CN110106572B - 一种周期性发光复合材料的制备方法 - Google Patents

一种周期性发光复合材料的制备方法 Download PDF

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CN110106572B
CN110106572B CN201910339376.8A CN201910339376A CN110106572B CN 110106572 B CN110106572 B CN 110106572B CN 201910339376 A CN201910339376 A CN 201910339376A CN 110106572 B CN110106572 B CN 110106572B
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崔小强
郭子旺
王峰
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Jilin University
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Abstract

本发明涉及一种新型周期性发光复合材料的制备，属于发光材料制备技术领域。所述的复合材料通过静电纺丝技术原位合成CH3NH3PbBr3纳米晶有序的排布在聚合物偏二氟乙烯‑聚六氟丙烯(PVDF‑HFP)纳米纤维上，从而形成周期性发光的复合材料。本发明所制备的复合材料不仅工艺简单而且稳定性好。本发明所获得的周期性发光的复合材料，在发光二极管、传感器、激光器以及高性能光电器件等领域有着广阔的应用前景。

Description

一种周期性发光复合材料的制备方法
技术领域
本发明涉及一种新型周期性发光的复合材料的制备方法，属于发光材料制备技术领域。
背景技术
有机-无机杂化钙钛矿材料从分子尺度上结合了有机材料和无机材料的优点，其独特的无机层和有机层交替堆积形成的量子阱结构使其在量子约束效应和介电约束效应双重作用下，具有独特的光电性能。研究发现CH3NH3PbBr3钙钛矿具有高吸收系数及大的载流子迁移率，使其在光伏领域有着很大的应用潜力。另外CH3NH3PbBr3钙钛矿由于其高色纯度、可调控带隙、半峰宽窄等特点，并且可以通过对有机组分和无机组分进行调控从而实现发光特性的调控，在发光二极管、光电探测器以及激光器等领域有着巨大的应用前景。然而，由于钙钛矿材料的不稳定性以及其制成的发光器件的稳定性差，发光效率低，甚至，发光之间的干扰等等都制约着其在光电领域的发展。因此提升钙钛矿纳米晶分散性和稳定性成为目前研究的重要方向。
发明内容
本发明的目的是提出一种周期性发光的复合材料的制备方法，实现了CH3NH3PbBr3纳米晶在聚合物PVDF-HFP纳米纤维上的原位合成，并有序的分布在聚合物纳米纤维上。
本发明采用如下技术方案：一种周期性发光的复合材料的制备方法，该方法为：将聚合物PVDF-HFP加入到钙钛矿前驱体溶液中，得到纺丝液前驱体；将纺丝液前驱体置于注射器中，然后放入静电纺丝设备中进行静电纺丝，通过锡箔接收，得到周期性发光的复合材料；其中静电纺丝中金属针头作阳极，锡箔作阴极，电压为16KV，纺丝距离为15cm，注射速度为0.1～2mL/h。
进一步地，所述钙钛矿前驱体溶液为：将73.4mg PbBr2和67.2mg CH3NH3Br混合于N,N-二甲基甲酰胺中。
进一步地，纺丝液前驱体中，PVDF-HFP的质量分数为16％-20％。
进一步地，CH3NH3PbBr3纳米晶有序的分布在聚合物PVDF-HFP纳米纤维上。
本发明实现了通过静电纺丝原位合成CH3NH3PbBr3纳米晶并有序的排布在聚合物PVDF-HFP纳米纤维上，从而形成一种周期性发光的复合材料。本发明所制备的周期性发光的复合材料与传统发光材料相比有着较长的荧光寿命，较高的稳定性，更重要的，如此的分散性提升了光学分辨率。
附图说明
图1为本发明所制得的复合材料CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的X射线衍射(XRD)图；
图2为本发明所制得的复合材料CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的扫描电镜(SEM)图；
图3为本发明所制得的复合材料CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的共聚焦暗场和明场像；
图4为本发明所制得的复合材料CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的荧光光谱图(左)与荧光寿命图(右)。
具体实施方式
以下是本发明的具体实施例，并结合附图说明对本发明的技术方案作进一步的描述，但本发明并不限于这些实施例。
实施例1
(1)将73.4mg PbBr2和67.2mg CH3NH3Br放入10mL样品瓶中，加入5mLN,N-二甲基甲酰胺(DMF)，60℃恒温搅拌半小时，得到钙钛矿前驱体。
(2)再向上述前驱体中加入0.948g聚合物PVDF-HFP，60℃恒温搅拌2小时，得到纺丝液前驱体。
(3)取1mL上述纺丝液前驱体置于1mL的注射器中，然后放入静电纺丝设备中，设置电压为16KV，纺丝距离为15cm，注射速度为0.1mL/h，进行静电纺丝，在锡箔上收集到复合的CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维。
本实施例所制备得到的CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维进行X射线衍射(XRD)，结果如图1所示。除了20°附近宽峰(来自PVDF-HFP)，复合物的其它XRD峰位置和模拟的CH3NH3PbBr3一致性的，表明静电纺丝成功的合成了钙钛矿结构。
图2为本实施例制得的CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的扫描电镜(SEM)图。边缘纳米颗粒修饰的纳米级纤维被看到。图3为本实施例制得的CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的共聚焦暗场和明场像。通过从图3中可以看出，周期性发光能够在纤维上被实现，表明通过静电纺丝，已原位合成CH3NH3PbBr3纳米晶并有序的排列在聚合物纳米纤维上，得到了周期性发光的效果。图4为本实施例制得的CH3NH3PbBr3/PVDF-HFP聚合物纳米纤维的荧光光谱图与荧光寿命图。绿色发光光谱进一步证实了，我们所合的材料是周期性发光的聚合物复合材料。而且，此材料展现了较长的荧光寿命，可能得益于PVDF-HFP通过F-N偶极介导的钝化所致。这不仅提升了钙钛矿的分散性，克服光干扰，也将可能提升钙钛矿的稳定性，进而，提升光学应用潜力。也为分辨和研究单颗粒与界面的相互作用提供的可能。
在实施例1的基础上，作如下进一步研究，并发现：
1.固定纺丝距离，设置为15cm；固定注射速度，设置为0.1mL/h；通过改变两极电压得到的聚合物纳米纤维上钙钛矿纳米晶的间距不同。
当电压过大时钙钛矿纳米晶的分布过于密集；当电压过小时钙钛矿纳米晶的分布过于稀疏。
2.固定电场电压，设置为16KV；固定注射速度，设置为0.1mL/h；通过改变纺丝距离得到的聚合物纳米纤维上钙钛矿纳米晶的间距不同。
当纺丝距离过大时，钙钛矿纳米晶的分布过于稀疏；当纺丝距离过小时，钙钛矿纳米晶的分布过于密集。
3.固定电场电压，设置为16KV；固定纺丝距离，设置为15cm；在0.1～2mL/h范围内改变注射速度得到的聚合物纳米纤维上钙钛矿纳米晶的间距大致相同。

Claims (2)

1.一种周期性发光的复合材料的制备方法，其特征在于，该方法为：将聚合物PVDF-HFP加入到钙钛矿前驱体溶液中，得到纺丝液前驱体；将纺丝液前驱体置于注射器中，然后放入静电纺丝设备中进行静电纺丝，通过锡箔接收，得到周期性发光的复合材料；其中静电纺丝中金属针头作阳极，锡箔作阴极，电压为16 KV，纺丝距离为15 cm，注射速度为0.1~2 mL/h；
所述钙钛矿前驱体溶液为：将73.4 mg PbBr2和67.2 mg CH3NH3Br混合于N,N-二甲基甲酰胺中；
纺丝液前驱体中，PVDF-HFP的质量分数为16%-20%。
2.如权利要求1所述方法制备得到的周期性发光的复合材料，其特征在于，CH3NH3PbBr3纳米晶有序的分布在聚合物PVDF-HFP纳米纤维上。
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Citations (3)

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CN101069821A (zh) * 2007-03-06 2007-11-14 天津大学 交联改性的pvdf－hfp超细纤维膜及其制备方法
CN107698907A (zh) * 2017-10-25 2018-02-16 中国地质大学（北京） 一种ZnS/PVDF‑HFP压电复合材料薄膜及其制备方法
CN107938175A (zh) * 2017-11-28 2018-04-20 北京理工大学 一种高取向柔性发光偏振复合纤维薄膜的制备方法及其用途

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KR101265093B1 (ko) * 2008-12-26 2013-05-16 한국과학기술연구원 나노 분말, 나노 잉크 및 마이크로 로드와 그 제조 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101069821A (zh) * 2007-03-06 2007-11-14 天津大学 交联改性的pvdf－hfp超细纤维膜及其制备方法
CN107698907A (zh) * 2017-10-25 2018-02-16 中国地质大学（北京） 一种ZnS/PVDF‑HFP压电复合材料薄膜及其制备方法
CN107938175A (zh) * 2017-11-28 2018-04-20 北京理工大学 一种高取向柔性发光偏振复合纤维薄膜的制备方法及其用途

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