CN107078170B - 制备金属硫属化物纳米颗粒的方法及基于其制造光吸光层薄膜的方法 - Google Patents
制备金属硫属化物纳米颗粒的方法及基于其制造光吸光层薄膜的方法 Download PDFInfo
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- CN107078170B CN107078170B CN201580047843.XA CN201580047843A CN107078170B CN 107078170 B CN107078170 B CN 107078170B CN 201580047843 A CN201580047843 A CN 201580047843A CN 107078170 B CN107078170 B CN 107078170B
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- chalcogenide
- nano particle
- zinc
- cupric
- metal
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Abstract
本发明公开了用于合成制造太阳能电池的光吸收层用的金属硫属化物纳米颗粒的单源前体、通过热处理至少一种类型的单源前体制造的金属硫属化物纳米颗粒、其制备方法、使用其制造的薄膜和制造所述薄膜的方法,所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)的任一种金属连接的第VI族元素。
Description
技术领域
本发明涉及用于制造CZTS基太阳能电池光吸收层的金属硫属化物纳米颗粒、制备其的方法、使用所述纳米颗粒制造的CZTS基太阳能电池光吸收层和制造太阳能电池的方法。
本申请要求于2014年11月13日向韩国知识产权局提交的韩国专利申请No.10-2014-0157951的权益,其公开内容通过引用整体并入本文。
背景技术
从其发展的早期阶段开始就已经使用以高成本形成的光吸收层以及作为半导体材料的硅(Si)来制造太阳能电池。为了更经济地制造工业上可行的太阳能电池,已经开发了利用廉价的光吸收材料(例如铜铟镓(二)硒(CIGS)或Cu(In,Ga)(S,Se)2)的薄膜太阳能电池结构。这样的CIGS基太阳能电池通常包括背面电极层、n型结部件和p型光吸收层。含有这类CIGS层的太阳能电池的功率转换效率大于19%。然而,虽然CIGS基薄膜太阳能电池具有潜能,但是铟(In)的供应不足及成本是使用CIGS基光吸收层的薄膜太阳能电池的广泛适用性和可行性的主要障碍。因此,迫切需要开发使用无铟(In)或低铟(In)且低成本的普遍元素的太阳能电池。
因此,作为CIGS基光吸收层的替代物,含有极廉价元素铜(Cu)、锌(Zn)、锡(Sn)、硫(S)或硒(Se)的CZTS(Cu2ZnSn(S,Se)4)基太阳能电池近来受到极大关注。有利地,CZTS具有约1.0eV至约1.5eV的直接带隙和104cm-1或更高的吸收系数,其储量相对高,且CZTS使用价格便宜的Sn和Zn。
1996年首次报道了CZTS异质结PV电池,但CZTS基太阳能电池在技术上不如CIGS基太阳能电池先进,并且CZTS基太阳能电池的光电效率为10%或更低,这远低于CIGS基太阳能电池。CZTS的薄膜通过溅射、混合溅射、脉冲激光沉积、喷雾热解、电沉积/热硫化、电子束加工、Cu/Zn/Sn/热硫化和溶胶-凝胶法制造。
同时,PCT/US/2010-035792公开了通过对使用包含CZTS/Se纳米颗粒的墨的基底进行热处理来形成薄膜。通常,当使用CZTS/Se纳米颗粒形成CZTS薄膜时,由于先前形成的小晶体而难以在随后的形成薄膜的过程中增大晶体尺寸。因此,当各晶粒小时,界面扩展并且在界面处发生电子损失。因此,效率不可避免地劣化。
因此,薄膜中使用的纳米颗粒应包括Cu、Zn和Sn,并且不应是CZTS晶型。然而,不利的是,在仅使用由单一金属元素构成的金属纳米颗粒的情况下,金属纳米颗粒易被氧化并且需要使用过量Se和高温除去氧的随后的附加工艺。
因此,越来越需要与保持整体均匀的金属组成的金属硫属化物纳米颗粒相关的且通过简化的方法制造的技术。
发明内容
技术问题
因此,进行本发明以解决尚未解决的上述问题和其他技术问题。
作为各种广泛和深入的研究和实验的结果,本发明人开发了包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)中任一种金属连接的第VI族元素的单源前体作为合成制造太阳能电池的光吸收层用的金属硫属化物纳米颗粒的单源前体,并且发现,在这种情况下,可制造具有整体均匀组成和高经济效率的金属硫属化物纳米颗粒而不引入另外的第VI族元素源。基于这些发现完成了本发明。
技术方案
根据本发明的一个方面,提供了用于合成制造太阳能电池的光吸收层用的金属硫属化物纳米颗粒的单源前体,
其包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)中任一种金属连接的第VI族元素。
当第VI族元素作为配体与上述金属连接时,不需要另外的第VI族元素源,因此有利地降低了工艺成本并简化了整个工艺。
根据本发明的用于合成制造太阳能电池的光吸收层用的金属硫属化物纳米颗粒的单源前体具体是铜(Cu)-配体络合物、锡(Sn)-配体络合物、或锌(Zn)-配体络合物。
在一个特定实施方案中,所述配体不受限制,只要其可用作第VI族元素源即可,并且例如包括选自以下化合物中的一种或更多种:
其中R表示具有n个或更多个碳原子(n≥1)的烷基,例如甲基、乙基或丙基。
在单源前体中,与金属结合的配体的数目没有特别限制,例如可以为2或4,与一种金属结合的配体的种类可以为一种或更多种。
本发明提供了通过热处理一种或更多种类型的单源前体制造的金属硫属化物纳米颗粒。
在此,“热处理一种或更多种类型的单源前体”意指可热处理可以可变地制备的仅一种类型的单源前体,或者可热处理两种或更多种类型的单源前体,“硫属化物”是指含有第VI族元素,例如硫(S)和/或硒(Se)的物质。
具体地,金属硫属化物纳米颗粒可通过热处理一种类型的单源前体制备,并且由此制备的金属硫属化物纳米颗粒可以是例如含铜(Cu)硫属化物纳米颗粒、含锡(Sn)硫属化物纳米颗粒、或含锌(Zn)硫属化物纳米颗粒。
具体地,含铜(Cu)硫属化物纳米颗粒可以是CuS和/或CuSe,含锡(Sn)硫属化物纳米颗粒可以是SnS和/或SnSe,以及含锌(Zn)硫属化物纳米颗粒可以是ZnS和/或ZnSe。
在一个特定实施方案中,金属硫属化物纳米颗粒可通过热处理两种类型的单源前体来制备,并且由此制备的金属硫属化物纳米颗粒可以是例如含铜(Cu)-锡(Sn)硫属化物纳米颗粒、含铜(Cu)-锌(Zn)硫属化物纳米颗粒、或含锡(Sn)-锌(Zn)硫属化物纳米颗粒。
具体地,含铜(Cu)-锡(Sn)硫属化物纳米颗粒可以是CuaSnSb(0.1≤a≤1.0,0.1≤b≤10.0)和/或CusSnSet(0.1≤s≤10.0,0.1≤t≤10.0),含铜(Cu)-锌(Zn)硫属化物纳米颗粒可以是CucZnSd(0.1≤c≤10.0,0.1≤d≤10.0)和/或CuuZnSev(0.1≤u≤10.0,0.1≤v≤10.0),或者含锡(Sn)-锌(Zn)硫属化物纳米颗粒可以是SneZnSf(0.1≤e≤10.0,0.1≤f≤10.0)和/或SnxZnSey(0.1≤x≤10,0.1≤y≤10.0)。
在一个特定实施方案中,金属硫属化物纳米颗粒可通过热处理三种类型的单源前体来制备,并且由此制备的金属硫属化物纳米颗粒可以是例如含铜(Cu)-锡(Sn)-锌(Zn)硫属化物纳米颗粒。
具体地,含铜(Cu)-锡(Sn)-锌(Zn)硫属化物纳米颗粒可以是CugZnhSnSi(1.0≤g≤10.0,0.5≤h≤3.0,0.1≤i≤10.0)和/或CupZnqSnSer(1.0≤p≤10.0,0.5≤q≤3.0,0.1≤r≤10.0)。
此外,根据本发明的金属硫属化物纳米颗粒可以是包含两种或更多种硫属化物的复合纳米颗粒。
在一个特定实施方案中,包含两种硫属化物的复合纳米颗粒可以是例如由含铜(Cu)硫属化物和含锡(Sn)硫属化物构成的复合纳米颗粒、由含铜(Cu)硫属化物和含锌(Zn)硫属化物构成的复合纳米颗粒,或者由含锡(Sn)硫属化物和含锌(Zn)硫属化物构成的复合纳米颗粒,以及也可以是由含铜(Cu)-锡(Sn)硫属化物和含锌(Zn)硫属化物构成的复合纳米颗粒,由含铜(Cu)-锌(Zn)硫属化物和含锡(Sn)硫属化物构成的复合纳米颗粒,或者由含锡(Sn)-锌(Zn)硫属化物和含铜(Cu)硫属化物构成的复合纳米颗粒。
更优选地,根据本发明的含铜(Cu)-锡(Sn)-锌(Zn)硫属化物纳米颗粒或者包含铜(Cu)、锡(Sn)和锌(Zn)的复合纳米颗粒不需要添加另外的金属源,并且因此可表现出改善的均匀性,原因是每个纳米颗粒包含铜(Cu)、锡(Sn)和锌(Zn)三者。
此外,与一般的纳米颗粒相反,复合纳米颗粒具有核-壳结构。具体地,包含含铜(Cu)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒可以是包括包含含铜(Cu)硫属化物的核和包含含锡(Sn)硫属化物的壳的核-壳结构纳米颗粒,包含含铜(Cu)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒可以是包括包含含铜(Cu)硫属化物的核和含锌(Zn)硫属化物的壳的核-壳结构纳米颗粒,包含含锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒可以是包括包含含锡(Sn)硫属化物的核和含锌(Zn)硫属化物的壳的核-壳结构纳米颗粒,包含含铜(Cu)-锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒可以是包括包含含铜(Cu)-锡(Sn)硫属化物的核和包含含锌(Zn)硫属化物的壳的核壳结构的纳米颗粒,包含含铜(Cu)-锌(Zn)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒可以是包括包含含铜(Cu)-锌(Zn)硫属化物的核和包含含锡(Sn)硫属化物的壳的核壳结构的纳米颗粒,以及包括含有锡(Sn)-锌(Zn)硫属化物和含铜(Cu)硫属化物的复合纳米颗粒可以是包含含锡(Sn)-锌(Zn)硫属化物的核和包含含铜(Cu)硫属化物的壳的核壳结构的纳米颗粒。在这种情况下,核-壳结构的纳米颗粒的粒径可为2纳米至200纳米。
核-壳结构的纳米颗粒对氧化是稳定的,使得在晶粒表面上氧化物的形成最小化,因此可在形成薄膜时改善反应性,原因是铜(Cu)、锡(Sn)和锌(Zn)进一步均匀混合,并且包含各颗粒的核被包含含金属硫属化物的壳所保护。
同时,制备金属硫属化物纳米颗粒的方法可根据纳米颗粒的形状(结构)而改变,并且本发明提供了根据其结构制备金属硫属化物纳米颗粒的方法。
在一个实施方案中,金属硫属化物纳米颗粒可通过热处理包含含有作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)中任一种金属连接的第VI族元素的至少一种类型的单源前体的混合物来制备。
通过上述方法,可制备含铜(Cu)硫属化物纳米颗粒、含锡(Sn)硫属化物纳米颗粒或含锌(Zn)硫属化物纳米颗粒和含铜(Cu)-锡(Sn)硫属化物纳米颗粒、含铜(Cu)-锌(Zn)硫属化物纳米颗粒、含锡(Sn)-锌(Zn)硫属化物纳米颗粒或含铜(Cu)-锡(Sn)锌(Zn)硫属化物纳米颗粒。
在另一个实施方案中,制备金属硫属化物纳米颗粒的方法可包括:
(a)热处理包含至少一种类型的单源前体的混合物,所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)的任一种金属连接的第VI族元素;以及
(b)向经热处理的混合物中添加包含至少一种类型的单源前体的混合物并对所得混合物进行热处理,所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)且步骤(a)中未选择的任一种金属连接的第VI族元素。
此外,所述方法还可包括在步骤(b)之后,添加包含至少一种类型的单源前体的混合物并对所得混合物进行热处理,所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)且步骤(a)和(b)中未选择的任一种金属连接的第VI族元素。
通过上述方法,可制造包含含铜(Cu)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒、包含含铜(Cu)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒、包含含锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒。此外,可制造包含含铜(Cu)-锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒、包含铜(Cu)-锌(Zn)硫属化物和含锡(Sn)的复合纳米颗粒,或者包含含锡(Sn)-锌(Zn)硫属化物和含铜(Cu)硫属化物的复合纳米颗粒。在这种情况下,复合纳米颗粒可以是如上所述的核-壳结构的纳米颗粒。
在制备金属硫属化物纳米颗粒的方法中,热处理在50℃至300℃的温度下进行。当在低于50℃的温度下进行热处理时,配体不能充分分解,并且难以合成根据本发明所期望的纳米颗粒,当在高于300℃的温度下进行热处理时,不利地,所期望的纳米颗粒会被分解或者可形成其他相以及期望的纳米颗粒。
根据本发明的制备金属硫属化物纳米颗粒的方法涉及简单热处理包含作为配体与金属连接的第VI族元素的单源前体,因此不需要另外的第VI族元素源、封端剂、还原剂等以提供低的工艺成本和简单的工艺。
此外,本发明提供一种用于制备包含分散在溶剂中的一种或更多种类型的金属硫属化物纳米颗粒的光吸收层的墨组合物和使用所述金属硫属化物纳米颗粒制造薄膜的方法。
如上所述,“包含根据本发明的一种或更多种类型的金属硫属化物纳米颗粒”是意指包含可根据本发明制备的所有类型的金属硫属化物纳米颗粒中的一种或更多种。
为了形成本发明的CZTS薄膜,墨组合物应包含铜(Cu)、锌(Zn)和锡(Sn)。因此,墨组合物可以由例如铜(Cu)、锌(Zn)和锡(Sn)中的至少一种的组合构成,例如含铜(Cu)硫属化物纳米颗粒和含锡(Sn)-锌(Zn)硫属化物纳米颗粒的组合、含铜(Cu)-锡(Sn)硫属化物纳米颗粒和含铜(Cu)-锌(Zn)硫属化物纳米颗粒的组合以及含铜(Cu)-锡(Sn)-锌(Zn)硫属化物纳米颗粒和含铜(Cu)-锡(Sn)硫属化物纳米颗粒的组合。
在这种情况下,墨组合物中包含的金属硫属化物纳米颗粒的组成可以是CujZnkS(1.0≤j≤4.0,0.5≤k≤2.0)。
当金属组成不在该范围内时,不利地,可能形成次生相并且太阳能电池无法正常地发挥作用,原因是该组合物不属于CZTS的一般组成。
此外,相对于1摩尔的总金属量,墨组合物中包含的金属硫属化物纳米颗粒中第VI族元素的含量可以为0.5至4.0。
当第VI族元素的比例不在该范围内并且例如低于0.5摩尔时,无法供应足够的第VI族元素,可形成部分缺乏第VI族元素的膜,并且该膜可被氧化,以及该比例超过4.0摩尔时,由于薄膜中第VI族元素的不均匀分布,薄膜可能不均匀地生长,并且在制造薄膜的热处理期间第VI族原蒸发,不利地导致在最终薄膜中产生过量的孔。
同时,根据本发明使用金属硫属化物纳米颗粒制造薄膜的方法包括:
(i)使一种或更多种类型的根据本发明的金属硫属化物纳米颗粒分散在溶剂中以制备墨;
(ii)用所述墨涂覆设置有电极的基底;以及
(iii)使涂覆在所述设置有电极的基底上的所述墨干燥,并进行热处理。
因此,当使用根据本发明的金属硫属化物纳米颗粒制造薄膜时,不具有相变的稳定金属硫属化物可抑制薄膜中次生相的形成并提供Cu、Zn和Sn的整体均匀组成。
在一个特定实施方案中,可使用步骤(i)的溶剂而没有特别限制,只要其是通常使用的有机溶剂即可。溶剂可以是选自以下的有机溶剂或其组合:烷烃、烯烃、炔烃、芳族化合物、酮、腈、醚、酯、有机卤化物、醇、胺、硫醇、羧酸、膦、磷酸酯、亚砜和酰胺。
具体地,醇溶剂可以是选自以下的至少一种混合溶剂:乙醇、1-丙醇、2-丙醇、1-戊醇、2-戊醇、1-己醇、2-己醇、3-己醇、庚醇、辛醇、乙二醇(EG)、二乙二醇单乙醚(DEGMEE)、乙二醇单甲醚(EGMME)、乙二醇单乙醚(EGMEE)、乙二醇二甲醚(EGDME)、乙二醇二乙醚(EGDEE)、乙二醇单丙醚(EGMPE)、乙二醇单丁醚(EGMBE)、2-甲基-1-丙醇、环戊醇、环己醇、丙二醇丙醚(PGPE)、二乙二醇二甲醚(DEGDME)、1,2-丙二醇(1,2-PD)、1,3-丙二醇(1,3-PD)、1,4-丁二醇(1,4-BD)、1,3-丁二醇(1,3-BD)、α-萜品醇、二甘醇(DEG)、甘油、2-(乙基氨基)乙醇、2-(甲基氨基)乙醇和2-氨基-2-甲基-1-丙醇。
胺溶剂可以是选自以下的至少一种混合溶剂:三乙胺、二丁胺、二丙胺、丁胺、乙醇胺、二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、三乙醇胺、2-氨基乙基哌嗪、2-羟基乙基哌嗪、二丁基胺、三(2-氨乙基)胺和己胺。
硫醇溶剂可以是选自以下的至少一种混合溶剂:1,2-乙二硫醇、戊硫醇、己硫醇和巯基乙醇。
烷烃溶剂可以是选自以下的至少一种混合溶剂:己烷、庚烷和辛烷。
芳族溶剂可以是选自以下的至少一种混合溶剂:甲苯、二甲苯、硝基苯和吡啶。
有机卤化物溶剂可以是选自以下的至少一种混合溶剂:氯仿、二氯甲烷、四氯化碳、二氯乙烷和氯苯。
腈溶剂可以是乙腈。
酮溶剂可以是选自以下的至少一种混合溶剂:丙酮、环己酮、环戊酮和乙酰丙酮。
醚溶剂可以是选自以下的至少一种混合溶剂:乙醚、四氢呋喃和1,4-二烷。
亚砜溶剂可以是选自以下的至少一种混合溶剂:二甲基亚砜(DMSO)和环丁砜。
酰胺溶剂可以是选自以下的至少一种混合溶剂:二甲基甲酰胺(DMF)和n-甲基-2-吡咯烷酮(NMP)。
酯溶剂可以是选自以下的至少一种混合溶剂:乳酸乙酯、γ-丁内酯和乙酰乙酸乙酯。
羧酸溶剂可以是选自以下的至少一种混合溶剂:丙酸、己酸、内消旋-2,3-二巯基琥珀酸、硫代乳酸和硫代乙醇酸。
然而,这些溶剂仅作为实例给出,本发明不限于此。
如果需要,可进一步加入添加剂以制备步骤(i)中的墨。
添加剂可包括例如选自以下的至少一种:分散剂、表面活性剂、聚合物、粘合剂、交联剂、乳化剂、消泡剂、干燥剂、填料、填量剂、增稠剂、膜调理剂、抗氧化剂、流化剂、流平剂和腐蚀抑制剂。特别地,添加剂可以包括选自以下的至少一种:聚乙烯吡咯烷酮(PVP)、聚乙烯醇(PVA)、Anti-terra 204、Anti-terra 205、乙基纤维素和DispersBYK110。
例如,形成步骤(ii)的涂层的方法可包括选自以下的一种或更多种:湿法涂覆、喷涂、旋涂、刮刀涂覆、接触印刷、顶部进料反转印刷、底部进料反转印刷、喷嘴进料反转印刷、凹版印刷、微型凹版印刷、反向微型凹版印刷、辊涂、狭缝模头涂覆、毛细管涂覆、喷墨印刷、喷射沉积和喷雾沉积。
步骤(iii)的热处理可在S或Se的存在下进行。该方法可任选地包括硒化以制备具有高密度的太阳能电池薄膜。可通过多种方法进行硒化。
在第一实例中,硒化可通过将颗粒形式的S和/或Se与步骤(i)的金属硫属化物纳米颗粒一起分散在溶剂中以制备墨并进行步骤(iii)的热处理来进行。
在第二实例中,硒化可通过在S或Se的存在下进行步骤(iii)的热处理来进行。
更具体地,S或Se的存在可通过供应H2S或H2Se气体或通过加热供应Se或S气体来实现。
在第三实例中,硒化可以通过在步骤(ii)之后在薄膜上沉积S或Se来进行。
此外,本发明提供通过该方法制造的薄膜。
薄膜可以具有0.5μm至3.0μm的厚度,更具体地,0.5μm至2.5μm的厚度。
当薄膜的厚度小于0.5μm时,由于光吸收层的密度和量不足,不能获得期望的光电效率,当薄膜的厚度超过3.0μm时,随着载流子的移动距离增加,导致复合的可能性增加,从而发生效率的降低。
此外,本发明提供使用所述薄膜制造的薄膜太阳能电池。
制造薄膜太阳能电池的方法是本领域技术人员已知的,因此省略其详细说明。
附图说明
图1是根据实施例1的金属硫属化物纳米颗粒的SEM图像;
图2是根据实施例1的金属硫属化物纳米颗粒的XRD图;
图3是根据实施例1的金属硫属化物纳米颗粒的放大的TEM图像;
图4是根据实施例4的金属硫属化物纳米颗粒的SEM图像;
图5是根据实施例4的金属硫属化物纳米颗粒的XRD图;
图6是根据实施例6的金属硫属化物纳米颗粒的SEM图像;
图7是根据实施例6的金属硫属化物纳米颗粒的XRD图;
图8是根据实施例6的金属硫属化物纳米颗粒的EDX分析表;
图9是实施例7中制造的薄膜的SEM图像;
图10是实施例7中制造的薄膜的XRD图;
图11是实施例8中制造的薄膜的SEM图像;
图12是实施例8中制造的薄膜的XRD图;
图13是实施例9中制造的薄膜的SEM图像;
图14是实施例9中制造的薄膜的XRD图;
图15是比较例4中制造的薄膜的SEM图像;
图16是比较例4中制造的薄膜的XRD图;
图17是由实施例7中制造的薄膜制造的太阳能电池的I-V图;
图18是由实施例8中制造的薄膜制造的太阳能电池的I-V图;
图19是由实施例9中制造的薄膜制造的太阳能电池的I-V图;以及
图20是由比较例4中制造的薄膜制造的太阳能电池的I-V图。
最佳实施方式
现在,将参照以下实施例更详细地描述本发明。提供这些实施例仅用于说明本发明,而不应被解释为限制本发明的范围和精神。
<实施例1>
金属硫属化物纳米颗粒(Cu2SnS3/ZnS)的合成
将4mmol Cu(CS2NEt2)2单源前体和2mmol Sn(CS2NEt2)4单源前体与20mL油酸和180mL 1-十八烯混合。使混合物加热至160℃并反应1小时以制备Cu2SnS3纳米颗粒。
使Cu2SnS3纳米颗粒的分散体离心并用1-十八碳烯洗涤三次。将所得物质与Zn(CS2OEt)2单源前体混合,随后加热至120℃并反应1小时以制备包括包含Cu2SnS3相和ZnS相的复合纳米颗粒和Cu2SnS3-ZnS纳米颗粒的金属硫属化物纳米颗粒。通过离心纯化金属硫属化物纳米颗粒。
所形成的金属硫属化物纳米颗粒的扫描电子显微镜(SEM)图像、XRD图和透射电子显微镜(TEM)图像示于图1至3。
作为XRD分析的结果,发现颗粒以Cu2SnS3晶相与ZnS晶相的组合形式存在,以及如从图3可以看出,颗粒以包含均匀分布的Cu2SnS3和ZnS相的复合纳米颗粒或Cu2SnS3-ZnS结构的纳米颗粒的形式存在。
<实施例2>
金属硫属化物纳米颗粒(Cu2SnS3/ZnS)的合成
将4mmol Cu(CS2NEt2)2单源前体和2mmol Sn(CS2NEt2)4单源前体与20mL油酸和180mL 1-十八烯混合。使混合物加热至160℃并反应1小时以制备Cu2SnS3纳米颗粒。
使Cu2SnS3纳米颗粒的分散体离心并用1-十八碳烯洗涤三次。将所得物质与Zn(CS2NEt2)2单源前体混合,随后加热至120℃并反应1小时以制备包括包含Cu2SnS3相和ZnS相的复合纳米颗粒和Cu2SnS3-ZnS纳米颗粒的金属硫属化物纳米颗粒。通过离心纯化金属硫属化物纳米颗粒。
<实施例3>
金属硫属化物纳米颗粒(Cu2SnS3)的合成
将4mmol Cu(CS2NEt2)2单源前体和2mmol Sn(CS2NEt2)4单源前体与20mL油酸和180mL 1-十八烯混合。使混合物加热至160℃并反应1小时以制备Cu2SnS3纳米颗粒。离心Cu2SnS3纳米颗粒。
<实施例4>
金属硫属化物纳米颗粒(ZnS)的合成
将4mmol Zn(CS2NEt2)2单源前体与100mL二甲苯混合。使混合物加热至130℃并反应1小时以制备ZnS纳米颗粒,然后通过离心纯化。
所形成的金属硫属化物纳米颗粒的扫描电子显微镜(SEM)图像和XRD图示于图4和5中。
<实施例5>
金属硫属化物纳米颗粒(ZnS)的合成
将4mmol Zn(CS2OEt2)2单源前体与100mL二甲苯混合。使混合物加热至130℃并反应1小时以制备ZnS纳米颗粒。离心ZnS纳米颗粒。
<实施例6>
将4mmol Cu(CS2NEt2)2单源前体、2mmol Sn(CS2NEt2)4单源前体和2.4mmol Zn(CS2NEt2)2单源前体与20mL的油酸和180mL 1-十八碳烯混合。使混合物加热至160℃并反应1小时以制备包括包含Cu2SnS3相和ZnS相的复合纳米颗粒和Cu2SnS3-ZnS纳米颗粒的金属硫属化物纳米颗粒。通过离心纯化金属硫属化物纳米颗粒。
所形成的金属硫属化物纳米颗粒的扫描电子显微镜(SEM)图像和XRD图示于图6和7中。
作为XRD分析的结果,发现颗粒以Cu2SnS3晶相与ZnS晶相的组合形式存在,以及如从图8可以看出的,Cu2SnS3相和ZnS相均匀分布。
<比较例1>
ZnS颗粒的合成
将5mmol硝酸锌和10mmol Na2S溶于50ml水中,向Na2S水溶液中滴加所得硝酸锌水溶液以合成ZnS。通过离心纯化所形成的颗粒。
<比较例2>
CuS颗粒的合成
将5mmol硝酸铜和10mmol Na2S溶于50ml水中,向Na2S水溶液中添加所得硝酸铜水溶液以合成CuS。通过离心纯化所形成的颗粒。
<比较例3>
SnS颗粒的合成
将5mmol氯化锡和10mmol Na2S溶于50ml水中,向Na2S水溶液中滴加所得氯化锡水溶液以合成SnS。通过离心纯化所形成的颗粒。
<实施例7>
薄膜的制造
将实施例1中制造的Cu2SnS3-ZnS颗粒分散在含有醇基溶剂的混合溶剂中以制备墨,并将墨涂覆至已涂覆有钼(Mo)的玻璃基底上。在涂覆膜干燥后,与Se沉积的玻璃基底一起加热以确保Se气氛,并在575℃下进行快速热退火(RTA)以制造CZTSSe基薄膜。所制造的薄膜的扫描电子显微镜(SEM)图像和XRD图示于图9和10中。
<实施例8>
制造薄膜
将实施例3中制造的Cu2SnS3和实施例5中制造的ZnS颗粒分散在含有醇基溶剂的混合溶剂中以制备墨,并将墨涂覆至已涂覆有钼(Mo)的玻璃基底上。在涂覆膜干燥后,与Se沉积的玻璃基底一起加热以确保Se气氛,并在575℃下进行快速热退火(RTA)以制造CZTSSe基薄膜。所制造的薄膜的扫描电子显微镜(SEM)图像和XRD图示于图11和12中。
<实施例9>
薄膜的制造
将实施例6中制造的Cu2SnS3-ZnS颗粒分散在含有醇基溶剂的混合溶剂中以制备墨,并将墨涂覆至已涂覆有钼(Mo)的玻璃基底上。在涂覆膜干燥后,与Se沉积的玻璃基底一起加热以确保Se气氛,并在575℃下进行快速热退火(RTA)以制造CZTSSe基薄膜。所制造的薄膜的扫描电子显微镜(SEM)图像和XRD图示于图13和14中。
<比较例4>
薄膜的制造
将比较例1至3中制造的CuS、SnS和ZnS颗粒分散在含有醇基溶剂的混合溶剂中以制备墨,将所述墨涂覆至已涂覆有钼(Mo)的玻璃基底上。在涂覆膜干燥后,与Se沉积的玻璃基底一起加热以确保Se气氛,并在575℃下进行快速热退火(RTA)以制造CZTSSe基薄膜。所制造的薄膜的扫描电子显微镜(SEM)图像和XRD图示于图15和16中。
<测试例1>
薄膜太阳能电池的制造
将实施例7至9和比较例4中制造的CZTSSe基薄膜用氰化钾(KCN)溶液蚀刻,通过化学浴沉积(CBD)层合CdS层(厚度:50nm),通过溅射依次层合ZnO层(厚度:100nm)和Al掺杂ZnO层(厚度:500nm)以制造薄膜,在该薄膜上形成铝(Al)电极以制造薄膜太阳能电池。下表1和图17至20中示出了由太阳能电池获得的特性。
表1
J<sub>sc</sub>(mA/cm<sup>2</sup>) | V<sub>oc</sub>(V) | FF(%) | 光电效率(%) | |
实施例7 | 11.6 | 0.268 | 26.4 | 0.82 |
实施例8 | 26.8 | 0.290 | 41.3 | 3.2 |
实施例9 | 3.568 | 0.15 | 28.9 | 0.15 |
比较例4 | 1.36 | 0.2 | 24.68 | 0.1 |
表1中所示的确定太阳能电池效率的参数Jsc是指电流密度,Voc是指在零输出电流下测量的开路电压,光电效率是指电池功率相对于入射到太阳能电池板上的能量量的比率,以及填充因子(FF)是指通过用在最大功率下的电流密度和电压的乘积获得的值除以Voc和Jsc的乘积而计算的值。
作为测试的结果,可以看出,与包含比较例4中制造的CZTSSe基薄膜的太阳能电池相比,包含实施例7至9中制造的CZTSSe基薄膜的太阳能电池显示出优异的电池特性。
此外,与包含实施例9中制造的CZTSSe基薄膜的太阳能电池相比,包含实施例8中制造的CZTSSe基薄膜的太阳能电池显示出优异的电池特性,例如Jsc、FF和光电效率。在根据本发明的硫属化物纳米颗粒中,Cu-Sn-Zn复合纳米颗粒提供了更优异的电池特性。
尽管出于说明的目的公开了本发明的优选实施方案,但是本领域技术人员将理解,在不脱离如所附权利要求中公开的本发明的范围和精神的情况下,可以进行各种修改、添加和替换。
工业实用性
从前述可以明显看出,用于制造太阳能电池的光吸收层的本发明的金属硫属化物纳米颗粒是通过使包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)中任一种金属连接的第VI族元素的至少一种类型的单源前体进行热处理来制造的,并且可以仅用单源进行制造而不引入另外的第VI族元素源。因此,在颗粒的经济效率方面是有利的并且合成了没有相变的金属硫属化物纳米颗粒。由这样的金属硫属化物纳米颗粒制造的薄膜可有利地使次生相的形成最小化。
特别地,核-壳结构复合纳米颗粒具有其中核被包含含金属的硫属化物的壳所保护的结构,因此,对氧化稳定,使在颗粒表面上的氧化物的形成最小化并改善薄膜形成期间的反应性。
Claims (24)
1.一种通过热处理至少一种类型的单源前体而不引入另外的第VI族元素源制造的金属硫属化物纳米颗粒,所述单源前体包含用于合成制造太阳能电池的光吸收层用的金属硫属化物纳米颗粒的单源前体,
其中所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)的任一种金属连接的第VI族元素,
其中所述金属硫属化物纳米颗粒包括包含含铜(Cu)-锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒、或者包含含铜(Cu)-锌(Zn)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒、或者包含含锡(Sn)-锌(Zn)硫属化物和含铜(Cu)硫属化物的复合纳米颗粒;并且
其中所述复合纳米颗粒具有核-壳结构。
2.根据权利要求1所述的金属硫属化物纳米颗粒,其中所述金属硫属化物纳米颗粒包括含铜(Cu)硫属化物纳米颗粒、含锡(Sn)硫属化物纳米颗粒、或含锌(Zn)硫属化物纳米颗粒。
3.根据权利要求1所述的金属硫属化物纳米颗粒,其中所述金属硫属化物纳米颗粒包括含铜(Cu)-锡(Sn)硫属化物纳米颗粒、含铜(Cu)-锌(Zn)硫属化物纳米颗粒、或含锡(Sn)-锌(Zn)硫属化物纳米颗粒。
4.根据权利要求1所述的金属硫属化物纳米颗粒,其中所述金属硫属化物纳米颗粒包括含铜(Cu)-锡(Sn)-锌(Zn)硫属化物纳米颗粒。
5.根据权利要求1所述的金属硫属化物纳米颗粒,其中所述金属硫属化物纳米颗粒包括包含含铜(Cu)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒、或者包含含铜(Cu)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒、或者包含含锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒。
6.根据权利要求5所述的金属硫属化物纳米颗粒,其中所述包含含铜(Cu)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒是包括包含含铜(Cu)硫属化物的核和包含含锡(Sn)硫属化物的壳的核-壳结构纳米颗粒;所述包含含铜(Cu)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒是包括包含含铜(Cu)硫属化物的核和包含含锌(Zn)硫属化物的壳的核-壳结构纳米颗粒;以及所述包含含锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒是包括包含含锡(Sn)硫属化物的核和包含含锌(Zn)硫属化物的壳的核-壳结构纳米颗粒。
7.根据权利要求1所述的金属硫属化物纳米颗粒,其中所述包含含铜(Cu)-锡(Sn)硫属化物和含锌(Zn)硫属化物的复合纳米颗粒是包括包含含铜(Cu)-锡(Sn)硫属化物的核和包含含锌(Zn)硫属化物的壳的核-壳结构纳米颗粒;所述包含含铜(Cu)-锌(Zn)硫属化物和含锡(Sn)硫属化物的复合纳米颗粒是包括包含含铜(Cu)-锌(Zn)硫属化物的核和包含含锡(Sn)硫属化物的壳的核-壳结构纳米颗粒;以及所述包含含锡(Sn)-锌(Zn)硫属化物和含铜(Cu)硫属化物的复合纳米颗粒是包括包含含锡(Sn)-锌(Zn)硫属化物的核和包含含铜(Cu)硫属化物的壳的核-壳结构纳米颗粒。
8.一种制备根据权利要求1所述的金属硫属化物纳米颗粒的方法,包括:
(a)热处理包含至少一种类型的单源前体的混合物,所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)的任一种金属连接的第VI族元素;以及
(b)向经热处理的混合物中添加包含至少一种类型的单源前体的混合物并对所得混合物进行热处理,所述单源前体包含作为配体与选自铜(Cu)、锌(Zn)和锡(Sn)且步骤(a)中未选择的任一种金属连接的第VI族元素。
9.根据权利要求8所述的方法,还包括:
在步骤(b)之后,添加包含至少一种类型的单源前体的混合物并对所得混合物进行热处理,所述单源前体包含作为配体与选自金属铜(Cu)、锌(Zn)和锡(Sn)且步骤(a)和(b)中未选择的任一种金属连接的第VI族元素。
10.根据权利要求8或9所述的方法,其中所述热处理在50℃至300℃的温度下进行。
11.一种墨组合物,包含分散在溶剂中的至少一种类型的根据权利要求1所述的金属硫属化物纳米颗粒。
12.根据权利要求11所述的墨组合物,其中所述墨组合物中包含的所述金属硫属化物纳米颗粒具有CujZnkSn(1.0≤j≤4.0,0.5≤k≤2.0)的组成。
13.根据权利要求11所述的墨组合物,其中相对于1摩尔的总金属量,所述墨组合物中包含的所述金属硫属化物纳米颗粒的第VI族元素的摩尔比为0.5至4.0。
14.一种使用根据权利要求1所述的金属硫属化物纳米颗粒制造薄膜的方法,包括:
(i)使至少一种类型的根据权利要求1所述的金属硫属化物纳米颗粒分散在溶剂中以制备墨;
(ii)用所述墨涂覆设置有电极的基底;以及
(iii)使涂覆在所述设置有电极的基底上的所述墨干燥,并进行热处理。
15.根据权利要求14所述的方法,其中步骤(i)的所述溶剂包括选自烷烃、烯烃、炔烃、芳族化合物、酮、腈、醚、酯、有机卤化物、醇、胺、硫醇、羧酸、膦、磷酸酯、亚砜和酰胺的至少一种有机溶剂。
16.根据权利要求14所述的方法,还包括加入添加剂以制备步骤(i)中的所述墨。
17.根据权利要求16所述的方法,其中所述添加剂包括选自聚乙烯吡咯烷酮(PVP)、聚乙烯醇(PVA)、Anti-terra 204、Anti-terra 205、乙基纤维素和DispersBYK110中的至少一种。
18.根据权利要求14所述的方法,其中步骤(ii)的所述涂覆通过湿法涂覆、喷涂、刮刀涂覆或喷墨打印来进行。
19.根据权利要求14所述的方法,其中步骤(iii)的所述热处理在S或Se的存在下进行。
20.根据权利要求19所述的方法,其中所述S或Se的存在通过供应H2S或H2Se气体或者通过加热供应Se或S气体来进行。
21.根据权利要求14所述的方法,还包括供应作为颗粒的S或Se和在热处理期间供应所述S或Se。
22.根据权利要求14所述的方法,还包括通过沉积在薄膜上供应S或Se。
23.一种通过根据权利要求14所述的方法制造的薄膜。
24.一种使用根据权利要求23所述的薄膜制造的薄膜太阳能电池。
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