CN114990699A - 一种二维双层有机-无机杂化钙钛矿半导体晶体及其制备方法和用途 - Google Patents

一种二维双层有机-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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CN114990699A
CN114990699A CN202210568432.7A CN202210568432A CN114990699A CN 114990699 A CN114990699 A CN 114990699A CN 202210568432 A CN202210568432 A CN 202210568432A CN 114990699 A CN114990699 A CN 114990699A
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罗军华
王道华
姬成敏
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Abstract

本发明涉及一种二维双层有机‑无机杂化钙钛矿半导体晶体、制备方法和用途，所述的无机‑有机杂化半导体材料的化学式为(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7。本发明的二维双层有机‑无机杂化钙钛矿半导体晶体制备成平面光电导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的激光照射采用本发明单晶制备的晶体探测器件，测试其光电响应，入射光的功率密度为10.2mW/cm2时，该晶体探测器件表现出明显的光电导效应Iph＝17nA，该结果表明该材料用作光电导探测器件具有潜在的应用价值。

Description

一种二维双层有机-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，具体涉及一种二维双层有机-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
三维(3D)有机-无机杂化钙钛矿的结构通式为ABX3，A是一价阳离子，如Cs+、甲铵离子(MA)、甲脒离子(FA)；而B是二价金属，如Pb2+、Sn2+等；X是卤素(Cl、Br或I)。从结构上来讲，3DABX3是BX6八面体通过顶点共享向三个方向无限延伸的网络，A位有机阳离子填充在由相邻BX6八面体组成的空隙当中，起到平衡电荷、稳定结构的作用。为了使3D结构稳定，A位有机阳离子的尺寸需在一定范围内，它们的选择受到Goldschmidt容忍因子(t)的限制，因此3D的ABX3结构具有相当严格的结构约束，通过改变组分特别是A的离子大小可以实现卓越的结构可调性得到二维(2D)，一维(1D)，乃至零维(0D)结构。对于组分相同的无机有机杂化钙钛矿，从3D到0D其带隙逐渐变宽。对于二维多层无机有机杂化钙钛矿，其Eg随着无机层厚度的增加而减小。如(C4H9NH3)2(MA)n-1SnnI3n+1,随着n增加，其从1.98eV(n＝1)减小到1.2eV(n＝∞)。更为重要的是，2D的无机有机杂化钙钛矿不受容忍因子的限制，可以容纳各种各样的阳离子，有机阳离子的分子动力学为对称破坏和电极的产生提供了驱动力。因此，2D无机有机杂化钙钛矿是设计具有优越半导体性质的理想体系。
发明内容
本发明提供一种二维双层有机-无机杂化钙钛矿半导体晶体、制备方法和用途，本发明的二维双层有机-无机杂化钙钛矿半导体晶体制成平面光电导探测器可实现对本征吸收光谱的高灵敏度探测。
本发明的技术方案如下：
方案一)
一种二维双层有机-无机杂化钙钛矿半导体晶体，所述的无机-有机杂化半导体材料的化学式为(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7。
所述的二维双层有机-无机杂化钙钛矿半导体晶体属于三斜晶系，空间群为P1。
所述晶体的晶胞参数为：
Figure BDA0003657140940000021
α＝96.815(18)°，β＝95.416(16)°，γ＝90.271(19)°，
Figure BDA0003657140940000022
Z＝2。
方案二)
一种有机-无机杂化双钙钛矿半导体晶体的制备方法，包括以下步骤：
称取氮甲基-1,3-丙二胺、碳酸铯、氧化铅并置于烧杯中，再向烧杯中加入HBr水溶液，加热到126～130℃并搅拌至得到黄色澄清溶液；
然后将得到的溶液密封放入55℃-60℃的烘箱中，以0.8～1(℃/天的速率冷却至室温，即得到所述的有机-无机杂化钙钛矿半导体；
所述的氮甲基-1,3-丙二胺、碳酸铯、氧化铅的摩尔比为(2～4)：(1～2)：(4～8)；
所述的PbO与HBr的摩尔比为1：(6～10)。
进一步地，所述的HBr水溶液中HBr的质量分数为47～48％。
方案三)
一种二维双层有机-无机杂化钙钛矿半导体的用途，所述的有机-无机杂化钙钛矿半导体(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7能应用在光电导探测器领域。
X射线单晶衍射的结果表明：该化合物的分子式为(N2C4H14)(Cs)Pb2Br7，结构简式为(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7。其中,(NH3CH2CH2CH2NH2CH3)2+代表氮甲基-1,3-丙二胺离子。在室温下(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7晶体属于三斜晶系，空间群为P1。该化合物的晶胞参数为
Figure BDA0003657140940000031
Figure BDA0003657140940000032
α＝96.815(18)°，β＝95.416(16)°，γ＝90.271(19)°，
Figure BDA0003657140940000033
Figure BDA0003657140940000034
Z＝2。
较之前的现有技术，本发明具有以下有益效果：本发明制备了一种二维双层有机-无机杂化钙钛矿半导体晶体，本发明的二维双层有机-无机杂化钙钛矿半导体晶体制备成平面光电导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的激光照射采用本发明单晶制备的晶体探测器件，测试其光电响应，入射光的功率密度为10.2mW/cm2时，该晶体探测器件表现出明显的光电导效应Iph＝17nA，该结果表明该材料用作光电导探测器件具有潜在的应用价值。
附图说明
图1是本发明中(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7晶体的照片。
图2是本发明中(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7晶体的晶体结构图。
图3是本发明中(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7的光学带隙。
图4是本发明中(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7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
制备二维双层有机-无机杂化钙钛矿半导体晶体(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7
采用降温结晶法合成晶体(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7，化学反应式为
2NH2CH2CH2CH2NHCH3+4PbO+Cs2CO3+14HBr→
2(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7+7H2O
称取氮甲基-1,3-丙二胺(1×10-3mol)、碳酸铯(0.5×10-3mol)、氧化铅(2×10- 3mol)并置于烧杯中，再向烧杯中加入HBr水溶液，加热到126℃并搅拌直至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封，放入温度为55℃的烘箱中，待溶液温度达到55℃之后，以0.8℃/天的速率冷却至室温，即得到所述的有机-无机杂化钙钛矿半导体；
所述的氧化铅与HBr水溶液中的HBr的摩尔比为1：6。
所述的HBr水溶液中HBr的质量分数为48％。
实施例2
二维双层有机-无机杂化钙钛矿半导体晶体(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7的制备
称取氮甲基-1,3-丙二胺(4×10-3mol)、碳酸铯(2×10-3mol)、氧化铅(8×10-3mol)并置于烧杯中，再向烧杯中加入HBr水溶液，加热到130℃并搅拌直至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封，放入温度为60℃的烘箱中，待溶液温度达到60℃之后，以1℃/天的速率冷却至室温，即得到所述的有机-无机杂化钙钛矿半导体；
所述的氧化铅与HBr水溶液中的HBr的摩尔比为1：10。
所述的HBr水溶液中HBr的质量分数为47。
本实施例溶液析出尺寸为3×3×1mm3的黄色片状晶体(如图1所示)，即(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7晶体。
经X射线单晶衍射分析，本实施例制备的(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7晶体室温下属于三斜晶系P1空间群，晶胞参数为
Figure BDA0003657140940000051
α＝90°，β＝90.052(3)°，γ＝90°，
Figure BDA0003657140940000052
Z＝2。
从图2中可以看出，(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7采用如下的结构：有机阳离子层(NH3CH2CH2CH2NH2CH3)2+和无机层CsPb2Br7 2+交错堆积构成二维杂化钙钛矿结构，无机部分二维双层钙钛矿结构框架，类似于典型的立方型钙钛矿CsPbBr3，无机的碱金属Cs+离子位于PbBr6八面体连接的钙钛矿孔隙中。
实施例3
称取氮甲基-1,3-丙二胺、碳酸铯、氧化铅并置于烧杯中，再向烧杯中加入HBr水溶液，加热到127℃并搅拌直至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封，放入温度为57℃的烘箱中，待溶液温度达到57℃之后，以0.9℃/天的速率冷却至室温，即得到所述的有机-无机杂化钙钛矿半导体；
所述的氮甲基-1,3-丙二胺、碳酸铯、氧化铅的摩尔比为3：1：5；
所述的氧化铅与HBr水溶液中的HBr的摩尔比为1：7。
所述的HBr水溶液中HBr的质量分数为47％。
将上述实施例制得的二维双层有机-无机杂化钙钛矿半导体晶体(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7通过紫外可见吸收光谱对(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7的光学吸收进行分析。(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7的吸收截止边为525nm。如图3所示，根据Tauc公式可以推导出该化合物的光学带隙值为2.36eV。
基于(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7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(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7在黑暗中和光照下的电流-电压(I-V)曲线。结果表明，在10V偏压下，(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7的暗电流(Idark)为9×10-10A，说明其单晶的结晶质量高，固有载流子密度低。当光照强度为10.2mW/cm2时，(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7的光电流(Iph)急剧增加至1.7×10-8A，得到Iph/Idark的值为18。该结果不仅揭示了(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7晶体的半导体性能，而且表明该材料能够用于制作光电导探测器件，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做出的替换和变更，都在本发明保护范围。

Claims (4)

1.一种二维双层有机-无机杂化钙钛矿半导体晶体，其特征在于：所述的二维双层有机-无机杂化钙钛矿半导体晶体的化学式为(NH3CH2CH2CH2NH2CH3)(Cs)Pb2Br7，属于三斜晶系，空间群为P1，晶胞参数为：
Figure FDA0003657140930000011
α＝96.815(18)°，β＝95.416(16)°，γ＝90.271(19)°，
Figure FDA0003657140930000012
Z＝2。
2.根据权利要求1所述的二维双层有机-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：
称取氮甲基-1,3-丙二胺、碳酸铯、氧化铅并置于烧杯中，再向烧杯中加入HBr水溶液，加热到126-130℃并搅拌直至得到黄色澄清溶液；
然后将得到的黄色澄清溶液密封，放入温度为55℃～60℃的烘箱中，待溶液温度达到55℃～60℃之后，以0.8～1℃/天的速率冷却至室温，即得到所述的有机-无机杂化钙钛矿半导体；
所述的氮甲基-1,3-丙二胺、碳酸铯、氧化铅的摩尔比为(2～4)：(1～2)：(4～8)；
所述的氧化铅与HBr水溶液中的HBr的摩尔比为1：(6～10)。
3.根据权利要求2所述的二维双层有机-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％。
4.根据权利要求1所述的一种二维双层有机-无机杂化钙钛矿半导体的用途，其特征在于：所述的二维双层有机-无机杂化钙钛矿半导体用于制备光电导探测器。
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