CN114989020A - 一种三维有机-无机杂化钙钛矿半导体晶体及其制备方法和用途 - Google Patents

一种三维有机-无机杂化钙钛矿半导体晶体及其制备方法和用途 Download PDF

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CN114989020A
CN114989020A CN202210658148.9A CN202210658148A CN114989020A CN 114989020 A CN114989020 A CN 114989020A CN 202210658148 A CN202210658148 A CN 202210658148A CN 114989020 A CN114989020 A CN 114989020A
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罗军华
范一蓬
姬成敏
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Mindu Innovation Laboratory
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Abstract

本发明提供一种三维有机‑无机杂化钙钛矿半导体晶体及其制备方法和用途，属于光电功能晶体材料领域。该化合物化学式为CH3NH2C3H9N)Pb2Br6，室温下为正交晶系，其空间群为Pbam。该晶体器件表现出明显的光电导效应，光电流和暗电流的比值(Iph/Idark)可以达到1.14×103。本发明的卤化物钙钛矿晶体具有良好的热稳定性，生长条件宽松。在制备过程中所采用的原料易得、化学合成路线简单、反应条件温和，容易得到大尺寸单晶，作为光电探测器件具有潜在的实施价值。

Description

一种三维有机-无机杂化钙钛矿半导体晶体及其制备方法和 用途
技术领域
本发明属于功能晶体材料领域中的人工晶体材料领域，具体涉及一种三维有机-无机杂化钙钛矿半导体晶体及其制备方法和用途。
背景技术
卤化铅钙钛矿因其易于制备和优异的耐缺陷物理性能，在光电探测等领域具有广阔的应用前景，成为光电子器件半导体材料的研究热点。其中，三维(3D)APbX3(A＝有机阳离子，X＝Cl,Br,I)钙钛矿因其独特的三维结构和优越的光电性能而倍受青睐。PbX3采用立方钙钛矿结构，由具有共享角的PbX6八面体的三维卤化铅骨架组成，A阳离子驻留在相邻PbX6八面体形成的孔中。但其A位阳离子的选择受到Goldschmidt容忍因子的限制，为了容纳超出公差因子可接受范围的阳离子，A阳离子受限于小尺寸的[CH3NH3]+和[NH2(CH)NH2]+等阳离子，通常会形成低维结构，这些结构至少会阻碍电荷在一个方向上的迁移。尽管，近年来，人们已经做出了巨大努力来扩展3D卤化物钙钛矿，但是，其合成仍是一个巨大的挑战，3D卤化物钙钛矿结构仍然非常稀少。
由于三维有机-无机杂化钙钛矿半导体晶体稳定性高、光电性能优异，且其制成的光电器件具有重要的理论和实际价值，因此需要研发新的三维有机-无机杂化钙钛矿晶体。
发明内容
本发明的目的在于提供一种三维有机-无机杂化钙钛矿半导体晶体及其制备方法和用途，本发明的三维有机-无机杂化钙钛矿半导体晶体稳定性高、光电性能优异，制备成平面光电探测器可实现对本征吸收光谱的高灵敏度探测，用作光电探测器件具有潜在的应用价值。
本发明的技术方案如下：
方案一)
一种三维有机-无机杂化钙钛矿半导体晶体，所述的有机-无机杂化半导体材料的化学式为(CH3NH2C3H9N)Pb2Br6。
进一步地，一种三维有机-无机杂化钙钛矿半导体晶体属于正交晶系，空间群为Pbam。
进一步地，所述晶体的晶胞参数为：
Figure BDA0003689236910000021
Figure BDA0003689236910000022
α＝90°，β＝90°，γ＝90°，Z＝2，
Figure BDA0003689236910000023
方案二)
三维有机-无机杂化钙钛矿半导体晶体的制备方法，包括以下步骤：
称取3-甲氨基丙胺、三水合乙酸铅置于烧杯中，再向烧杯中加入氢溴酸水溶液，加热到95～100℃并搅拌至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封放入65℃-70℃的烘箱中，以0.8～1℃/天的速率冷却至室温，即得到所述的三维有机-无机杂化钙钛矿半导体晶体；
所述的3-甲氨基丙胺、三水合乙酸铅、HBr的摩尔比为1：2：(8～15)。
进一步地，所述的HBr水溶液中HBr的质量分数为47～48％。
方案三)
三维有机-无机杂化钙钛矿半导体晶体的用途，所述的三维有机-无机杂化钙钛矿半导体晶体用于制备光电探测器件。
X射线单晶衍射的结果表明：该化合物的分子式为C4H14Br6Pb2N2，结构简式为(CH3NH2C3H9N)Pb2Br6。其中，CH3NH2C3H9N代表3-甲氨基丙铵阳离子。在室温下(CH3NH2C3H9N)Pb2Br6晶体属于正交晶系，空间群为Pbam。该化合物的晶胞参数为
Figure BDA0003689236910000024
α＝90°，β＝90°，γ＝90°，Z＝2，单胞体积为
Figure BDA0003689236910000025
较之前的现有技术，本发明具有以下有益效果：本发明制备了一种三维有机-无机杂化钙钛矿半导体晶体，该晶体稳定性高、光电性能优异，该晶体制备成平面光电探测器可实现对本征吸收光谱的高灵敏度探测。利用波长为405nm的激光照射该单晶晶体探测器件，测试其光电响应。当入射光的功率密度为34.53mW/cm2时，该晶体器件表现出明显的光电导效应，光电流和暗电流的比值(Iph/Idark)可以达到1.14×103。该结果表明该材料用作光电探测器件具有潜在的应用价值。
附图说明
图1是实施例制得的(CH3NH2C3H9N)Pb2Br6晶体的照片；
图2是本发明中(CH3NH2C3H9N)Pb2Br6晶体的结构堆积图；
图3是本发明中(CH3NH2C3H9N)Pb2Br6的紫外可见吸收光谱；
图4是本发明中(CH3NH2C3H9N)Pb2Br6晶体的光电导性能。
具体实施方式
下面结合具体实施例对本发明进一步阐述
实施例1
三维有机-无机杂化钙钛矿晶体(CH3NH2C3H9N)Pb2Br6的制备
称取3-甲氨基丙胺、三水合乙酸铅置于烧杯中，再向烧杯中加入氢溴酸水溶液，加热到98℃并搅拌至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封放入68℃的烘箱中，以0.9℃/天的速率冷却至室温，即得到所述的三维有机-无机杂化钙钛矿半导体晶体；所述的三维有机-无机杂化钙钛矿半导体晶体为黄色片状晶体；
所述的3-甲氨基丙胺、三水合乙酸铅、HBr的摩尔比为1：2：10。
所述的HBr水溶液中HBr的质量分数为48％。
实施例2
制备三维有机-无机杂化钙钛矿晶体(CH3NH2C3H9N)Pb2Br6
称取3-甲氨基丙胺(1.2×10-2mol)、三水合乙酸铅(2.4×10-2mol)置于烧杯中，再向烧杯中加入氢溴酸水溶液，加热到95℃并搅拌至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封放入65℃的烘箱中，以0.8℃/天的速率冷却至室温，即得到所述的三维有机-无机杂化钙钛矿半导体晶体；
所述的3-甲氨基丙胺、三水合乙酸铅、HBr的摩尔比为1：2：8。
所述的HBr水溶液中HBr的质量分数为48％。
本实施例制备得到的黄色片状晶体的尺寸为20×2×2mm3(如图1所示)，即(CH3NH2C3H9N)Pb2Br6晶体。
实施例3
称取3-甲氨基丙胺、三水合乙酸铅置于烧杯中，再向烧杯中加入氢溴酸水溶液，加热到100℃并搅拌至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封放入70℃的烘箱中，以1℃/天的速率冷却至室温，即得到所述的三维有机-无机杂化钙钛矿半导体晶体；所述的三维有机-无机杂化钙钛矿半导体晶体为黄色片状晶体；
所述的3-甲氨基丙胺、三水合乙酸铅、HBr的摩尔比为1：2：15。
所述的HBr水溶液中HBr的质量分数为48％。
上述实施例1-3制得的晶体，经X射线单晶衍射分析，室温下均属于单斜晶系Pbam空间群，晶胞参数为
Figure BDA0003689236910000041
Figure BDA0003689236910000042
α＝90°，β＝90°，γ＝90°，Z＝2，
Figure BDA0003689236910000043
从图2中可以看出，(CH3NH2C3H9N)Pb2Br6采用如下的结构：晶体结构中含有角部和边部共用的PbBr6八面体无机骨架，PbBr6八面体通过边共享方式与相邻八面体连接形成[Pb2Br6]2-二聚体，[Pb2Br6]2-二聚体再通过角共享方式与相邻二聚体连接形成三维网络。三维网络中空隙被取向紊乱的3-甲氨基丙胺阳离子占据，通过阴离子骨架与阳离子之间弱的N-H···Br氢键作用，呈现出三维有机-无机杂化钙钛矿结构。
将上述实施例1-3制得的三维有机-无机杂化钙钛矿半导体晶体(CH3NH2C3H9N)Pb2Br6通过紫外可见吸收光谱进行分析。如图3所示，(CH3NH2C3H9N)Pb2Br6的吸收截止边为448nm。根据Tauc公式可以推导出该化合物的光学带隙值为2.75eV。
基于(CH3NH2C3H9N)Pb2Br6单晶制成的平面电极采用405nm激光为激发光源研究了其光电导行为。图4显示了在黑暗中和光照下的电流-电压(I-V)曲线，受到光激发效应的影响，随着入射光强的增加，I-V曲线的光电流呈现明显的上升趋势，从4.8 X 10-12A增加到4.2 X 10-9A，得到Iph/Idark的值为1.14×103，说明其单晶的结晶质量高，固有载流子密度低。该结果不仅揭示了(CH3NH2C3H9N)Pb2Br6晶体的半导体性能，而且表明该材料能够用于制作光电探测器件，表明材料在集成光电功能器件领域具有潜在的应用价值。
本发明不仅限于上述实施例，凡是依据本发明上述实施例所作出的替换和变更，都在本发明保护范围之内。

Claims (6)

1.一种三维有机-无机杂化钙钛矿半导体晶体，其特征在于：所述的三维有机-无机杂化钙钛矿半导体晶体的化学式为(CH3NH2C3H9N)Pb2Br6。
2.根据权利要求1所述的一种三维有机-无机杂化钙钛矿半导体晶体，其特征在于：所述的三维有机-无机杂化钙钛矿半导体晶体属于正交晶系，空间群为Pbam。
3.根据权利要求2所述的三维有机-无机杂化钙钛矿半导体晶体，其特征在于：所述晶体的晶胞参数为：
Figure FDA0003689236900000011
Figure FDA0003689236900000012
α＝90°，β＝90°，γ＝90°，Z＝2，
Figure FDA0003689236900000013
4.根据权利要求1-3中任一项所述的一种三维有机-无机杂化钙钛矿半导体晶体的制备方法，其特征在于：包括以下步骤：
称取3-甲氨基丙胺、三水合乙酸铅置于烧杯中，再向烧杯中加入氢溴酸水溶液，加热到95～100℃并搅拌至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封放入65℃-70℃的烘箱中，以0.8～1℃/天的速率冷却至室温，即得到所述的三维有机-无机杂化钙钛矿半导体晶体；
所述的3-甲氨基丙胺、三水合乙酸铅、HBr的摩尔比为1：2：(8～15)。
5.根据权利要求4所述的一种三维有机-无机杂化钙钛矿半导体晶体的制备方法，其特征在于：所述的HBr水溶液中HBr的质量分数为47～48％。
6.根据权利要求1-3中任一种三维有机-无机杂化钙钛矿半导体晶体的用途，其特点在于：所述的三维有机-无机杂化钙钛矿半导体晶体用于制备光电探测器件。
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