CN114907398B - 一种手性有机无机杂化共生钙钛矿单晶、生长方法及其应用 - Google Patents
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Abstract
本发明涉及一种手性有机无机杂化共生钙钛矿单晶、生长方法及其应用。所述的手性有机无机杂化共生钙钛矿的单晶为四[左旋(4‑氯苯基)乙胺]一甲脒三铅十一碘,化学式为Pb6I11Cl8C33N12H49,室温下属于单斜晶系,空间群为P21,晶胞参数为α=90°,β=92.619°,γ=38.4523°,Z=2,本发明的手性有机无机杂化共生钙钛矿单晶稳定性较高、缺陷密度小、光响应范围优良,反应条件温和。
Description
技术领域
本发明属于涉及功能材料领域,具体涉及一种手性有机无机杂化共生钙钛矿单晶、生长方法及其应用。
背景技术
无机有机杂化钙钛矿因为拥有无机组分优异的半导体性能和有机组分的多样化官能团修饰,近些年来在太阳能电池以及光电材料领域具有广阔的运用。其中,手性无机有机杂化钙钛矿因为手性有机胺和无机骨架之间的手性转移,具有手性量子阱合手性半导体的特性,近些年来在铁电材料、非线性光学和自旋电子传输领域拥有广泛的前景,有望在圆偏振光探测与量子通讯领域发挥重大应用。然而,传统手性无机有机杂化钙钛矿吸收带隙较宽,光电性能普遍较差,且量子阱结构单一,这些都限制了手性无机有机杂化钙钛矿的进一步应用。
引入共生结构为手性无机有机杂化钙钛矿的发展提供了一条新路径。共生结构指的是在一种晶体结构中,通过物理或化学手段,将另一种晶体的结构呈一定的周期重复规律引入到已有的晶体结构当中,形成一种新的晶体结构。共生结构能够表现出其两种前体的物理化学特征,为整合各个材料的优势实现高性能光电功能材料提供良好的平台。
发明内容
本发明提供种手性有机无机杂化共生钙钛矿单晶、生长方法及其应用,本发明的手性有机无机杂化共生钙钛矿单晶稳定性较高、缺陷密度小、光响应范围优良,反应条件温和。
手性有机无机杂化共生钙钛矿单晶,所述的手性有机无机杂化共生钙钛矿的单晶为四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘,化学式为Pb6I11Cl8C33N12H49,室温下属于单斜晶系,空间群为P21,晶胞参数为 α=90°,β=92.619°,γ=38.4523°,Z=2,/>
所述的手性有机无机杂化共生钙钛矿单晶的生长方法,包括如下步骤:
室温下,将2~3克三水合醋酸铅和0.5~0.7克醋酸甲脒加入20~30mL氢碘酸水溶液中,然后滴入0.05~0.7克左旋(4-氯苯基)乙胺,接着加热至120~130℃并搅拌20~30分钟之后于1小时内降温至20℃~30℃,然后以0.5~1℃/h的速率降温到5~10℃,即得所述的手性有机无机杂化共生钙钛矿单晶。
所述的氢碘酸水溶液中氢碘酸的质量份数为47~48%。
一种手性有机无机杂化共生钙钛矿单晶的应用:所述的一种手性有机无机杂化共生钙钛矿单晶能用于制备可见-近红外圆偏振探测器。
X-射线单晶衍射测试结构表明:该化合物的化学式为Pb6I11 Cl8C33N12H49,室温下属于单斜晶系,空间群为P21,晶胞参数为 α=90°,β=92.619°,γ=38.4523°,Z=2,/>本发明晶体结构具有单层钙钛矿和双层钙钛矿交替排列的的特征,在单层与双层之间整齐排列手性胺左旋(4-氯苯基)乙胺,双层的孔洞内填充着甲脒阳离子。
较之前的现有技术,本发明具有以下有益效果:
本发明制得的手性有机无机杂化共生钙钛矿单晶稳定性较高、缺陷密度小、光响应范围优良,反应条件温和。紫外-可见-近红外吸收光谱表明,该晶体拥有台阶状吸收图谱,吸收截止边为850nm,覆盖全部紫外与可见光区,覆盖部分近红外光区,具有潜在的可见-近红外圆偏振探测的潜质。
附图说明
图1是本发明手性有机无机杂化共生钙钛矿单晶的晶体结构图。
图2是本发明手性有机无机杂化共生钙钛矿单晶的照片。
图3是本发明手性有机无机杂化共生钙钛矿单晶的紫外-可见-近红外吸收图谱。
具体实施方式
以下结合附图合具体实施方式对本发明作进一步地说明。
实施例1
手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的制备:
室温下,将2克三水合醋酸铅和0.5克醋酸甲脒加入20mL氢碘酸水溶液中,然后滴入0.05克左旋(4-氯苯基)乙胺,接着加热至120℃并搅拌20分钟之后于1小时内降温至20℃,然后以1℃/h的速率降温到5℃,即得所述的手性有机无机杂化共生钙钛矿单晶。
所述的氢碘酸水溶液中氢碘酸的质量份数为47%。
实施例2
手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的制备:
室温下,将3克三水合醋酸铅和0.7克醋酸甲脒加入30mL氢碘酸水溶液中,然后滴入0.7克左旋(4-氯苯基)乙胺,接着加热至130℃并搅拌30分钟之后于1小时内降温至30℃,然后以0.5℃/h的速率降温到10℃,即得所述的手性有机无机杂化共生钙钛矿单晶。
所述的氢碘酸水溶液中氢碘酸的质量份数为48%。
实施例3
手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的制备:
室温下,将2.5克三水合醋酸铅和0.6克醋酸甲脒加入25mL氢碘酸水溶液中,然后滴入0.1克左旋(4-氯苯基)乙胺,接着加热至125℃并搅拌25分钟之后于1小时内降温至25℃,然后以0.6℃/h的速率降温到6℃,即得所述的手性有机无机杂化共生钙钛矿单晶。
所述的氢碘酸水溶液中氢碘酸的质量份数为47%。
将实施例1-3所得到的手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的微型单晶挑选至载晶座上,选择曝光时间为1s,扫描步长为0.5度,收集分辨率为0.77埃的单晶衍射数据。选择点群为单斜P,空间群为P21,利用单晶解析软件shelx-XS的直接法进行单晶解析,用shelx-XL的最小二乘法进行精修,均可得到如图1所示的手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的单层钙钛矿-双层钙钛矿的手性共生交替结构。
上述实施例得到的化合物的化学式均为Pb6I11 Cl8C33N12H49,室温下属于单斜晶系,空间群为P21,晶胞参数为 α=90°,β=92.619°,γ=38.4523°,Z=2,/>本发明晶体结构具有单层钙钛矿和双层钙钛矿交替排列的的特征,在单层与双层之间整齐排列手性胺左旋(4-氯苯基)乙胺,双层的孔洞内填充着甲脒阳离子。
手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的紫外-可见-近红外吸收光谱的表征:
将上述实施例制得的手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘晶体研磨成粉末,将其均匀铺在干燥压实的硫酸钡基底表面,置入紫外-可见-近红外吸收光谱仪的积分球模块中,选定扫描区间为200nm至1000nm,扫描速率为2nm每秒,数据收集方式为漫反射,得到如图3所示的紫外-可见-近红外吸收图谱。由图谱可知,手性层状钙钛矿四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘的吸收边远至近红外波段,具有实现可见-近红外圆偏振探测的潜质。
上述实施例仅用来进一步说明本发明,凡是依据本发明原理所做出的简单修改、等同替换均在本发明保护范围之内。
Claims (4)
1.一种手性有机无机杂化共生钙钛矿的单晶,其特征在于:所述的手性有机无机杂化共生钙钛矿的单晶为四[左旋(4-氯苯基)乙胺]一甲脒三铅十一碘,化学式为Pb6I11Cl8C33N12H49,室温下属于单斜晶系,空间群为P21,晶胞参数为α=90°,β=92.619°,γ=38.4523°,Z=2,/>
2.如权利要求1所述的一种手性有机无机杂化共生钙钛矿单晶的生长方法,其特征在于:包括如下步骤,
室温下,将2~3克三水合醋酸铅和0.5~0.7克醋酸甲脒加入20~30mL氢碘酸水溶液中,然后滴入0.05~0.7克左旋(4-氯苯基)乙胺,接着加热至120~130℃并搅拌20~30分钟之后于1小时内降温至20℃~30℃,然后以0.5~1℃/h的速率降温到5~10℃,即得所述的手性有机无机杂化共生钙钛矿单晶。
3.如权利要求2所述的一种手性有机无机杂化共生钙钛矿单晶的生长方法,其特征在于:所述的氢碘酸水溶液中氢碘酸的质量份数为47~48%。
4.如权利要求1所述的一种手性有机无机杂化共生钙钛矿单晶的应用,其特征在于:所述的一种手性有机无机杂化共生钙钛矿单晶能用于制备可见-近红外圆偏振探测器。
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