CN116356422B - 一种基于cof结构的钙钛矿单晶及其制备方法和应用 - Google Patents
一种基于cof结构的钙钛矿单晶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于COF结构的钙钛矿单晶及其制备方法和应用,属于半导体材料技术领域。所述基于COF结构的钙钛矿单晶为以COF层为配合物基团替代钙钛矿中A位阳离子,以四价金属阳离子替代钙钛矿中B位Pb2+,从而形成COF层和无机八面体层交叠结构的COF‑BX4钙钛矿单晶;其中,B为Zr4+、Ni4+或Sn4+,X为Cl‑、Br‑或I‑。该钙钛矿单晶不仅保留钙钛矿原有的维度可调的特性以及优异的光物理性能,还融合了COF高比功率、高能量密度、出色的长期循环性能和高灵敏度的优点。基于该钙钛矿单晶制备的钙钛矿光电探测器具有优异的响应灵敏度、稳定性和响应频率。
Description
技术领域
本发明属于半导体材料技术领域,具体涉及一种基于COF结构的钙钛矿单晶及其制备方法和应用。
背景技术
近年来,能够将入射光(紫外线,可见光或红外线)转换为电信号的光电探测器对于各种工业和科学应用(包括成像,光通信,环境监测和生物传感)至关重要。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,其光电探测方面的应用更已成为当下的研究热点。虽然光电探测器制造工艺和技术已经变得成熟和可靠,但是它们复杂且昂贵的制造、机械不灵活性和高驱动电压都限制了它们的广泛应用和对于新技术的扩展,兼容性和多功能性。
发明内容
本发明的目的在于提供一种基于COF结构的钙钛矿单晶及其制备方法和应用。通过以COF作为A位有机插层将无机八面体骨架分隔开形成层层结构的新型钙钛矿结构,不仅保留钙钛矿原有的维度可调的特性以及优异的光物理性能,还融合了COF高比功率、高能量密度、出色的长期循环性能和高灵敏度的优点,制备的光电探测器探测率D*达到了8×1015Jones,截止频率f3dB达到了10kHz,200次开关相应损失为3%,光探测器在5V/mm的场强下老化30s,暗电流仅提高了12%,具有巨大的应用潜力和创新竞争力。
为实现上述目的,本发明提供了如下技术方案:
本发明技术方案之一:提供一种基于COF结构的钙钛矿单晶,具体为:以COF层为配合物基团替代钙钛矿中A位阳离子,以四价金属阳离子替代钙钛矿中B位Pb2+,从而形成COF层和无机八面体层交叠结构的COF-BX4钙钛矿单晶;其中,B为Zr4+、Ni4+或Sn4+,X为Cl-、Br-或I-。
本发明通过对钙钛矿中AB位传统的结合方式进行改进,以COF有机插层和无机八面体层交替构建新型钙钛矿的结构,有机层之间以π-π的强烈堆积作用结合,有机层与无机层之间以多氢键结构连接。以其为原料制备的钙钛矿光电探测器具有融合COF层的高灵敏高迁移率超快动力学、钙钛矿的维度带隙可调的优异光电性能。
优选地,所述COF层的原料为COF-609或BT-PTO COF。
更优选地,所述COF-609的制备步骤包括:
通过2,4,6-三(4-甲酰基苯基)-1,3,5-三嗪(TFPT)和4,4-二氨基苯甲胺(DABA)的亚胺缩合反应合成了一种多孔、结晶的亚胺连接的COF-609-Im,其分子式为[(TFPT)2(DABA)3];
所述BT-PTO COF的制备步骤包括:
2,7-二氨基比林-4,5,9,10-四酮(PTO-NH2,21.9mg,0.075mmol.)和1,3,5-苯三甲醛(Bt,10.5mg,0.05mmol.)在10mL试管中分散于1.3mL均三甲苯/二氧六环/6-甲基乙酸(体积比9:3:1)的混合溶液中;将混合物超声作用2分钟,以获得均匀分散,然后在氩气下冷冻和脱气三次;将试管密封,在120℃保存3天;黑色沉淀物冷却至室温后,经过滤分离,用甲醇、四氢呋喃和丙酮洗涤,用四氢呋喃提取12h,然后在80℃真空下干燥24h,得到BT-PTOCOF。
本发明技术方案之二:提供一种上述基于COF结构的钙钛矿单晶的制备方法,包括以下步骤:
将所述COF层的COF原料和无机八面体层的金属盐原料溶于氢卤酸中并稀释,得到钙钛矿前驱体溶液;所述钙钛矿前驱体溶液反应后降温结晶,得到所述基于COF结构的钙钛矿单晶。
优选地,所述氢卤酸为质量浓度36~45%的盐酸、氢溴酸或氢碘酸;所述稀释使用的稀释液为乙醇。
优选地,所述COF原料与所述金属盐原料的摩尔比为1:2。
优选地,所述金属盐原料在氢卤酸中的浓度为0.03~0.06mol/L;所述COF原料在氢卤酸中的浓度为0.03mol/L。
更优选地,所述COF原料为COF-609或BT-PTO COF,所述金属盐为ZrCl4或SnCl2,所制得的基于COF结构的钙钛矿单晶为(BT-PTO COF)SnCl4、(BT-PTO COF)ZrCl4、(COF-609)ZrCl4或(COF-609)SnCl4。
优选地,所述反应的温度为140℃,时间为5h;由于原料的溶解度随温度变化明显,故所述降温采用梯度降温,具体为搅拌状态下以1~2℃/h的速率降温至120℃,以1~2℃/h的速率降温至90℃并停止搅拌,保温10h后以1~2℃/h的速率冷却。此特定的降温结晶步骤有利于产生微晶核,得到的单晶结构稳定,杂质较少,且有很高的产率。
优选地,降温结晶后还包括冲洗步骤,冲洗液为异丙醇或乙酸乙酯。
本发明技术方案之三:提供一种上述基于COF结构的钙钛矿单晶在光电探测器或钙钛矿电池中的应用。
本发明的有益技术效果如下:
本发明通过新型高价金属锡,锆等取代了高毒性重金属铅离子作为钙钛矿的B位,降低了毒性的同时引入了新型金属离子的特性,合成了无毒、稳定性高的非铅钙钛矿材料,解决了传统钙钛矿中铅的生物毒性带来的问题。
本发明以新型COF有机插层替换传统钙钛矿中的A位离子,并实现有机-无机层之间的紧密耦合,所得钙钛矿单晶具有高稳定性结构和出色的长期循环性能。
本发明合成的基于COF结构的钙钛矿单晶为有机层-无机层交叠钙钛矿材料,该材料的层层结构可通过传输方向上的超高迁移率和层间的紧密耦合特性,使基于该钙钛矿单晶制备的钙钛矿光电探测器具有优异的响应灵敏度、稳定性和响应频率。
附图说明
图1为本发明实施例1中光电探测器的结构示意图。
图2为实施例1制备的(COF-609)SnCl4钙钛矿单晶的热重分析图。
图3为实施例1制备的光电探测器对紫外光响应速度的测试结果图。
图4为实施例1制备的光电探测器的衰减与频率的关系图。
图5为实施例2制备的光电探测器对紫外光响应速度的测试结果图。
图6为实施例2制备的光电探测器在暗态、光照环境下电流随电压的变化曲线图。
图7为实施例3制备的光电探测器对紫外光响应速度的测试结果图。
图8为实施例3制备的光电探测器在暗态、光照环境下电流随电压的变化曲线图。
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。
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。
本发明实施例所用COF-609的制备步骤为:
将TFPT(15.7mg,0.04mmol)和DABA(13.6mg,0.06mmol)混合在0.85mL均三甲苯和0.15mL正丁醇中,放入8×10mm的硼硅酸盐玻璃管中进行合成。将混合物超声5min,然后加入0.05mL醋酸溶液(在去离子水中浓度为9molL-1)。获得的悬浮液进一步超声5分钟,在77K的液氮浴中闪速冷冻,抽真空至150mTorr以下的内压,并火焰密封。密封后,管子的长度减少到10厘米左右。升温至室温后,在140℃下加热4天,得到黄色固体。收集固体,用丙酮和甲醇在索氏萃取器中洗涤1d,用超临界CO2干燥,在140℃脱气24h,得到黄色固体COF-609-Im。
本发明实施例所用BT-PTO COF的制备步骤为:
将2,7-二氨基比林-4,5,9,10-四酮(PTO-NH2,21.9mg,0.075mmol.)和1,3,5-苯三甲醛(Bt,10.5mg,0.05mmol.)在10mL试管中分散于1.3mL均三甲苯/二氧六环/6-甲基乙酸(体积比9:3:1)的混合溶液中;将混合物超声作用2分钟,以获得均匀分散,然后在氩气下冷冻和脱气三次;将试管密封,在120℃保存3天;黑色沉淀物冷却至室温后,经过滤分离,用甲醇、四氢呋喃和丙酮洗涤,用四氢呋喃提取12h,然后在80℃真空下干燥24h,得到黑色粉末(29mg,89%),即BT-PTO COF。
实施例1
制备COF-609层和[SnCl6]2+层交叠的(COF-609)SnCl4钙钛矿单晶:
(1)称取0.1mmol COF-609,0.2mmol SnCl2溶解到1mL浓度为36-37%的市售浓盐酸溶液中,并加入4mL乙醇稀释,得到(COF-609)SnCl4混合溶液;
(2)将配制的(COF-609)SnCl4混合溶液放置于140℃加热台上加热5h并磁力搅拌,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,或者添加浓盐酸溶剂促进其溶解;溶解完全的溶液为澄清深色液体;
(3)溶液溶解完全后开始降温结晶过程,以1℃/h的速率降温至120℃,以1℃/h的速率降温至90℃并停止搅拌,然后在90℃下保温10h,以2℃/h的速率快速降至室温,所得结晶利用异丙醇冲洗,得到COF-609层和[SnCl6]2+层交叠的(COF-609)SnCl4钙钛矿单晶。
对所制得的(COF-609)SnCl4钙钛矿单晶及以其为原料制备的光电探测器(结构示意图见图1)进行性能测定。
光电探测器的具体制备方法为:用特制的栅极电极模板,在单晶上表面镀上一层厚度大概为100nm的金电极;镀好电极后,将单晶下表面固定在玻璃基板上,用导电金丝和银胶将电极的两端引出来,方便接线测试。
图2为实施例1制备的(COF-609)SnCl4钙钛矿单晶的热重分析图。由图2可知,其分解温度为335.7℃,具备良好的热稳定性。
图3为实施例1制备的光电探测器对紫外光响应速度的测试结果图。由图3可知,该光电探测器收到紫外光辐照时,光电流上升时间为0.3ms,下降时间为0.56ms,表明该光电探测器对紫外光展现出快速的响应。
图4为实施例1制备的光电探测器的衰减与频率的关系图。由图4可知,该光电探测器的截止频率f3dB达到了10kHz,具有较高的带宽。
实施例2
制备COF-609层和[ZrCl6]2+层交叠的(COF-609)ZrCl4钙钛矿单晶:
与实施例1相比,区别仅在于,称取的原料为0.1mmol COF-609和0.2mmol ZrCl4。
以实施例2所制得(COF-609)ZrCl4钙钛矿单晶为原料制备光电探测器,方法与实施例1相同。
图5为实施例2制备的光电探测器对紫外光响应速度的测试结果图。由图5可知,该光电探测器收到紫外光辐照时,光电流上升时间为0.67ms,下降时间为1.04ms,表明该光电探测器对紫外光展现出快速的响应。
图6为实施例2制备的光电探测器在暗态、光照环境下电流随电压的变化曲线图。由图6可知,电压为0.6V时,开关比为75。
实施例3
制备BT-PTO COF层和[SnCl6]2+层交叠的(BT-PTO COF)SnCl4钙钛矿单晶:
与实施例1相比,区别仅在于,称取的原料为0.1mmol BT-PTO COF和0.2mmolSnCl2。
图7为实施例3制备的光电探测器对紫外光响应速度的测试结果图。由图7可知,该光电探测器收到紫外光辐照时,光电流上升时间为0.53ms,下降时间为0.87ms,表明该光电探测器对紫外光展现出快速的响应。
图8为实施例3制备的光电探测器在暗态、光照环境下电流随电压的变化曲线图。由图8可知,电压为0.7V时,开关比为500。光电探测器探测率D*达到了8×1015Jones,截止频率f3dB达到了10kHz,200次开关相应损失为3%,光探测器在5V/mm的场强下老化30s,暗电流仅提高了12%。
实施例4
制备COF-609层和[SnCl6]2+层交叠的(COF-609)SnCl4钙钛矿单晶:
与实施例1相比,区别仅在于,将降温过程改为未搅拌,其余降温结晶速率和步骤均与实施例1一致。未搅拌的样品结晶性相比实施例1样品结晶性较差,结果表明,降温初期的前驱体溶解对后期晶体质量具有显著影响。较高的溶解程度将生长得到较高质量的单晶。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (8)
1.一种基于COF结构的钙钛矿单晶,其特征在于,所述基于COF结构的钙钛矿单晶为COF层和无机八面体层交叠结构的COF-BX4钙钛矿单晶;其中,B为Zr4+、Ni4+或Sn4+,X为Cl-、Br-或I-。
2.根据权利要求1所述的基于COF结构的钙钛矿单晶,其特征在于,所述COF层的原料为COF-609或BT-PTO COF。
3.一种权利要求1或2所述基于COF结构的钙钛矿单晶的制备方法,其特征在于,包括以下步骤:
将所述COF层的COF原料和无机八面体层的金属盐原料溶于氢卤酸中并稀释,得到钙钛矿前驱体溶液;所述钙钛矿前驱体溶液反应后降温结晶,得到所述基于COF结构的钙钛矿单晶。
4.根据权利要求3所述的制备方法,其特征在于,所述氢卤酸为质量浓度36~45%的盐酸、氢溴酸或氢碘酸;所述稀释使用的稀释液为乙醇。
5.根据权利要求3所述的制备方法,其特征在于,所述COF原料与所述金属盐原料的摩尔比为1:2。
6.根据权利要求3所述的制备方法,其特征在于,所述金属盐原料在氢卤酸中的浓度为0.03~0.06mol/L;所述COF原料在氢卤酸中的浓度为0.03mol/L。
7.根据权利要求3所述的制备方法,其特征在于,所述反应的温度为140℃,时间为5h;所述降温为梯度降温,具体为搅拌状态下以1~2℃/h的速率降温至120℃,以1~2℃/h的速率降温至90℃并停止搅拌,保温10h后以1~2℃/h的速率冷却。
8.一种权利要求1或2所述基于COF结构的钙钛矿单晶在光电探测器或钙钛矿电池中的应用。
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