CN106847985A - 异质结激子太阳能电池及制备方法 - Google Patents
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Abstract
本发明公开了一种异质结激子太阳能电池及制备方法,包括五层结构,最下层为下电极、第二层为金属衬底、第三层为应变层黑磷烯、第四层为自由层黑磷烯、最上层为上电极和防反射层。通过机械剥离的方法得到单层黑磷,再通过机械压缩对单层黑磷施加应变。沿着黑磷扶椅形方向施加应变与未施加应变的单层黑磷构成半导体异质结,吸收光谱范围广,光电转换效率高;与不同材料构成的异质结相比,同种材料更容易达到晶格匹配,制备工艺也更简单。在日光照射下,本发明的太阳能电池其开路电压理论上达到0.55V,太阳能电池的能量转换效率高达20%。
Description
技术领域
本发明属于新能源技术领域,尤其涉及一种异质结激子太阳能电池及制备方法。
背景技术
在众多新能源中,太阳能作为一种可再生能源,因其蕴藏量丰富,无地域限制,清洁无污染,增长最快速,环境最友好,取之不尽等独特的优势,备受科学研究者们的青睐。而且,目前全球的能源危机和生态危机更驱动着人们将目光聚焦在太阳能电池的研究上。太阳能电池是指通过光电效应或者光化学效应直接把光能转换成电能的装置。
传统的基于同质PN结技术的硅基太阳能电池具有成本高、效率低且污染环境等缺点,异质结技术的引入成为解决该问题的一个关键途径。异质结吸收光谱范围广,有利于效率的提高,并且使用异质结能减少硅消耗,降低成本等。
具有原子层厚度的2D材料由于其不同于体材料的优越性质而受到人们的广泛研究,如石墨烯,MoS2等等。近年来,一种新的2D材料少层黑磷已经能在实验条件下通过机械剥离的方法制备得到,并且受到了人们的广泛关注。黑磷是一种具有金属光泽的晶体,可由白磷或红磷转化而来,黑磷具有直接半导体带隙,且表现出与层数相关的特性,少层黑磷的电子迁移率为1000cm2/Vs,还具有非常高的漏电流调制率,使得其在未来的纳米电子器件中的应用有很大潜力。另外因其为直接带隙,其光学性质相比其他材料也有很大的优势,是目前新型二维材料研究的热点之一。
通过给材料施加应变是可以改变其能带结构,因此给黑磷烯施加应变后就可以将其用作受主材料。单层黑磷烯的光学带隙是1.6ev,远小于电学带隙2.15ev,表明黑磷烯存在着很明显的激子效应,并且存在很大的激子结合能为0.55ev,这样的优点使得黑磷烯在制备激子太阳能方面具有很大的应用前景。
发明内容
发明目的:针对以上问题,本发明提出一种异质结激子太阳能电池及制备方法。
技术方案:为实现本发明的目的,本发明所采用的技术方案是:一种异质结激子太阳能电池,其特征在于:包括下电极、金属衬底、应变层黑磷烯、自由层黑磷烯、上电极和防反射层;最下层为下电极、第二层为金属衬底、第三层为应变层黑磷烯、第四层为自由层黑磷烯、最上层为上电极和防反射层。
应变层黑磷烯为p型应变层黑磷烯,自由层黑磷烯为n型自由层黑磷烯,p型应变层黑磷烯和n型自由层黑磷烯构成异质结。应变层黑磷烯和自由层黑磷烯是单层纳米材料。应变层黑磷烯是由自由层黑磷烯沿扶椅形方向压缩应变得到。
一种异质结激子太阳能电池制备方法,具体包括以下步骤:
(1)对衬底表面进行抛光、清洗及退火处理;
(2)制备单层黑磷;
(3)用衬底捞出单层黑磷,放在50-60℃的加热台上烘干;
(4)将步骤(3)得到的单层黑磷在电子显微镜下,通过探针剥离的方法,得到双层黑磷,再通过探针对下层的黑磷施加应变,得到衬底-应变层黑磷烯一自由层黑磷烯的结构;
(5)通过表面蒸镀金属的方法,在衬底-应变层黑磷烯-自由层黑磷烯结构的上下分别蒸镀一薄金属层,作为上、下电极;通过等离子刻蚀方法将金属薄层刻蚀出叉指型,在最上层溅射一层防反射层。
步骤(1)具体包括:
(1.1)将衬底表面用金刚石泥浆进行抛光,配合光学显微镜观察衬底表面,直到没有划痕,然后再用化学机械抛光的方法进行抛光处理;
(1.2)将衬底放入去离子水中,在室温下超声清洗3分钟,去除铜衬底表面粘污颗粒,再依次经过丙酮、乙醇洗涤,去除表面有机物,用高纯干燥氮气吹干;
(1.3)将衬底放入反应室内,在500℃下空气氛围中对铜衬底进行3小时退火处理,然后在空气中冷却至室温。
步骤(2)具体包括:将白磷在1000-1200Pa大气压下加热到200-250℃,得到片状黑磷,通过机械剥离方法从黑磷晶体剥离出多层黑磷烯,再通过Ar+等离子体剥离方法剥离得到少层黑磷。
步骤(2)具体包括:获取黑磷块体,将块体浸入过氧化氢异丙苯溶剂中,加声波,最后使用离心机使其分离得到层状物。
有益效果:与现有技术相比,本发明具有如下有益效果:使用不同应变的黑磷烯构成异质结作为太阳能电池的主体,提高了太阳能电池的转化效率,其激子结合能达到0.55ev,开路电压理论上达到0.55V,太阳能电池的AM1.5能量转换效率高达20%;选取二维材料黑磷,可以把太阳能电池做得很薄,黑磷克服了石墨烯没有能隙的缺点,大大提升了黑磷在光学方面的应用;异质结采用同一种材料,异质结组合更容易达到晶格匹配,制备异质结薄膜的工艺方法相比不同材料构成的异质结也更为便捷简单。
附图说明
图1是本发明所述的异质结激子太阳能电池示意图;
图2是应变层黑磷烯和自由层黑磷烯构成的异质结;
图3是应变黑磷烯和自由黑磷烯的能带结构示意图;
图4是自由黑磷烯和应变黑磷烯的能带排列。
具体实施方式
下面结合附图和实施例对本发明的技术方案作进一步的说明。
如图1所示是本发明所述的异质结激子太阳能电池,包括下电极1、金属衬底2、p型应变层黑磷烯3、n型自由层黑磷烯4、上电极5和防反射层6。第一层即最下层为下电极、第二层为金属衬底、第三层为p型应变层黑磷烯、第四层为n型自由层黑磷烯、最上层为上电极和防反射层。上电极为金属接触栅。金属衬底可以为铜衬底。
如图2所示是应变层黑磷烯和自由层黑磷烯构成的异质结,是太阳能电池的核心部分,应变层黑磷烯施加-2%的应变。自由层黑磷烯薄膜和应变层黑磷烯薄膜组成异质结,为同一种材料在不同应变程度下构成的异质结,分别为零应变的黑磷烯与-2%应变的黑磷烯,前者作为给体部分,后者作为受体部分。异质结太阳能电池中p型应变层黑磷烯和n型自由层黑磷烯厚都是单层纳米材料,具有良好的透光性和导电性。需要通过机械剥离技术将黑磷剥离到单层厚度,约为在间。应变层黑磷烯结构是将单层自由层黑磷烯沿着扶椅形方向压缩2%的应变。
应变黑磷烯相较于未施加应变的黑磷烯,在施加了2%压应变下的黑磷烯的导带底(CBM)下降了0.11ev。因此将有应变和无应变的两层黑磷烯叠放在一起可以构成一种新型异质结。同时黑磷烯的机械特性也证明,其能承受的最大应变可达到30%,施加了2%压缩应变的黑磷烯可以在金属衬底上实现,因为应变黑磷烯与金属衬底之间存在很小的晶格失配。
使用同一种材料在不同应变程度下构成的异质结太阳能电池,相比不同材料构成的异质结,制备条件更方便,成本低廉,且转换效率能达到20%以上,可以有效的进行光能到电能的转化。
沿着黑磷扶椅形方向施加-2%应变的单层黑磷与未施加应变的单层黑磷可构成半导体异质结,以未施加应变的单层黑磷为给体,其电学带隙为2.15eV,光学带隙为1.6ev,激子结合能达到0.55ev,能吸收的光谱范围较广,光电转换效率高,以施加应变的单层黑磷为受体。与不同材料构成的异质结相比,本发明选用的异质结是同种材料,因此更容易达到晶格匹配,制备工艺也更简单。通过机械剥离的方法来得到单层黑磷,再通过机械压缩对单层黑磷施加应变。在日光照射下,太阳能电池其开路电压理论上达到0.55V。
异质结激子太阳能电池的制备方法,具体包括以下步骤:
(1)金属衬底的清洗:以铜衬底为例,对衬底表面进行抛光、清洗以及退火处理。首先,将铜衬底表面用金刚石泥浆进行抛光,配合光学显微镜观察衬底表面,直到没有划痕,然后再用化学机械抛光的方法进行抛光处理;其次,将铜衬底放入去离子水中,在室温下超声清洗3分钟,去除铜衬底表面粘污颗粒,再依次经过丙酮、乙醇洗涤,去除表面有机物,用高纯干燥氮气吹干;最后,将铜衬底放入反应室内,在500℃下空气氛围中对铜衬底进行3小时退火处理,然后在空气中冷却至室温。
(2)单层黑磷的制备:将白磷在1000-1200Pa大气压下加热到200-250℃,可得到片状黑磷,通过机械剥离方法从黑磷晶体剥离出多层黑磷烯,然后再通过Ar+等离子体剥离方法剥离得到少层黑磷。
或者获取黑磷块体,然后将块体浸入过氧化氢异丙苯(CHP)的溶剂中,再加声波;最后,使用离心机使其分离得到层状物。
(3)用铜衬底捞出黑磷薄膜,放在50-60℃的加热台上烘干,去除黑磷薄膜与铜衬底之间的水分,同时能将少层黑磷更牢固的与铜衬底结合。
(4)将步骤(3)得到的少层黑磷结构在电子显微镜下,通过探针剥离的方法,得到双层黑磷结构,再通过探针对下层的单层黑磷施加2%压应变,从而得到铜衬底-应变层黑磷烯-自由层黑磷烯的结构。如图3所示是施加2%压缩应变黑磷烯(实线)和未施加应变黑磷烯(虚线)的能带结构示意图,费米能级设置为价带顶。如图4所示是自由黑磷烯和-2%应变黑磷烯的能带排列,其中,自由黑磷为n型材料,应变黑磷烯为p型材料。
(5)通过表面蒸镀金属的方法,在已有结构的上下层分别蒸镀一层薄的铝层,作为上、下电极,通过等离子刻蚀方法将铝薄膜刻蚀出叉指型,最后在最上层溅射一层TiO2薄膜作为防反射层。
Claims (10)
1.一种异质结激子太阳能电池,其特征在于:包括下电极、金属衬底、应变层黑磷烯、自由层黑磷烯、上电极和防反射层;最下层为下电极、第二层为金属衬底、第三层为应变层黑磷烯、第四层为自由层黑磷烯、最上层为上电极和防反射层。
2.根据权利要求1所述的异质结激子太阳能电池,其特征在于:上电极为金属接触栅。
3.根据权利要求1所述的异质结激子太阳能电池,其特征在于:金属衬底为铜衬底。
4.根据权利要求1所述的异质结激子太阳能电池,其特征在于:应变层黑磷烯为p型应变层黑磷烯,自由层黑磷烯为n型自由层黑磷烯,p型应变层黑磷烯和n型自由层黑磷烯构成异质结。
5.根据权利要求1所述的异质结激子太阳能电池,其特征在于:应变层黑磷烯和自由层黑磷烯是单层纳米材料。
6.根据权利要求1所述的异质结激子太阳能电池,其特征在于:应变层黑磷烯是由自由层黑磷烯沿扶椅形方向压缩应变得到。
7.一种异质结激子太阳能电池制备方法,其特征在于:具体包括以下步骤:
(1)对衬底表面进行抛光、清洗及退火处理;
(2)制备单层黑磷;
(3)用衬底捞出单层黑磷,放在50-60℃的加热台上烘干;
(4)将步骤(3)得到的单层黑磷在电子显微镜下,通过探针剥离的方法,得到双层黑磷,再通过探针对下层的黑磷施加应变,得到衬底-应变层黑磷烯-自由层黑磷烯的结构;
(5)通过表面蒸镀金属的方法,在衬底-应变层黑磷烯-自由层黑磷烯结构的上下分别蒸镀一薄金属层,作为上、下电极;通过等离子刻蚀方法将金属薄层刻蚀出叉指型,在最上层溅射一层防反射层。
8.根据权利要求7所述的异质结激子太阳能电池制备方法,其特征在于:所述步骤(1)具体包括:
(1.1)将衬底表面用金刚石泥浆进行抛光,配合光学显微镜观察衬底表面,直到没有划痕,然后再用化学机械抛光的方法进行抛光处理;
(1.2)将衬底放入去离子水中,在室温下超声清洗3分钟,去除铜衬底表面粘污颗粒,再依次经过丙酮、乙醇洗涤,去除表面有机物,用高纯干燥氮气吹干;
(1.3)将衬底放入反应室内,在500℃下空气氛围中对铜衬底进行3小时退火处理,然后在空气中冷却至室温。
9.根据权利要求7所述的异质结激子太阳能电池制备方法,其特征在于:所述步骤(2)具体包括:将白磷在1000-1200Pa大气压下加热到200-250℃,得到片状黑磷,通过机械剥离方法从黑磷晶体剥离出多层黑磷烯,再通过Ar+等离子体剥离方法剥离得到少层黑磷。
10.根据权利要求7所述的异质结激子太阳能电池制备方法,其特征在于:所述步骤(2)具体包括:获取黑磷块体,将块体浸入过氧化氢异丙苯溶剂中,加声波,最后使用离心机使其分离得到层状物。
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