CN114920763B - 一种具有单组分白光和温度门控的磷光光波导材料及其制备方法 - Google Patents

一种具有单组分白光和温度门控的磷光光波导材料及其制备方法 Download PDF

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CN114920763B
CN114920763B CN202210536349.1A CN202210536349A CN114920763B CN 114920763 B CN114920763 B CN 114920763B CN 202210536349 A CN202210536349 A CN 202210536349A CN 114920763 B CN114920763 B CN 114920763B
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闫东鹏
周博
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Abstract

本发明公开了一种具有单组分白光和温度门控的磷光光波导材料及其制备方法。该方法的具体操作为：将苯并三唑或5‑甲基苯并三唑、金属卤化盐、盐酸或氢溴酸混合，加水超声溶解后，加热或不加热，溶剂挥发后析出晶体，即得具有单组分白光和温度门控的磷光光波导材料。本发明将苯并三唑类有机物与金属卤化物通过自组装形成一类新型零维配位结构的材料。所合成的系列金属‑有机卤化物材料具有激发态能级可调、光波导损耗低、热稳定性好等优点。本发明不仅实现了基于荧光‑磷光双发射的单组分白光发射，还利用磷光的温敏性开发了一类高安全性和高信息密度的微型温度门控磷光有源光波导系统，并展示了这类新型波导材料在光子信息加密方面的应用。

Description

一种具有单组分白光和温度门控的磷光光波导材料及其制备 方法
技术领域
本发明属于光功能材料技术领域，特别涉及一种基于荧光-磷光双发射的单组分白光发射和温度门控磷光光波导金属卤化物材料及其制备方法。
背景技术
基于单组分材料实现荧光-磷光双发射一直是固体发光领域中备受关注的问题。根据洪特规则，激发三线态能级比对应的单线态能级更低，因此，三线态激子产生的磷光发射比单线态激子产生的荧光发射波长更长。此外，相比于荧光，具有三线态激子属性的磷光对环境中的水、氧气、温度更加敏感。因此，通过调控激发单线态和三线态能级位置，不仅有望实现基于荧光-磷光双发射的单组分白光发射，还能利用磷光的温敏性来构建温度门控磷光光波导系统。金属-有机卤化物材料由于具有可调的化学组成和激发态性质，在照明显示、信息加密、光电探测、催化等领域受到了各界研究者们越来越多的关注。
发明内容
本发明的目的在于提供一种具有单组分白光和温度门控的磷光光波导材料及其制备方法。本发明采用易于操作的溶剂挥发法，与有机物前驱体相比，所合成的系列金属-有机卤化物材料具有激发态能级可调、光波导损耗低、热稳定性好等优点。本发明为具有优质光学特性的新型智能材料、传感材料和光学信息加密器件的制备提供了新的思路和途径。
所述的具有单组分白光和温度门控的磷光光波导材料的制备方法为：将苯并三唑或5-甲基苯并三唑、金属卤化盐、盐酸或氢溴酸混合，加水超声溶解后，加热或不加热，溶剂挥发后析出晶体，即得具有单组分白光和温度门控的磷光光波导材料。
所述的金属卤化盐为氯化锌、氯化镉、溴化锌或溴化镉。
所述的苯并三唑或5-甲基苯并三唑、金属卤化盐、盐酸或氢溴酸的摩尔比范围为1:0.5-1.5:0.5-1.5。
本发明将苯并三唑类有机物与金属卤化物通过自组装形成一类新型零维配位结构的金属-有机卤化物材料。苯并三唑类有机物与金属卤化物的自组装能有效促进单线态和三线态之间的系间窜越，实现荧光-磷光双发射。通过调节配位卤离子的种类，可以进一步改变单线态和三线态能级位置，实现单组分标准白光发射。同时，由于存在强烈的配位作用和分子间相互作用，所制备的金属-有机卤化物磷光材料具有很好的热稳定性，在模拟各种极端自然温度条件下(温度范围>300K)仍然能实现磷光有源光波导特性。并且在不同温度下，有源光波导的磷光发射波长呈线性变化规律，具有温控多色磷光性质。本发明不仅实现了基于荧光-磷光双发射的单组分白光发射，还利用磷光的温敏性开发了一类高安全性和高信息密度的微型温度门控磷光有源光波导系统，并展示了这类新型波导材料在光子信息加密方面的应用。
附图说明
图1实施例1、2、3制备的金属-有机卤化物配位结构图。
图2极端温度下实施例1制备的金属-有机卤化物荧光(Prompt模式)和磷光光波导(Delayed模式)衰减曲线。
图3实施例3制备的金属-有机卤化物白光LED器件和相应色坐标图。
具体实施方式
实施例1
将苯并三唑119.1mg、氯化锌136.3mg、与36wt％浓盐酸80μL溶解于5mL去离子水中，超声5分钟后放入20mL的玻璃瓶中；用保鲜膜密封玻璃瓶，然后在保鲜膜上扎5个针孔；再将反应混合物加热至45℃，维持此温度18小时，待溶剂挥发后，即可得到一维棒状晶体，将该单晶分离出来，依次经洗涤、干燥处理，得到目标产物。
对产物进行表征：
对单晶产物进行单晶X-射线衍射分析可知，金属-有机卤化物属于单斜晶系，P21/n空间群，其中Zn2+以四配位的方式分别和两个氯离子以及两个来自苯并三唑上的氮原子进行配位形成独立的零维配位结构(如图1)。晶体生长主要依靠有机配体和氯离子之间强烈的氢键相互作用和有机配体之间的π-π相互作用。
由光谱分析可知，在365纳米处激发，该金属-有机卤化物的荧光发射峰和磷光发射峰分别在392纳米和583纳米。该金属-有机卤化物在紫外光激发下呈现出浅蓝光发射，而在停止光激发后，则可以发出1秒左右人眼可见的橙红色磷光余辉。发光寿命为0.68毫秒，发光量子产率为13.01％。
热重-差式扫描量热测量即TGA-DSC表征显示该金属-有机卤化物可以稳定到479K。
变温光波导表征显示该金属-有机卤化物在不同温度条件下(典型条件：400K和90K)具有荧光和磷光光波导特性，其光波导损耗系数在90K条件下最低可达到6.2×10–4dB/mm(如图2)，低于大多数分子光波导材料。此外，磷光光波导的发射波长呈线性变化规律，具有温度控制多色磷光光射性质。
实施例2
将5-甲基苯并三唑133.1mg、氯化锌136.3mg、与36wt％浓盐酸80μL溶解于5mL去离子水中，超声5分钟后放入20mL的玻璃瓶中；用保鲜膜密封玻璃瓶，然后在保鲜膜上扎5个针孔；再将反应混合物在45℃条件下，维持此温度18小时，待溶剂挥发后，即可得到一维棒状晶体，将该单晶分离出来，依次经洗涤、干燥处理，得到目标产物。
对产物进行表征：
对单晶产物进行单晶X-射线衍射分析可知，金属-有机卤化物属于三斜晶系，P-1空间群，其中Zn2+以四配位的方式分别和两个氯离子以及两个来自5-甲基苯并三唑上的氮原子进行配位形成独立的零维配位结构(如图1)。晶体生长主要依靠有机配体和氯离子之间强烈的氢键相互作用和有机配体之间的π-π相互作用。
由光谱分析可知，在365纳米处激发，该金属-有机卤化物的荧光发射峰和磷光发射峰分别在376纳米和583纳米。该金属-有机卤化物在紫外光激发下呈现出蓝光发射，而在停止光激发后，则可以发出1秒左右人眼可见的橙红色磷光余辉。发光寿命为1.84毫秒，发光量子产率为5.43％。
热重-差式扫描量热测量即TGA-DSC表征显示该金属-有机卤化物可以稳定到501K。
实施例3
将苯并三唑119.1mg、溴化锌225.2mg、与47wt％氢溴酸120μL溶解于5mL去离子水中超声5分钟后放入20mL的玻璃瓶中。用保鲜膜密封玻璃瓶，然后在保鲜膜上扎5个针孔；再将反应混合物加热至45℃，维持此温度18小时，待溶剂挥发后，即可得到一维棒状晶体，将该单晶分离出来，依次经洗涤、干燥处理，得到目标产物。
LED器件制备：
将上述制备的金属-有机卤化物与高折光LED贴片硅胶按质量比1:2充分混合；随后将混合物涂覆在商用365纳米紫外芯片上即可制得LED器件(如图3)。
对产物进行表征：
对单晶产物进行单晶X-射线衍射分析可知，金属-有机卤化物属于单斜晶系，P21/n空间群，其中Zn2+以四配位的方式分别和两个溴离子以及两个来自苯并三唑上的氮原子进行配位形成独立的零维配位结构(如图1)。晶体生长主要依靠有机配体和溴离子之间强烈的氢键相互作用和有机配体之间的π-π相互作用。
由光谱分析可知，在365纳米处激发，该金属-有机卤化物的荧光发射峰和磷光发射峰分别在408纳米和574纳米。该金属-有机卤化物在紫外光激发下呈现出白光发射，而在停止光激发后，则可以发出1秒左右人眼可见的橙红色磷光余辉。发光寿命为22.10毫秒，发光量子产率为8.01％。
热重-差式扫描量热测量即TGA-DSC表征显示该金属-有机卤化物可以稳定到493K。

Claims (1)

1.一种具有单组分白光和温度门控的磷光光波导材料的制备方法，其特征在于，所述制备方法的具体操作为：将苯并三唑或5-甲基苯并三唑、金属卤化盐、盐酸或氢溴酸混合，加水超声溶解后，加热或不加热，溶剂挥发后析出晶体，即得具有单组分白光和温度门控的磷光光波导材料；
所述的金属卤化盐为氯化锌或溴化锌；
所述的苯并三唑或5-甲基苯并三唑、金属卤化盐、盐酸或氢溴酸的摩尔比范围为1:0.5-1.5: 0.5-1.5。
CN202210536349.1A 2022-05-17 2022-05-17 一种具有单组分白光和温度门控的磷光光波导材料及其制备方法 Active CN114920763B (zh)

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Mechanochemical and thermal formation of 1H-benzotriazole coordination polymers and complexes of 3d-transition metals with intriguing dielectric properties;Franziska A. Brede等;Dalton Transactions;第45卷;10609–10619 *
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