CN110304651A - 一种具有包覆结构的钙钛矿纳米晶及其制备方法 - Google Patents
一种具有包覆结构的钙钛矿纳米晶及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有包覆结构的钙钛矿纳米晶及其制备方法,该钙钛矿纳米晶包括小粒径钙钛矿纳米晶,以及包覆在小粒径钙钛矿纳米晶外的大粒径钙钛矿纳米晶;小粒径钙钛矿纳米晶的粒径为10~20nm;大粒径钙钛矿纳米晶的粒径为100~200nm;大粒径钙钛矿纳米晶呈立方体形,由小粒径钙钛矿纳米晶组装而成。本发明公开了一种具有全新形貌的钙钛矿纳米晶材料,兼具小尺寸钙钛矿纳米晶优异的光电性能,和大尺寸钙钛矿纳米晶的高稳定性与载流子迁移距离长等优点,有望在太阳能电池以及LED等光电领域有着广泛的应用前景。
Description
技术领域
本发明涉及钙钛矿材料及其制备领域,尤其涉及一种具有包覆结构的钙钛矿纳米晶及其制备方法。
背景技术
钙钛矿纳米材料鉴于其具有宽光谱范围、高吸收系数、浅缺陷能级等物理特性,在发光和显示器件、太阳能光伏电池、光电探测器等方面展现出了诱人的应用前景。
钙钛矿纳米材料从维度上一般分为零维的纳米晶、一维的纳米线以及多维的纳米片等等,其中,零维的钙钛矿纳米晶具有很好的荧光特性从而被广泛应用在光伏材料、发光材料等领域。
众所周知,小尺寸的钙钛矿纳米晶具有更好的光电性能,比如具有更窄的PL荧光峰、更高的吸收系数,但是由于其尺寸较小,载流子的迁移距离短、表面缺陷严重,会加剧了电子、空穴的复合,不利于电子和空穴的有效分离,且小尺寸的钙钛矿材料稳定性差,不利于长期使用和保存。大尺寸的钙钛矿材料具有高稳定性,载流子迁移距离长,但是其光电性能不及小尺寸的钙钛矿材料。
申请公布号为CN 108190944A的中国专利文献中公开了一种钙钛矿纳米晶的制备方法,具体包括:步骤b1:将10mL十八烯加入到20mL的试剂瓶中,加入0.5-1mL的油酸和0.5-1mL的油胺,然后加入0.5-2mL的有机钛酯,不断搅拌;步骤b2:称量0.1-0.4mmol的PbBr2和0.1mmol的Cs2CO3加入到上述不断搅拌的溶液中反应;步骤b3:将反应后的溶液在11000rpm条件下离心5分钟,保留下层沉淀中的CsPbBr3纳米晶并用甲苯分散保存,即得到所述钙钛矿纳米晶。
上述技术方案中制备得到的钙钛矿纳米晶材料的尺寸为10~100nm,该产物中,虽然同时包含有大尺寸与小尺寸的钙钛矿纳米晶,但这种小尺寸和大尺寸的钙钛矿纳米晶无法协同作用,此外,这种制备方法得到的纳米晶尺寸分布跨度比较大,也不是特别的均匀,也就会造成材料性能的不稳定。
因此,如果能制备一种兼具小尺寸钙钛矿纳米晶与大尺寸钙钛矿纳米晶优势的钙钛矿纳米晶材料,将有望在太阳能电池以及LED等光电领域获得更广泛的应用前景。
发明内容
针对现有技术存在的上述问题,本发明公开了一种具有全新形貌的钙钛矿纳米晶材料,兼具小尺寸钙钛矿纳米晶优异的光电性能,和大尺寸钙钛矿纳米晶的高稳定性与载流子迁移距离长等优点,有望在太阳能电池以及LED等光电领域有着广泛的应用前景。
具体技术方案如下:
一种具有包覆结构的钙钛矿纳米晶,包括小粒径钙钛矿纳米晶,以及包覆在所述小粒径钙钛矿纳米晶外的大粒径钙钛矿纳米晶;
所述大粒径钙钛矿纳米晶呈立方体形,由所述小粒径钙钛矿纳米晶组装而成;
所述小粒径钙钛矿纳米晶的粒径为10~20nm;
所述大粒径钙钛矿纳米晶的粒径为100~200nm。
本发明公开的钙钛矿纳米晶,具有大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的独特形貌,由于该形貌中同时包含了粒径为10~20nm的小粒径钙钛矿纳米晶与粒径为100~200nm的大粒径钙钛矿纳米晶,因此兼具了小尺寸钙钛矿纳米晶优异的光电性能,和大尺寸钙钛矿纳米晶的高稳定性与载流子迁移距离长等优点,使得光生载流子可以更高效的产生与分离。
所述钙钛矿纳米晶的结构通式为APbX3;
其中,A选自CH3NH3 +、CH2(NH2)3 +或Cs+,X选自Cl、Br或I。
当A选自CH3NH3 +或CH2(NH2)3 +时,所述钙钛矿纳米晶为无机有机杂化钙钛矿纳米晶;当A选自Cs+时,所述钙钛矿纳米晶为全无机钙钛矿纳米晶。
本发明还公开了所述具有包覆结构的钙钛矿纳米晶的制备方法,包括如下步骤:
(1)将PbX2、AX、脂肪酸、脂肪胺Ⅰ与极性有机溶剂混合均匀,得到混合溶液;
(2)将混合溶液与非极性有机溶剂混合,剧烈搅拌,得到溶胶;
(3)向溶胶中缓慢滴加脂肪胺Ⅱ,搅拌均匀后,再经后处理得到所述具有包覆结构的钙钛矿纳米晶;
所述脂肪胺Ⅰ和脂肪胺Ⅱ的碳数均选自8~18,且所述脂肪胺Ⅱ的碳数大于所述脂肪胺Ⅰ的碳数,两者之差为4~10。
本发明首先采用常规的共沉淀法制备得到小尺寸的钙钛矿纳米晶,再通过后续添加不同碳数的脂肪胺作为表面配体,使得原小尺寸的钙钛矿纳米晶发生自组装反应,得到新的钙钛矿包覆结构。
经试验发现,要获得该特殊形貌的关键在于两点:一是后续添加的脂肪胺Ⅱ的碳数要大于脂肪胺Ⅰ的碳数,两者之差为4~10。二是要对后续添加的脂肪胺Ⅱ的添加量进行控制,添加量不能过小,过小会反应不彻底,过大也会对新结构造成破坏。
步骤(1)中:
所述脂肪酸的碳数选自8~18,优选为油酸。
所述极性有机溶剂需要满足可以同时溶解PbX2、AX、脂肪酸、脂肪胺Ⅰ,可选自本领域常见的种类,如N,N-二甲基甲酰胺(DMF)、N,N-二甲基甲酰胺(DMAc)或二甲基亚砜(DMSO)等等。
所述混合溶液中,PbX2的浓度为0.01~0.1mol/L,优选为0.03~0.04mol/L。
所述PbX2、AX、脂肪酸与脂肪胺Ⅰ的摩尔比为1:1:5~10:1~5;优选为1:1:7~8:1~2。
步骤(2)中:
所述非极性溶剂可选自本领域常见的种类,如甲苯、环己烷等等。
所述混合溶液与所述非极性有机溶剂的体积比为1:10~40;优选为1:10~20。
步骤(3)中:
所述脂肪胺Ⅱ与所述溶胶的体积比为1:100~500;优选为1:250~300。
所述后处理包括将反应液离心、分离和洗涤处理。
优选地:
所述混合溶液中,PbX2的浓度为0.036mol/L;
所述PbX2、AX、脂肪酸与脂肪胺Ⅰ的摩尔比为1:1:7.5:1.5;
所述混合溶液与所述非极性有机溶剂的体积比为1:10;
所述脂肪胺Ⅱ与所述溶胶的体积比为1:275。
进一步优选:
所述脂肪胺Ⅰ的碳数为8,即选自油胺,所述脂肪胺Ⅱ的碳数选自12~18。
再进一步优选,所述脂肪胺Ⅰ选自正辛胺,所述脂肪胺Ⅱ选自十二胺或油胺。
更优选,所述脂肪胺Ⅰ选自正辛胺,所述脂肪胺Ⅱ选自油胺。
经试验发现,相对于以脂肪胺Ⅰ选自正辛胺、脂肪胺Ⅱ选自十二胺制备的产物,以脂肪胺Ⅰ选自正辛胺、脂肪胺Ⅱ选自油胺制备的产物,其形貌更为规整,呈规则的正方体型,且大粒径钙钛矿纳米晶内部的小粒径钙钛矿纳米晶的分布更为均匀。
与现有技术相比,本发明具有如下优点:
本发明公开了一种具有全新的独特形貌的钙钛矿纳米晶,该钙钛矿纳米晶具有包覆结构,由大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶构成,其中,小粒径钙钛矿纳米晶的粒径为10~20nm,大粒径钙钛矿纳米晶的粒径为100~200nm,因此兼具了小尺寸钙钛矿纳米晶与大尺寸钙钛矿纳米晶的优势,有望在太阳能电池以及LED等光电领域有着广泛的应用前景。
附图说明
图1为实施例1制备产物的XRD图谱;
图2为实施例1中步骤(2)制备产物的TEM照片;
图3为实施例1中制备产物的TEM照片;
图4为实施例2中制备产物的TEM照片。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
(1)取146.8mg PbBr2(0.4mmol)、44.8mg甲基溴化铵(0.4mmol,CAS号:6876-37-5)、1mL油酸(3mmol)、0.1mL正辛胺(0.6mmol)溶解在10mL DMF中,超声搅拌至充分溶解,得到混合溶液;
(2)取0.5mL混合溶液缓慢滴入5mL甲苯中,充分搅拌10min,得到CH3NH3PbBr3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CH3NH3PbBr3纳米晶溶液中,搅拌10min后,将反应液离心、分离、洗涤,得到产物。
图1为本实施例制备产物的XRD图谱,从图中可以看出,所得产物为CH3NH3PbBr3,为钙钛矿型结构。
将步骤(2)制备的CH3NH3PbBr3纳米晶溶液进行离心、分离、洗涤处理,所得产物的TEM图见图2,观察图2发现,纳米晶的粒径为10nm的独立的立方结构。
图3为本实施例制备产物的TEM图,由图见,粒径为10~20nm的小粒径的钙钛矿纳米晶均匀的分布在粒径为150~200nm的大粒径的钙钛矿纳米晶内,形成大粒径包覆小粒径的结构,大粒径的钙钛矿纳米晶形貌为立方体。
对比例1
(1)取146.8mg PbBr2、44.8mg甲基溴化铵、1mL油酸、0.2mL油胺溶解在10mL DMF(N,N-二甲基甲酰胺)中,超声搅拌至充分溶解,得到混合溶液;
(2)取0.5mL混合溶液缓慢滴入5mL甲苯中,充分搅拌10min,得到CH3NH3PbBr3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CH3NH3PbBr3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
将步骤(2)制备的CH3NH3PbBr3纳米晶溶液进行离心、分离、洗涤处理,对比该产物与最终产物的TEM照片发现,最终产物与步骤(2)中得到的纳米晶相比,粒径稍有变小,但并未组装形成大粒径钙钛矿纳米晶,没有包覆结构出现。
对比例2
(1)取146.8mg PbBr2、44.8mg甲基溴化铵、1mL油酸、0.1mL正辛胺溶解在10mL DMF(N,N-二甲基甲酰胺)中,超声搅拌至充分溶解,得到溶液Ⅰ;
(2)取0.5mL溶液Ⅰ缓慢滴入5mL中,充分搅拌10min,得到CH3NH3PbBr3纳米晶溶液;
(3)取10μL正辛胺缓慢滴入上述CH3NH3PbBr3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
将步骤(2)制备的CH3NH3PbBr3纳米晶溶液进行离心、分离、洗涤处理,对比该产物与最终产物的TEM照片发现,同样只是粒径变小,并未组装形成大粒径钙钛矿纳米晶,没有包覆结构出现。
实施例2
(1)取146.8mg PbBr2、44.8mg甲基溴化铵、1mL油酸、110mg(0.6mmol)十二胺溶解在10mL DMF中,超声搅拌至充分溶解,得到混合溶液;
(2)取0.5mL混合溶液缓慢滴入5mL甲苯中,充分搅拌10min,得到CH3NH3PbBr3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CH3NH3PbBr3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
经XRD测试发现,所得产物为CH3NH3PbBr3。
图4为本实施例制备的产物的TEM图,观察发现,产物虽然也具备大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的结构,但大粒径钙钛矿纳米晶的形貌不规整,并非规则的正方体型,且内部的小粒径钙钛矿纳米晶的分布不均匀。
实施例3
(1)取184.4mg PbI2、44.8mg甲基溴化铵(CAS号:6876-37-5)、1mL油酸、0.1mL正辛胺溶解在10mL DMSO中,超声搅拌至充分溶解,得到混合溶液;
(2)取0.5mL混合溶液缓慢滴入5mL环己烷中,充分搅拌10min,得到CH3NH3PbI3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CH3NH3PbI3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
经XRD测试发现,所得产物为CH3NH3PbI3。
观察其TEM照片发现,产物形貌为大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的结构,大粒径钙钛矿纳米晶为立方体型,粒径为150~200nm,小粒径钙钛矿纳米晶的粒径为10~20nm。
实施例4
(1)取111.2mg PbCl2、44.8mg甲基溴化铵(CAS号:6876-37-5)、1mL油酸、0.1mL正辛胺溶解在10mL DMAc中,超声搅拌至充分溶解,得到混合溶液;
(2)取0.5mL混合溶液缓慢滴入5mL环己烷中,充分搅拌10min,得到CH3NH3PbCl3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CH3NH3PbCl3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
经XRD测试发现,所得产物为CH3NH3PbCl3。
观察其TEM照片发现,产物形貌为大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的结构,大粒径钙钛矿纳米晶为立方体型,粒径为100~150nm,小粒径钙钛矿纳米晶的粒径为10~20nm。
实施例5
(1)取146.8mg PbBr2、85.1mg溴化铯、1mL油酸、0.1mL正辛胺溶解在10mL DMF中,超声搅拌至充分溶解,得到混合溶液;
(2)取0.5mL混合溶液缓慢滴入5mL甲苯中,充分搅拌10min,得到CsPbBr3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CsPbBr3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
经XRD测试发现,所得产物为CsPbBr3。
观察其TEM照片发现,产物形貌为大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的结构,大粒径钙钛矿纳米晶为立方体型,粒径为100~200nm,小粒径钙钛矿纳米晶的粒径为10~20nm。
实施例6
(1)取184.4mg PbI2、104mg碘化铯、1mL油酸、0.1mL正辛胺溶解在10mL DMF(N,N-二甲基甲酰胺)中,超声搅拌至充分溶解,得到溶液Ⅰ;
(2)取0.5mL溶液Ⅰ缓慢滴入5mL甲苯中,充分搅拌10min,得到CsPbI3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CsPbI3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
经XRD测试发现,所得产物为CsPbI3。
观察其TEM照片发现,产物形貌为大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的结构,大粒径钙钛矿纳米晶为立方体型,粒径为150~200nm,小粒径钙钛矿纳米晶的粒径为10~20nm。
实施例7
(1)取111.2mg PbCl2、67.3mg氯化铯、1mL油酸、0.1mL正辛胺溶解在10mL DMF(N,N-二甲基甲酰胺)中,超声搅拌至充分溶解,得到溶液Ⅰ;
(2)取0.5mL溶液Ⅰ缓慢滴入5mL环己烷中,充分搅拌10min,得到CsPbCl3纳米晶溶液;
(3)取20μL油胺缓慢滴入上述CsPbCl3纳米晶溶液中,搅拌10min,反应后将反应液离心、分离、洗涤,得到产物。
经XRD测试发现,所得产物为CsPbCl3。
观察其TEM照片发现,产物形貌为大粒径钙钛矿纳米晶包覆小粒径钙钛矿纳米晶的结构,大粒径钙钛矿纳米晶为立方体型,粒径为100~150nm,小粒径钙钛矿纳米晶的粒径为10~20nm。
Claims (10)
1.一种具有包覆结构的钙钛矿纳米晶,其特征在于,包括小粒径钙钛矿纳米晶,以及包覆在所述小粒径钙钛矿纳米晶外的大粒径钙钛矿纳米晶;
所述大粒径钙钛矿纳米晶呈立方体形,由所述小粒径钙钛矿纳米晶组装而成;
所述小粒径钙钛矿纳米晶的粒径为10~20nm;
所述大粒径钙钛矿纳米晶的粒径为100~200nm。
2.根据权利要求1所述的具有包覆结构的钙钛矿纳米晶,其特征在于,所述钙钛矿纳米晶的结构通式为APbX3;
其中,A选自CH3NH3 +、CH2(NH2)3 +或Cs+,X选自Cl、Br或I。
3.一种根据权利要求1或2所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,包括如下步骤:
(1)将PbX2、AX、脂肪酸、脂肪胺Ⅰ与极性有机溶剂混合均匀,得到混合溶液;
(2)将混合溶液与非极性有机溶剂混合,剧烈搅拌,得到溶胶;
(3)向溶胶中缓慢滴加脂肪胺Ⅱ,经反应后再经后处理得到所述具有包覆结构的钙钛矿纳米晶;
所述脂肪胺Ⅰ和脂肪胺Ⅱ的碳数均选自8~18,且所述脂肪胺Ⅱ的碳数大于所述脂肪胺Ⅰ的碳数,两者之差为4~10。
4.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,步骤(1)中:
所述脂肪酸的碳数选自8~18;
所述混合溶液中,PbX2的浓度为0.01~0.1mol/L;
所述PbX2、AX、脂肪酸与脂肪胺Ⅰ的摩尔比为1:1:5~10:1~5。
5.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,步骤(2)中:
所述混合溶液与所述非极性有机溶剂的体积比为1:10~40。
6.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,步骤(3)中:
所述脂肪胺Ⅱ与所述溶胶的体积比为1:100~500。
7.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,步骤(3)中:
所述后处理包括将反应液离心、分离和洗涤处理。
8.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,所述脂肪胺Ⅰ的碳数为8,所述脂肪胺Ⅱ的碳数选自12~18。
9.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,所述脂肪胺Ⅰ选自正辛胺,所述脂肪胺Ⅱ选自十二胺或油胺。
10.根据权利要求3所述的具有包覆结构的钙钛矿纳米晶的制备方法,其特征在于,所述脂肪胺Ⅰ选自正辛胺,所述脂肪胺Ⅱ选自油胺。
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