CN111501087B - 一种维度可调的非铅钙钛矿单晶及其制备方法和应用 - Google Patents
一种维度可调的非铅钙钛矿单晶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种维度可调的非铅钙钛矿单晶及其制备方法和应用,所述维度可调的非铅钙钛矿单晶,结构式为AIII(3py)2BIIIX6,其中AIII为Ni3+、Co3+、Cr3+,BIII为Bi3+、In3+、Ga3+、Sb3+,X为Cl‑、Br‑、I‑。其通过在ABX3型钙钛矿生长单晶的溶液中用过渡金属配合物替换A位金属阳离子以及添加卤化金属盐制备而成。该类维度可调的非铅钙钛矿材料具有的低维形态能有效的改善单晶内部结构从而形成的主客体系统,有机基团将有效地保护嵌入其中的金属卤化物,提高单晶稳定性,并使材料表现出各个金属卤化物的固有特性。
Description
技术领域
本发明属于半导体光电检测技术领域,具体涉及一种维度可调的非铅钙钛矿单晶及其制备方法和应用。
背景技术
自2009年以来,有机-无机杂化钙钛矿材料APbX3[A=(CH3NH3)+(MA+)、CH(NH2)2+(FA+)、Cs+;X=I-、Br-、Cl-],因其简单的制备方式和优良的光电性能(禁带宽度可调、高迁移率、高消光系数)备受关注,出色的结构可调性使这些材料在分子水平上具有三(3D),两(2D),一(1D)和零维(0D)结构。维度的调控可以有效改变钙钛矿单晶的稳定性以及光物理特性,因此低维形貌(2D、1D、0D)无铅钙钛矿材料备受科研人员的关注,其光电探测方面的应用更已成为当下的研究热点。
尽管Pb基卤化钙钛矿具有优良的光电特性,但是Pb的水溶性以及毒性造成的环境健康问题极大地限制了它在社会上的广泛应用,因此寻找一种可取代Pb2+且同时具有优良光物理特性的离子以及一种可取代A位阳离子且具有疏水性的大分子基团是解决上述问题的关键。目前,通过过渡金属配合物有机基团取代A位离子,通过掺杂/取代的方法减少或消除B位Pb2+的毒性形成具有ABX3或APb(XI 1-xXII x)3[A=(CH3NH3)+(MA+)、CH(NH2)2+(FA+)、CH3(CH2)3NH3 +(BA+)、AIII(3py)2 3+、Cs+;B=Sn2+、Bi3+、In3+、Sb3+、Ga3+;X=I-、Br-、Cl-]型结构的钙钛矿,拥有维度可调的特性以及优异的光物理性能,使其成为Pb基卤化钙钛矿光电探测器的有前途的竞争者,成为制备环境友好型光电探测器的优良材料。
发明内容
基于上述问题,本发明提供一种维度可调的非铅钙钛矿单晶及其制备方法和应用。
本发明的技术方案之一,一种维度可调的非铅钙钛矿单晶,所述维度可调的非铅钙钛矿单晶,结构式为AIII(3py)2BIIIX6,其中AIII为Ni3+、Co3+、Cr3+,BIII为Bi3+、In3+、Ga3+、Sb3 +,X为Cl-、Br-、I-。
本发明的技术方案之二,上述维度可调的非铅钙钛矿单晶的制备方法,以三联吡啶为配体的过渡金属配合物AIII(3py)2 3+取代ABX3中的A位阳离子,形成具有AIII(3py)2BIIIX6结构的钙钛矿材料。
优选的,制备方法包括以下步骤:
(1)将溶质AIII、三联吡啶和BⅢX3以摩尔比为1:2:1溶解在氢卤酸、水和乙腈组成的混合溶液中,形成钙钛矿前驱体溶液。因为有机物在单一氢卤酸溶液中难以溶解,无法结晶形成单晶,加入水和乙腈后形成的混合溶液有助于有机溶质在后续140℃持续加热下充分溶解,
(2)将步骤(1)所述钙钛矿前驱体溶液140℃加热至完全溶解成透明澄清溶液,然后降温结晶,生长出来的晶体经冲洗,得到所述维度可调非铅钙钛矿单晶。
优选的,所述步骤(1)中,氢卤酸溶液为盐酸、氢溴酸、氢碘酸中的至少一种;所述氢卤酸溶液的浓度为36~45%;所述混合溶液中的水:乙腈:氢卤酸的体积比为1:3:2;所述溶质BIIIX在混合溶液中的浓度为0.03mol/L,溶质AIII在混合溶液的浓度为0.03mol/L。
优选的,所述步骤(2)中,降温结晶速率为1~2℃/h。
优选的,所述步骤(2)中,降温结晶分三阶段进行,第一阶段以2℃/h的速率降温至100℃,然后在100℃下保温4h,第二阶段以1℃/h的速率降温至60℃,然后在60℃下保温3h,第三阶段以2℃/h的速率降至室温。分步降温结晶是为了避免降温过快导致结晶速率不稳定造成晶体界面失配与缺陷态增多,生长出来的单晶体积小光泽差,形状不规则,器件性能不好。通过分步结晶可以使单晶生长速率趋于稳定,实现连续结晶,生长出来的晶体体积大形状规则,缺陷态密度小,光电性能稳定。
优选的,所述步骤(2)中,冲洗指将生长出来的晶体通过异丙醇或乙酸乙酯冲洗,以去除晶体表面残留的附着物。
优选的,将步骤(2)制备的维度可调非铅钙钛矿单晶在空气中373K退火2h可以改善其晶体质量。
本发明的技术方案之三,上述的维度可调的非铅钙钛矿单晶在光电探测器和太阳能电池领域中的应用。
本发明还提供一种光电探测器,包括上述维度可调的非铅钙钛矿单晶、玻璃基板、栅极电极、导电金丝。
优选的,所述导电金丝直径为0.5mm,栅极电极为Au。
所述玻璃基板用于单晶的固定,所述电极使用栅极模板进行电极蒸镀,蒸镀约为100nm;将维度可调的非铅钙钛矿单晶固定在玻璃基板上,用导电金丝和银胶将电极的两端引出来,方便接线测试。
与现有技术相比,本发明具有以下有益效果:
(1)本发明通过过渡金属AIII、三价重金属BⅢ完全代替传统钙钛矿材料中的铅;X位为卤族元素,合成了无毒、稳定性高的维度可调非铅钙钛矿材料,解决了传统钙钛矿中铅的生物毒性带来的问题;将钙钛矿中的Pb2+用一个三价金属阳离子代替,A位阳离子用以三联吡啶为配体过渡金属配合物AIII(3py)2 3+取代,形成具有AIII(3py)2BIIIX6结构的钙钛矿材料,更大尺度A位离子或有机基团的引入,会进一步撑开3D钙钛矿结构,形成低维钙钛矿结构。
(2)本发明通过将钙钛矿中A位离子进行合理设计,通过合理的A位有机阳离子掺杂/取代,在一定程度上将钙钛矿晶格结构加固,降低自由离子在晶格中的负面迁移,从而提高材料的环境稳定性和光伏特性。
(3)本发明合成的维度可调非铅钙钛矿材料形成的低维结构通过有机基团保护金属卤化物,比传统低维钙钛矿材料具有更好的热稳定性,在室温以及高温条件下可以保持优良性能。
附图说明
图1为本发明实施例1制备的Ni(3py)2BiBr6钙钛矿单晶的热重及同步热分析(TGA/DSC)结果图;
图2为实施例1中的Ni(3py)2BiBr6紫外光电探测器的响应速度测试结果图;
图3为实施例1中的Ni(3py)2BiBr6钙钛矿单晶结构示意图;
图4为实施例2中的Ni(3py)2InCl6紫外光电探测器的响应速度测试结果;
图5为实施例3中的Cr(3py)2GaBr6紫外光电探测器的响应速度测试结果;
图6为实施例4中的Co(3py)2SbI6紫外光电探测器的响应速度测试结果;
图7为实施例5中的Ni(3py)2BiBr6紫外光电探测器的响应速度测试结果;
图8为实施例1中的Ni(3py)2BiBr6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线;
图9为实施例2中的Ni(3py)2InCl6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线;
图10为实施例3中的Cr(3py)2GaBr6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线;
图11为实施例4中的Co(3py)2SbI6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
实施例1
过渡金属配合物取代A位的Ni(3py)2BiBr6非铅钙钛矿单晶的制备;
1)将溶质乙酰丙酮镍、三联吡啶、BiBr3按照摩尔质量比为1:2:1的比例配制,即称取0.1mmol(0.0128g)乙酰丙酮镍,0.2mmol(0.0234g)三联吡啶,0.1mmol(0.0225g)BiBr3溶解到1mL浓度为45%的市售氢溴酸和0.5mL的去离子水以及1.5mL的无水乙腈的混合溶液中,得前驱体溶液。
2)将配好的前驱体溶液放置在140℃加热台上加热,观察溶质是否充分溶解,若未完全溶解,可以适当摇晃促进其溶解;延长加热时间促进其溶解,或者添加氢溴酸溶剂促进其溶解。溶解完全的溶液为澄清透明液体。
3)溶液溶解完全后开始降温结晶过程,先由140℃降温至100℃,然后在100℃下保温4h,降温速率为2℃/h;然后由100℃降温至60℃,降温速率为1℃/h;然后在60℃下保温3h;最后由60℃降温至30℃,降温速率为2℃/h。
4)将生长出的非铅钙钛矿晶体通过异丙醇或乙酸乙酯冲洗得到Ni(3py)2BiBr6非铅钙钛矿单晶,并在空气中373K退火2h。
(5)用特制的栅极电极模板,在晶体表面镀上一层厚度大概为100nm的金电极。镀好电极后,将单晶固定在玻璃基板上,用导电金丝和银胶将电极的两端引出来,方便接线测试。
对制备的Ni(3py)2BiBr6钙钛矿单晶进行热重及同步热分析,结果见图1;结果显示,其分解温度为220.3℃,展现出较好的热稳定性;
将制备的紫外光电探测器在365nm下进行响应速度检测,结果见图2;结果显示,上升时间为0.48ms,下降时间为0.71ms,对紫外光展现快速的响应;
制备的Ni(3py)2BiBr6钙钛矿单晶结构示意图见图3,由图可得过渡金属配合物Ni(3py)2 3+将钙钛矿3D晶格结构撑开,导致金属卤化物八面体[BiBr6]3-彼此分离,形成零维结构钙钛矿单晶。
制备的紫外光电探测器在365nm下在暗态、光照环境下电流随电压的变化曲线见图8,在1V下的开关比为3.75×103。
实施例2
过渡金属配合物取代A位的Ni(3py)2InCl6非铅钙钛矿单晶的制备;
在步骤1)中将溶质乙酰丙酮镍、三联吡啶、InCl3按照摩尔质量比为1:2:1的比例配制,即称取0.1mmol(0.0128g)乙酰丙酮镍,0.2mmol(0.0234g)三联吡啶,0.2mmol(0.0221g)InCl3,溶解到1mL浓度为45%的市售盐酸和0.5mL的去离子水以及1.5mL的无水乙腈的混合溶液中。其余步骤与实施例1相同。
图4为实施例2中Ni(3py)2InCl6紫外光电探测器的响应速度测试结果。上升时间为0.67ms,下降时间为1.04ms,对紫外光展现快速的响应。
图9为实施例2中Ni(3py)2InCl6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线,在1V下的开关比为3.75×103。
图4、图9均在365nm下测试的,该波长位于紫外光区域。
实施例3
过渡金属配合物取代A位的Cr(3py)2GaBr6非铅钙钛矿单晶的制备;
在步骤1)中将溶质三乙酸铬、三联吡啶、GaBr3按照摩尔质量比为1:2:1的比例配置,即称取0.1mmol(0.0229g)三乙酸铬,0.2mmol(0.0234g)三联吡啶,0.1mmol(0.0309g)GaBr3,溶解到1mL浓度为45%的市售氢溴酸和0.5mL的去离子水以及1.5mL的无水乙腈的混合溶液中。其余步骤与实施例1相同。
图5为实施例3中Cr(3py)2GaBr6紫外光电探测器的响应速度测试结果。上升时间为0.53ms,下降时间为0.87ms,对紫外光展现快速的响应。
图10为实施例3中Cr(3py)2GaBr6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线,在1V下的开关比为3.75×103。
图5、图10均在365nm下测试的,该波长位于紫外光区域。
实施例4
过渡金属配合物取代A位的Co(3py)2SbI6非铅钙钛矿单晶的制备;
在步骤1)中将溶质醋酸钴、三联吡啶、SbI3按照摩尔质量比为1:2:1的比例配置,即称取0.1mmol(0.0177g)醋酸钴,0.2mmol(0.0234g)三联吡啶,0.1mmol(0.0502g)SbI3,溶解到1mL浓度为45%的市售氢碘酸和0.5mL的去离子水以及1.5mL的无水乙腈的混合溶液中。其余步骤与实施例1相同。
图6为实施例4中Co(3py)2SbI6紫外光电探测器的响应速度测试结果。上升时间为0.72ms,下降时间为1.24ms,对紫外光展现快速的响应。
图11为实施例4中Co(3py)2SbI6紫外光电探测器在暗态、光照环境下电流随电压的变化曲线,在1V下的开关比为3.75×103。
图6、图11均在365nm下测试的,该波长位于紫外光区域。
实施例5
同实施例1,区别在于,步骤(3)中,降温过程为:待溶液溶解完全后开始降温结晶过程,采用一步降温法,从140℃开始降温,降温速率为2℃/h,一直到降到室温时停止降温过程。
图7为实施例5中Ni(3py)2BiBr6紫外光电探测器的响应速度测试结果。可见光电响应效果被大大衰减,因此分步降温结晶法有助于单晶生长以及器件性能的提高。
此外,采用和实施例1~4相同的方法分别制备省略在空气中373K退火2h的操作步骤制备非铅钙钛矿单晶,并对其产品进行缺陷态密度检测,结果见表1;
表1实施例1~4的钙钛矿单晶在不同降温方式下进行退火和未退火处理的缺陷态密度。
由上可知,生长好之后的单晶在经过退火后能有效降低缺陷态密度,提高单晶质量,而且采用分步降温的方式能有效改善器件的光电性能。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种维度可调的非铅钙钛矿单晶,其特征在于,所述维度可调的非铅钙钛矿单晶,结构式为AIII(3py)2BIIIX6,其中AIII为Ni3+、Co3+、Cr3+,BIII为Bi3+、In3+、Ga3+、Sb3+,X为Cl-、Br-、I-;
所述维度可调的非铅钙钛矿单晶以三联吡啶为配体的过渡金属配合物AIII(3py)2 3+取代ABX3中的A位阳离子,形成具有AIII(3py)2BIIIX6结构的钙钛矿材料。
2.一种根据权利要求1所述的维度可调的非铅钙钛矿单晶的制备方法,其特征在于,包括以下步骤:
(1)将溶质AIII、三联吡啶和BⅢX3以摩尔比为1:2:1溶解在氢卤酸、水和乙腈组成的混合溶液中,形成钙钛矿前驱体溶液;
(2)将步骤(1)所述钙钛矿前驱体溶液在140℃条件下加热至完全溶解成透明澄清溶液,然后降温结晶,生长出来的晶体经冲洗,得到所述维度可调的非铅钙钛矿单晶。
3.根据权利要求2所述的维度可调的非铅钙钛矿单晶的制备方法,其特征在于,所述步骤(1)中,氢卤酸溶液为盐酸、氢溴酸、氢碘酸中的至少一种;所述氢卤酸溶液的浓度为36~45%;所述混合溶液中的水:乙腈:氢卤酸的体积比为1:3:2;所述溶质BIIIX在混合溶液中的浓度为0.03mol/L,溶质AIII在混合溶液的浓度为0.03mol/L。
4.根据权利要求2所述的维度可调的非铅钙钛矿单晶的制备方法,其特征在于,所述步骤(2)中,降温结晶速率为1~2℃/h。
5.根据权利要求2所述的维度可调的非铅钙钛矿单晶的制备方法,其特征在于,所述步骤(2)中,降温结晶分三阶段进行,第一阶段以2℃/h的速率降温至100℃,然后在100℃下保温4h,第二阶段以1℃/h的速率降温至60℃,然后在60℃下保温3h,第三阶段以2℃/h的速率降至室温。
6.根据权利要求2所述的维度可调的非铅钙钛矿单晶的制备方法,其特征在于,所述步骤(2)中,冲洗指将生长出来的晶体通过异丙醇或乙酸乙酯冲洗。
7.一种根据权利要求1所述的维度可调的非铅钙钛矿单晶在光电探测器和太阳能电池领域中的应用。
8.一种光电探测器,其特征在于,包括权利要求1所述的维度可调的非铅钙钛矿单晶、玻璃基板、栅极电极、导电金丝。
9.根据权利要求8所述的光电探测器,其特征在于,所述导电金丝直径为0.5mm,栅极电极为Au。
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