磷化铟量子点进行界面修饰,钝化其薄膜表面缺陷,增强其稳定性,从而解决磷化铟量子点由于配体不稳定导致的器件亮度与发光效率较低的问题。
本发明的目的通过以下技术方案实现:
一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,包括以下步骤:在ITO基板上依次制备电子传输层、磷化铟量子点发光层、界面修饰层、空穴传输层、空穴注入层及金属阳极;
所述界面修饰层为硫醇类化合物界面修饰层;所述硫醇类化合物包括含有硫醇基团的烷烃或芳香族化合物,优选为2-苯乙硫醇、3-甲硫基丙醇中一种以上。所述界面修饰层采用溶液加工工艺成膜;
界面修饰层采用溶液加工工艺成膜时,所采用的溶剂为乙醇、异丙醇等;溶液加工工艺包括旋涂、提拉、刮涂、喷墨打印等溶液加工工艺。
所述电子传输层,是指金属氧化物的无机纳米粒子材料(例如:氧化锌、氧化锌镁、氧化钛中一种以上),具有电子注入和传输的功效;在通过溶液加工制备成膜时,所采用的溶剂可以是乙醇、异丙醇等。所述电子传输层的材料优选为氧化锌镁。电子传输层的厚度为40-80nm。
所述磷化铟量子点发光层的材料包括不同核壳结构及不同粒径大小(例如:2nm、4nm、6nm)的量子点,所述量子点包括核壳结构的InP/ZnS、核壳结构的InP/ZnSe/ZnS等;量子点材料包括红光、绿光、蓝光等量子点,如:核壳结构的绿光InP/ZnS量子点。
所述磷化铟量子点发光层采用溶液加工法(如:旋涂工艺)制备薄膜,其溶剂可以是溶剂为正辛烷、甲苯、二甲苯、氯苯中一种单一溶剂或单一溶剂与高沸点醚类(如:间苯二甲醚,二甲基茴香醚)等共混的复合溶剂。
所述磷化铟量子点发光层的厚度:20-35nm。
所述空穴传输层可以是具有低电离能的芳香族化合物或咔唑类化合物以及有机金属配合物薄膜,优选为4,4',4”-三(咔唑-9-基)三苯胺。
所述空穴传输层具体为4,4',4”-三(咔唑-9-基)三苯胺(TCTA)、聚(9,9-二辛基芴-2,7-二基)-共(4,4'-(N-(4-仲-丁基苯基)二苯胺))(TFB)、聚(N,N'-双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(Poly-TPD)中一种以上;优选为TCTA;
所述空穴传输层的厚度:30-60nm。
所述空穴注入层由以碳或硅做主链的共轭或非共轭高电导体系构成的薄膜;优选为聚苯胺、聚噻吩、聚吡咯、或聚对苯乙炔薄膜,或者无机氧化物材料氧化钼。
所述金属阳极层包括金属铝、金、银等金属材料或者两种以上金属的合金。
所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,具体包括以下步骤:
1)将ITO基板进行氧气等离子处理,然后在ITO基板上通过溶液加工工艺依次制备电子传输层、磷化铟量子点发光层、界面修饰层;
2)在界面修饰层上通过溶液加工工艺或真空蒸镀工艺依次制备空穴传输层、空穴注入层;
3)在空穴注入层上制备金属阳极。
通过溶液加工工艺依次制备电子传输层时,采用的溶剂为乙醇、异丙醇中一种以上;
通过溶液加工工艺制备磷化铟量子点发光层时,溶剂为正辛烷、甲苯、二甲苯、氯苯中一种或其与间苯二甲醚,二甲基茴香醚重一种以上共混的复合溶剂;
通过溶液加工工艺制备界面修饰层时,溶剂为乙醇、异丙醇中一种以上。
本发明的优点和效果:本发明利用硫醇类化合物对磷化铟量子点表面配体进行置换,钝化表面缺陷,实现了硫醇类化合物界面修饰磷化铟量子点电致发光器件,能有效降低量子点器件的启亮电压,提升其电致发光效率与亮度,推动量子点材料在下一代显示和照明领域的应用。
附图说明
图1为本发明的磷化铟量子点电致发光器件结构示意图;1-ITO基板、2-电子传输层、3-磷化铟量子点发光层、4-界面修饰层、5-空穴传输层、6-空穴注入层、7-金属阳极;
图2为实施例1和实施例2的绿光磷化铟量子点电致发光器件性能图;a、b分别为实施例1与实施例2中制备的器件的电流密度-电压-亮度(J-V-I)图和电流效率-电流密度(L-E)图;c为实施例1和2中器件的电致发光(E-L)谱图。
具体实施方式
下面结合具体实施例对本发明作进一步详细地描述,但本发明的实施方式不限于此。本发明的磷化铟量子点电致发光器件结构示意图如图1所示,包括依次层叠的ITO基板1、电子传输层2、磷化铟量子点发光层3、界面修饰层4、空穴传输层5、空穴注入层6及金属阳极7;
界面修饰层为2-苯乙硫醇、3-甲硫基丙醇中一种以上。
实施例1
选用图1所示的器件结构,采用ITO基板,分别用洗液、去离子水、异丙醇超声清洗10分钟,清洗表面污染物,高压氮气吹干后,采用氧气等离子对其进行表面修饰,然后在氮气手套箱内旋涂氧化锌镁作为电子传输层(厚度~70nm),所用溶剂是乙醇;在氧化锌镁之上旋涂绿光磷化铟量子点材料(核壳结构的绿光InP/ZnS量子点)制备量子点发光层(厚度~30nm),所用溶剂是正辛烷;再在绿光磷化铟量子点发光层上旋涂界面修饰层2-苯乙硫醇,所用溶剂是乙醇;最后在高真空蒸镀仓(3×10-4Pa)分别蒸镀空穴传输层4,4',4”-三(咔唑-9-基)三苯胺(厚度~50nm)、空穴注入层MoOx(厚度~10nm)和金属电极Al(厚度~150nm),最后用环氧树脂粘贴玻璃封装片并进行紫外固化封装。
实施例2
选用图1所示的器件结构,采用ITO基板,分别用洗液、去离子水、异丙醇超声清洗10分钟,清洗表面污染物,高压氮气吹干后,采用氧气等离子对其进行表面修饰,然后在氮气手套箱内旋涂氧化锌镁作为电子传输层(厚度~70nm),所用溶剂是乙醇;在氧化锌镁之上旋涂绿光磷化铟量子点材料(核壳结构的绿光InP/ZnS量子点)制备量子点发光层(厚度~30nm),所用溶剂是正辛烷;再在绿光磷化铟量子点发光层上旋涂界面修饰层3-甲硫基丙醇,所用溶剂是乙醇,最后在高真空蒸镀仓(3×10-4Pa)分别蒸镀空穴传输层4,4',4”-三(咔唑-9-基)三苯胺(厚度~50nm)、空穴注入层MoOx(厚度~10nm)和金属电极Al(厚度~150nm),最后用环氧树脂粘贴玻璃封装片并进行紫外固化封装。
图2为实施例1和实施例2的绿光磷化铟量子点电致发光器件性能图;a、b分别为实施例1与实施例2中制备的器件的电流密度-电压-亮度(J-V-I)图和电流效率-电流密度(L-E)图;c为实施例1和2中器件的电致发光(E-L)谱图。
上述列举了本发明的实例方式,但本发明的上述实施方案都只能认为是对本发明的说明而不能限制本发明,权利要求书指出了本发明的范围。因此,只要通过涉及以硫醇类化合物界面修饰磷化铟量子点,采用磷化铟量子点材料作为发光层的电致发光器件,都应认为属于本发明的保护范围。
Claims (10)
1.一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:包括以下步骤:在ITO基板上依次制备电子传输层、磷化铟量子点发光层、界面修饰层、空穴传输层、空穴注入层及金属阳极;
所述界面修饰层为硫醇类化合物界面修饰层;所述硫醇类化合物包括含有硫醇基团的烷烃或芳香族化合物。
2.根据权利要求1所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:所述硫醇类化合物为2-苯乙硫醇、3-甲硫基丙醇中一种以上。
3.根据权利要求1所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:
所述电子传输层为氧化锌、氧化锌镁、氧化钛中的一种以上;电子传输层的厚度为40-80nm;
所述磷化铟量子点发光层的材料包括核壳结构的InP/ZnS量子点、InP/ZnSe/ZnS量子点;所述量子点为红光量子点、绿光量子点、蓝光量子点;
所述磷化铟量子点发光层的厚度为20-35nm。
4.根据权利要求3所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:所述电子传输层为氧化锌镁。
5.根据权利要求1所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:所述空穴传输层为4,4',4”-三(咔唑-9-基)三苯胺、聚(9,9-二辛基芴-2,7-二基)-共(4,4'-(N-(4-仲-丁基苯基)二苯胺))、聚(N,N'-双(4-丁基苯基)-N,N'-双(苯基)联苯胺)中一种以上;
所述空穴传输层的厚度为30-60nm;
所述空穴注入层的材料为聚苯胺、聚噻吩、聚吡咯、聚对苯乙炔、或氧化钼中一种以上;
所述空穴注入层的厚度为6-12nm。
6.根据权利要求5所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:所述空穴传输层为4,4',4”-三(咔唑-9-基)三苯胺;所述空穴注入层为氧化钼。
7.根据权利要求1所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:所述金属阳极层包括金属铝、金、银中一种以上,厚度100~160nm。
8.根据权利要求1所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:具体包括以下步骤:
1)将ITO基板进行氧气等离子处理,然后在ITO基板上通过溶液加工工艺依次制备电子传输层、磷化铟量子点发光层、界面修饰层;
2)在界面修饰层上通过溶液加工工艺或真空蒸镀工艺依次制备空穴传输层、空穴注入层;
3)在空穴注入层上制备金属阳极。
9.根据权利要求8所述硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法,其特征在于:通过溶液加工工艺依次制备电子传输层时,采用的溶剂为乙醇、异丙醇中一种以上;
通过溶液加工工艺制备磷化铟量子点发光层时,溶剂为正辛烷、甲苯、二甲苯、氯苯中一种或其与间苯二甲醚,二甲基茴香醚重一种以上共混的复合溶剂;
通过溶液加工工艺制备界面修饰层时,溶剂为乙醇、异丙醇中一种以上。
10.根据权利要求1~9任一项所述方法得到的电致发光器件,其特征在于:包括依次层叠的在ITO基板、电子传输层、磷化铟量子点发光层、界面修饰层、空穴传输层、空穴注入层及金属阳极。
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