CN113845142B - 一种铯铅碘钙钛矿纳米晶及其制备方法和应用 - Google Patents
一种铯铅碘钙钛矿纳米晶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开一种铯铅碘钙钛矿纳米晶及其制备方法和应用。该方法包括如下步骤:将铅碘前驱体和铯前驱体加入N,N‑二甲基甲酰胺中,至前驱体完全溶解后,得到混合前驱体溶液A;将表面活性剂和憎溶剂混合均匀,得到溶液B;在室温搅拌下,将混合前驱体溶液A快速滴入溶液B中反应,得到黑相铯铅碘钙钛矿纳米晶。上述过程在常温下进行,设备简单、不需要任何保护气体,操作简便高效,可规模化生产,有效弥补了现有技术中黑相铯铅碘钙钛矿纳米晶无法高效室温直接合成的短板。
Description
技术领域
本发明属于新型纳米光电子材料技术领域,尤其涉及一种铯铅碘钙钛矿纳米晶及其制备方法和应用。
背景技术
近年来,钙钛矿材料受到人们的广泛关注,主要由于该类材料的合成成本低,且具有电子迁移率快,激子结合能大、扩散距离长等优异的电学性能,以及高的发光效率、窄发光半峰宽以及禁带宽度可调等光学性质。黑相铯铅碘(CsPbI3)纳米晶,包括α(立方相),β(四方相)和γ(正交相),是一种具有理想带隙的钙钛矿材料,相对于有机-无机杂化钙钛矿,其具有更优异的热稳定性和环境稳定性,适合于太阳能和发光二极管的光学特性,是光电子材料中最为重要和稀缺的材料之一。现有钙钛矿纳米晶的制备方法主要有热注入法和溶剂辅助共沉淀法。而热注入法的实验条件苛刻,如高温、惰性气体保护等,操作繁琐,产率低,不可避免地增加了制备成本,且其大规模制备存在重现性差等问题,不符合工业生产需求(Nano Letters,2015,6,3692)。溶剂辅助共沉淀法可以作为一个更有效的选择,例如“一种室温大产率无机卤素钙钛矿荧光量子点的制备方法”(专利公告号CN 105331362 B)选择二甲基甲酰胺作为良溶剂,将PbX2和CsX(X=Cl,Br或I)溶于二甲基甲酰胺中,然后加入到甲苯、正己烷等不良溶剂中,在常温下可以合成CsPbX3纳米晶,该方法无需任何气体保护,具有操作简便等优点,在CsPbX3纳米晶合成中具有很大的优势,但由于铯铅碘稳定性较差,目前仍然无法采用该方法直接合成黑相的铯铅碘纳米晶。另外,该合成方法需要使用大量的有毒有机溶剂,尚不适合工业化生产。因此,开发一种具有高重现性、简单、绿色的制备方法,用于室温下直接合成黑相铯铅碘纳米晶具有重要意义和经济价值。
发明内容
本发明提供一种铯铅碘钙钛矿纳米晶(其化学式为CsPbI3)的制备方法,所述制备方法包括如下步骤:
(1)将铅碘前驱体和铯前驱体加入N,N-二甲基甲酰胺中,至前驱体完全溶解后,得到混合前驱体溶液A;
(2)将表面活性剂和憎溶剂混合均匀,得到溶液B;
(3)在室温搅拌下,将所述混合前驱体溶液A快速滴入所述溶液B中反应,得到黑相铯铅碘钙钛矿纳米晶。
根据本发明的实施方案,步骤(1)中,所述的铅碘前驱体为氢铅碘(HPbI3)和二甲基铵铅碘(DMAPbI3)中的至少一种,例如为氢铅碘。
根据本发明的实施方案,步骤(1)中,所述的铯前驱体为碘化铯、乙酸铯和碳酸铯中的至少一种,例如为碘化铯。
根据本发明的实施方案,步骤(1)中,所述的混合前驱体溶液A中Pb和Cs的摩尔比为5:1~1:2,例如2:1或3:1。
根据本发明的实施方案,步骤(1)中,所述铅碘前驱体与N,N-二甲基甲酰胺(DMF)的摩尔体积比为(0.01-1)mmol:(0.1-1)mL,例如为(0.1-0.5)mmol:(0.3-0.8)mL,示例性为0.2mmol:0.5mL或0.4mmol:0.5mL。
根据本发明的实施方案,步骤(1)中,可以通过本领域已知方法使前驱体溶解,例如通过超声分散的方式。
根据本发明的实施方案,步骤(2)中,所述的表面活性剂为油酸、油胺、巯基乙酸、烷基硫醇、三正辛基膦(TOP)和三正丁基膦(TBP)中的至少一种,例如为油酸、油胺和三正辛基膦中的至少一种。
根据本发明的实施方案,步骤(2)中,所述的憎溶剂选自石油醚、正己烷、环己烷、环戊烷、二氯甲烷、正丁醇、氯仿、乙酸丁酯、乙酸乙酯、四氢呋喃、异丙醇和无水乙醇中的至少一种,例如为异丙醇、正丙醇、乙醇和乙酸乙酯中的至少一种。
根据本发明的实施方案,步骤(2)中,所述的表面活性剂和憎溶剂的体积比为0.04-0.4,优选为0.1-0.3,示例性为0.14、0.2或0.24。
根据本发明的实施方案,步骤(2)中,所述混合可以通过本领域已知方式实现,例如搅拌方式。优选地,所述搅拌的速度为500-2000r/min,例如为800-1500r/min。优选地,所述搅拌的时间为5-60min,例如为5-30min。
根据本发明的实施方案,步骤(3)中,所述的混合前驱体溶液A和溶液B的体积比为1:(10-500),例如1:(15-100),示例性为1:17、1:17.5、1:30、1:60。
根据本发明的实施方案,步骤(3)中的快速滴加在搅拌条件下进行。例如,所述搅拌的速度为1000-1500r/min,例如1000-1300r/min。例如,所述搅拌的时间为0.5-10min,例如1-5min。
根据本发明的实施方案,步骤(3)中,所述反应得到红棕色产物,而后进行离心处理,得到的沉淀物为黑相铯铅碘钙钛矿纳米晶。
根据本发明的实施方案,所述铯铅碘钙钛矿纳米晶的制备方法,所述制备方法包括如下步骤:
(1)将铅碘前驱体和铯前驱体加入N,N-二甲基甲酰胺中,至前驱体完全溶解后,得到混合前驱体溶液A;
所述的铅碘前驱体为氢铅碘(HPbI3)和二甲基铵铅碘(DMAPbI3)中的至少一种,例如为氢铅碘;
(2)将表面活性剂和憎溶剂混合均匀,得到溶液B;
所述的表面活性剂为油酸、油胺、巯基乙酸、烷基硫醇、三正辛基膦(TOP)和三正丁基膦(TBP)中的至少一种;
所述的憎溶剂选自石油醚、正己烷、环己烷、环戊烷、二氯甲烷、正丁醇、氯仿、乙酸丁酯、乙酸乙酯、四氢呋喃、异丙醇和无水乙醇中的至少一种;
(3)在室温搅拌下,将所述混合前驱体溶液A快速滴入所述溶液B中反应,得到黑相铯铅碘钙钛矿纳米晶。
本发明还提供由上述方法制备得到的黑相铯铅碘钙钛矿纳米晶。优选地,所述铯铅碘钙钛矿纳米晶为四方相铯铅碘钙钛矿纳米晶。
本发明还提供所述黑相铯铅碘钙钛矿纳米晶在光电领域中的应用,例如用于太阳能电池、发光二极管、光电探测器、激光器、X射线成像等领域中。
本发明的有益效果:
为了解决现有技术的不足,本发明提供了一种铯铅碘钙钛矿纳米晶及其制备方法和应用,以解决黑相铯铅碘纳米晶无法室温直接合成,热注入法制备产率低,且需要惰性气体保护或高温等问题。相对于传统方法,本发明采用更易于溶解的铅碘前驱体替代碘化铅,同时采用异丙醇或无水乙醇等作为憎溶剂,且大大减少毒性溶剂N,N-二甲基甲酰胺的使用,并严格限定物料配比,使铯铅碘钙钛矿纳米晶的稳定性更好,有效弥补了现有技术中无法在室温下直接合成黑相铯铅碘钙钛矿纳米晶的短板。该制备方法具有制备工艺简单、快速、原料来源广泛以及有毒有机溶剂消耗量小的特点,在室温下操作,无需惰性气体保护,时间短,成本低,操作简便高效,更绿色环保,适合大规模批量生产。
附图说明
图1为本发明实施例1-7黑相铯铅碘纳米晶合成示意图。
图2为本发明实施例1中黑相铯铅碘纳米晶的XRD衍射图谱。
图3为本发明实施例1中黑相铯铅碘纳米晶溶液在365nm紫外光照射下的发光图。
图4为本发明实施例1中黑相铯铅碘纳米晶的透射电子显微镜图。
图5为本发明实施例1中黑相铯铅碘纳米晶的紫外可见吸收光谱和发射光谱。
图6为本发明实施例6中黑相铯铅碘纳米晶的紫外可见吸收光谱和发射光谱。
图7为本发明对比例1中黄相铯铅碘的XRD衍射图谱。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明,以下实施例中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
实施例1
如图1所示的制备过程,步骤1、取0.235g HPbI3和0.052g CsI称量好装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取1mL油酸和0.2mL油胺加入到装有5mL异丙醇的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 60μL快速注入到溶液B中,1000rpm/min下持续搅拌1min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
实施例1所得的CsPbI3纳米晶的XRD图谱见图2,由图可见合成的纳米晶为四方晶相结构(黑相)。该纳米晶在紫外光下,可发明亮的红光(图3)。从图4透射电子显微镜图可以看出合成的纳米晶为立方形,粒径较为均一,且分散性好;如图5所示,制备的纳米晶的最大发射波长为718nm。
实施例2
如图1所示的制备过程,步骤1、取0.353g HPbI3和0.052g CsI称量好装入4mL样品瓶中装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取1mL油酸和0.2mL油胺加入到装有5mL异丙醇的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 60μL快速注入到溶液B中,1000rpm/min下持续搅拌1min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
实施例3
如图1所示的制备过程,步骤1、取0.353g HPbI3和0.052g CsI称量好装入4mL样品瓶中装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取1mL油酸、0.2mL油胺和50μL三正辛基膦加入到装有5mL异丙醇的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 60μL快速注入到该溶液B中,1000rpm/min下持续搅拌1min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
实施例4
如图1所示的制备过程,步骤1、取0.235g HPbI3和0.052g CsI称量好装入4mL样品瓶中装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取1mL油酸加入到装有5mL异丙醇的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、步骤1制得的前驱体溶液A 60μL快速注入到该溶液B中,1000rpm/min下持续搅拌1min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
实施例5
如图1所示的制备过程,步骤1、取0.235g HPbI3和0.052g CsI称量好装入4mL样品瓶中装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取1mL油酸、0.2mL油胺加入到装有5mL乙酸乙酯的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 50μL快速注入到该溶液B中,1200rpm/min下持续搅拌3min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
实施例6
如图1所示的制备过程,步骤1、取0.235g HPbI3和0.052g CsI称量好装入4mL样品瓶中装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取0.5mL油酸、0.2mL油胺加入到装有5mL环己烷的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 40μL快速注入到该混合溶液B中,1200rpm/min下持续搅拌3min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
实施例7
如图1所示的制备过程,步骤1、取0.235g HPbI3和0.052g CsI称量好装入4mL样品瓶中装入4mL样品瓶中。然后加入0.5mL DMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取0.5mL油酸、0.2mL油胺加入到装有5mL无水乙醇的烧杯中,在1200rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 40μL快速注入到该混合溶液B中,1000rpm/min下持续搅拌0.5min,即得到红棕色产物,然后10000r/min离心处理,弃去上层清液,沉淀物即为黑相铯铅碘纳米晶。所以操作过程中均为开放环境且在室温下完成,无需惰性保护气体和严格的脱水脱氧处理。
如图6所示,制备的纳米晶的最大发射波长为725nm。
对比例1
步骤1、取0.184g PbI2和0.052g CsI称量好装入4mL样品瓶中。然后加入0.5mLDMF,超声5min使其完全溶解,形成前驱体溶液A。
步骤2、取1mL油酸和0.2mL油胺加入到装有5mL异丙醇的烧杯中,在800rpm/min下持续搅拌5min使其混合均匀,得到溶液B。
步骤3、取步骤1制得的前驱体溶液A 60μL快速注入到混合溶液B中,1000rpm/min下持续搅拌1min,即得到黄色产物。所有操作过程中均为开放环境且在室温下完成,无惰性保护气体和严格的脱水脱氧处理。
对比例1所得的产物的XRD图谱见图7,由图可见使用PbI2作为前驱体合成的产物为正交相晶相结构(黄相)。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种铯铅碘钙钛矿纳米晶的制备方法,其特征在于,所述铯铅碘钙钛矿纳米晶的化学式为CsPbI3,所述制备方法包括如下步骤:
(1)将铅碘前驱体和铯前驱体加入N,N-二甲基甲酰胺中,至前驱体完全溶解后,得到混合前驱体溶液A;
(2)将表面活性剂和憎溶剂混合均匀,得到溶液B;
(3)在室温搅拌下,将所述混合前驱体溶液A快速滴入所述溶液B中反应,得到黑相铯铅碘钙钛矿纳米晶;
步骤(1)中,所述的铅碘前驱体为氢铅碘和二甲基铵铅碘中的至少一种;
步骤(2)中,所述的憎溶剂选自石油醚、正己烷、环己烷、环戊烷、二氯甲烷、正丁醇、氯仿、乙酸丁酯、乙酸乙酯、四氢呋喃、异丙醇和无水乙醇中的至少一种。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述的铅碘前驱体为氢铅碘;
和/或,步骤(1)中,所述的铯前驱体为碘化铯、乙酸铯和碳酸铯中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述的混合前驱体溶液A中Pb和Cs的摩尔比为5:1~1:2;
和/或,步骤(1)中,所述铅碘前驱体与N,N-二甲基甲酰胺的摩尔体积比为(0.01-1)mmol:(0.1-1)mL。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述的表面活性剂为油酸、油胺、巯基乙酸、烷基硫醇、三正辛基膦和三正丁基膦中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述的憎溶剂选自异丙醇、无水乙醇和乙酸乙酯中的至少一种。
6.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述的表面活性剂和憎溶剂的体积比为0.04-0.4;
和/或,步骤(2)中,所述混合为搅拌方式;所述搅拌的速度为500-2000 r/min;所述搅拌的时间为5-60 min。
7.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,所述的混合前驱体溶液A和溶液B的体积比为1:(10-500);
和/或,步骤(3)中的快速滴加在搅拌条件下进行;
和/或,步骤(3)中,所述反应得到红棕色产物,而后进行离心处理,得到的沉淀物为黑相铯铅碘钙钛矿纳米晶。
8.权利要求1-7任一项所述方法制备得到的黑相铯铅碘钙钛矿纳米晶。
9.权利要求8所述黑相铯铅碘钙钛矿纳米晶在光电领域中的应用。
10.根据权利要求9所述的应用,其特征在于,用于太阳能电池、发光二极管、光电探测器、激光器、X射线成像领域中。
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