CN101552296B - 太阳能电池 - Google Patents

太阳能电池 Download PDF

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CN101552296B
CN101552296B CN200810066508.6A CN200810066508A CN101552296B CN 101552296 B CN101552296 B CN 101552296B CN 200810066508 A CN200810066508 A CN 200810066508A CN 101552296 B CN101552296 B CN 101552296B
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孙海林
姜开利
李群庆
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Abstract

本发明涉及一种太阳能电池，该太阳能电池包括一背电极、一单晶硅衬底和一碳纳米管结构。所述背电极设置于所述单晶硅衬底的下表面，且与该单晶硅衬底的下表面欧姆接触。所述碳纳米管结构设置于所述单晶硅衬底的上表面，且与该单晶硅衬底的上表面接触。该碳纳米管结构包括多个有序排列的碳纳米管。

Description

太阳能电池
技术领域
本发明涉及一种太阳能电池，尤其涉及一种基于碳纳米管薄膜的太阳能电池。
背景技术
太阳能是当今最清洁的能源之一，取之不尽、用之不竭。太阳能的利用方式包括光能-热能转换、光能-电能转换和光能-化学能转换。太阳能电池是光能-电能转换的典型例子，是利用半导体材料的光生伏特原理制成的。目前，太阳能电池以硅基太阳能电池为主。在硅基太阳能电池中，以单晶硅作为光电转换的材料，因此，要获得高转换效率的硅太阳能电池，就需要制备出高纯度的单晶硅。然而，目前单晶硅的制备工艺远不能满足太阳能电池发展的需要，并且制备单晶硅需要消耗大量的电能，这不但提高了硅太阳能电池的成本，并且对环境产生很大的污染。因此发展其他类型的太阳能电池就具有重要的战略意义。
从1991年日本科学家Iijima首次发现碳纳米管以来(请参见Helical microtubules of graphitic carbon，Nature，Sumio Iijima，vol 354，p56(1991))，以碳纳米管为代表的纳米材料以其独特的结构和性质引起了人们极大的关注。研究发现，碳纳米管具有很高的导电能力，且碳纳米管具有很高得吸收太阳光能力，其在可见光和红外光区的吸收率高达99％以上。因此，将碳纳米管应用在太阳能电池领域，将具有传统材料无可比拟的优势。
请参阅图1，现有技术中基于碳纳米管的太阳能电池30包含一背电极32、一单晶硅衬底34和一碳纳米管薄膜36。所述背电极32设置于所述单晶硅衬底34的下表面342。所述碳纳米管薄膜36设置于所述单晶硅衬底34的上表面341。所述碳纳米管薄膜36作为光电转换材料，同时作为上电极。所述碳纳米管薄膜36的厚度为50纳米～200纳米，其中的碳纳米管无序分布。所述太阳能电池30的制备方法具体包括以下步骤：提供一单晶硅衬底34；在该单晶硅衬底34的一侧表面蒸镀一金属薄膜作为背电极32，并用导线引出；提供一碳纳米管薄膜36；将该碳纳米管薄膜36铺设到所述单晶硅衬底34的另一侧表面上，使碳纳米管薄膜36与单晶硅衬底34紧密接触，并用导线引出。所述碳纳米管薄膜36的制备方法具体包括以下步骤：首先，将碳纳米管在空气中氧化；其次，将氧化后的碳纳米管浸泡在双氧水中；再次，加入强酸后，漂洗碳纳米管至漂洗液呈中性；再次，在碳纳米管的水溶液中滴加酒精或丙酮，使碳纳米管浮出水面，展开形成一碳纳米管薄膜36。然而，现有技术中太阳能电池具有以下不足：所述碳纳米管薄膜36中碳纳米管无序分布，阻值较大，使得该碳纳米管薄膜36的导电性较差，故，导致所制得的太阳能电池的光电转换效率低。另外，所述碳纳米管薄膜36的制备方法复杂，不适于批量生产。
因此，确有必要提供一种光电转换效率较高、阻值分布均匀及透光性好太阳能电池，且太阳能电池的制备方法简单、容易实现。
发明内容
一种太阳能电池包括一背电极、一单晶硅衬底和一碳纳米管结构。所述背电极设置于所述单晶硅衬底的下表面，且与该单晶硅衬底的下表面欧姆接触。所述碳纳米管结构设置于所述单晶硅衬底的上表面，且与该单晶硅衬底的上表面接触。所述碳纳米管结构包括至少两个重叠设置的有序碳纳米管薄膜，每一序碳纳米管薄膜包括多个首尾相连且长度相等的碳纳米管束，该碳纳米管束的两端通过范德华力相互连接，所述碳纳米管薄膜中碳纳米管沿固定方向择优取向排列，相邻的两个有序碳纳米管薄膜中的碳纳米管具有一交叉角度α，且0度＜α≤90度。
与现有技术相比较，所述太阳能电池的碳纳米管结构中碳纳米管有序排列，具有较均匀的结构，导电性好，故，采用碳纳米管结构作上电极，可使得太阳能电池具有均匀的电阻，从而使得太阳能电池具有较高的光电转换效率。
附图说明
图1是现有技术中太阳能电池的结构示意图。
图2是本技术方案实施例的太阳能电池的侧视结构示意图。
图3是本技术方案实施例的太阳能电池中碳纳米管结构的部分放大示意图。
图4是本技术方案实施例的太阳能电池的俯视结构示意图。
具体实施方式
以下将结合附图详细说明本技术方案太阳能电池。
请参阅图2及图4，本技术方案实施例提供一种太阳能电池10包括一背电极12、一单晶硅衬底14和一碳纳米管结构16。所述背电极12设置于所述单晶硅衬底14的下表面141，且与该单晶硅衬底14的下表面141欧姆接触。所述碳纳米管结构16设置于所述单晶硅衬底14的上表面142，且与该单晶硅衬底14的上表面142接触。
所述太阳能电池10进一步包括至少一电极18，该电极18的材料为银、金或者碳纳米管等导电材料。所述电极18的形状和厚度不限，可设置于所述碳纳米管结构16的上表面161或者下表面162，并与碳纳米管结构16的上表面161或者下表面162电接触。所述电极18的设置可用于收集流过所述碳纳米管结构16中的电流，并与外电路连接。
所述太阳能电池10进一步包括至少一钝化层20，该钝化层20的材料为二氧化硅或者四氮化三硅等。所述钝化层20的形状和厚度不限，可设置于所述单晶硅衬底14的上表面142和碳纳米管结构16的下表面162之间，用以降低电子和空穴在所述单晶硅衬底14和所述碳纳米管结构16接触面的复合速度，从而进一步提高所述太阳能电池10的光电转换效率。
所述背电极12的材料可为铝、镁或者银等金属。所述背电极12的厚度为10微米～300微米。所述背电极12的形状和厚度不限。
所述单晶硅衬底14为p型单晶硅片或者n型单晶硅片。该单晶硅衬底14的厚度为200微米～300微米。所述单晶硅衬底14与所述碳纳米管结构16形成异质结结构，从而实现所述太阳能电池10中光能到电能的转换。
所述碳纳米管结构16为一层状结构，包括多个有序排列的碳纳米管。所述碳纳米管结构16中的碳纳米管均匀分布且平行于所述碳纳米管结构16的表面，以使所述太阳能电池10具有均匀的电阻。所述的多个碳纳米管沿固定方向择优取向排列，以使所述太阳能电池10具有良好的导电性以及较高的光电转换效率。
所述碳纳米管结构16中的碳纳米管为单壁碳纳米管、双壁碳纳米管或者多壁碳纳米管。其中，多壁碳纳米管是金属性质的，单壁碳纳米管根据其手性和直径不同分为半导体和金属两种，双壁碳纳米管的属性是金属性质的。当所述碳纳米管结构16中的碳纳米管为单壁碳纳米管时，该单壁碳纳米管的直径为0.5纳米～50纳米。当所述碳纳米管结构16中的碳纳米管为双壁碳纳米管时，该双壁碳纳米管的直径为1.0纳米～50纳米。当所述碳纳米管结构16中的碳纳米管为多壁碳纳米管时，该多壁碳纳米管的直径为1.5纳米～50纳米。由于所述碳纳米管结构16中的碳纳米管非常纯净，且由于碳纳米管本身的比表面积非常大，所以该碳纳米管结构16本身具有较强的粘性。该碳纳米管结构16可利用其本身的粘性直接固定于所述单晶硅衬底14的表面。
具体地，所述碳纳米管结构16包括一有序碳纳米管薄膜163。请参阅图3，该有序碳纳米管薄膜163可通过直接拉伸一碳纳米管阵列获得。该有序碳纳米管薄膜163包括沿拉伸方向定向排列的碳纳米管。具体地，所述有序碳纳米管薄膜163包括多个首尾相连且长度相等的碳纳米管束164。所述碳纳米管束164的两端通过范德华力相互连接。每个碳纳米管束164包括多个长度相等且平行排列的碳纳米管165。所述相邻的碳纳米管165之间通过范德华力紧密结合。所述有序碳纳米管薄膜163是由碳纳米管阵列经进一步处理得到的，故其长度与宽度和碳纳米管阵列所生长的基底的尺寸有关。可根据实际需求制得。本实施例中，采用气相沉积法在4英寸的基底生长超顺排碳纳米管阵列。所述有序碳纳米管薄膜163的宽度可为0.01厘米～10厘米，厚度为10纳米～100微米。所述有序碳纳米管薄膜163中，多个碳纳米管均匀分布且平行于所述碳纳米管结构16的表面。所述的多个碳纳米管沿拉伸方向择优取向排列。
可以理解，所述碳纳米管结构16还可包括至少两个重叠设置的上述有序碳纳米管薄膜163。具体地，相邻的两个有序碳纳米管薄膜163中的碳纳米管具有一交叉角度α，且0度≤α≤90度，具体可依据实际需求制备。可以理解，由于碳纳米管结构16中的多个有序碳纳米管薄膜163可重叠设置，故，上述碳纳米管结构16的厚度不限，可根据实际需要制成具有任意厚度的碳纳米管结构16。所述碳纳米管结构16中，多个碳纳米管均匀分布且平行于所述碳纳米管结构16的表面。所述的多个碳纳米管沿拉伸方向择优取向排列。
所述太阳能电池10在应用时，太阳光照射到所述碳纳米管结构16，入射光子被所述碳纳米管结构16吸收后，在所述单晶硅衬底14和碳纳米管结构16的接触面上产生大量的激子，即电子和空穴对。这些激子将会分离成两种自由载流子，其中自由空穴载流子通过所述单晶硅衬底14向背电极12传输，而由所述背电极12收集。自由电子载流子通过所述碳纳米管结构的传输，被本身也作为上电极的碳纳米管结构16传输、收集。进一步，通过碳纳米管结构16所收集的电流被所述至少一电极18再次收集。所述至少一钝化层20的设置可以降低电子和空穴在所述单晶硅衬底14和所述碳纳米管结构16接触面的复合速度，从而进一步提高所述太阳能电池10的光电转换效率。如果在所述太阳能电池10中背电极12与至少一电极18的两端接上负载，在外电路就会有电流通过负载。
所述太阳能电池的碳纳米管结构中碳纳米管有序排列，具有较均匀的结构，导电性好，故，采用碳纳米管结构作上电极，可使得太阳能电池具有均匀的电阻，从而使得太阳能电池具有较高的光电转换效率。
所述有序碳纳米管薄膜163的制备方法包括以下步骤：
首先，提供一碳纳米管阵列形成于一基底，优选地，该阵列为超顺排碳纳米管阵列。
本实施例中，超顺排碳纳米管阵列的制备方法采用化学气相沉积法，其具体步骤包括：(a)提供一平整基底，该基底可选用P型或N型硅基底，或选用形成有氧化层的硅基底，本实施例优选为采用4英寸的硅基底；(b)在基底表面均匀形成一催化剂层，该催化剂层材料可选用铁(Fe)、钴(Co)、镍(Ni)或其任意组合的合金之一；(c)将上述形成有催化剂层的基底在700℃～900℃的空气中退火约30分钟～90分钟；(d)将处理过的基底置于反应炉中，在保护气体环境下加热到500℃～740℃，然后通入碳源气体反应约5分钟～30分钟，生长得到超顺排碳纳米管阵列，其高度为200微米～400微米。该超顺排碳纳米管阵列为至少两个彼此平行且垂直于基底生长的碳纳米管形成的纯碳纳米管阵列。通过上述控制生长条件，该超顺排碳纳米管阵列中基本不含有杂质，如无定型碳或残留的催化剂金属颗粒等。该碳纳米管阵列中的碳纳米管彼此通过范德华力紧密接触形成阵列。该碳纳米管阵列的面积与上述基底面积基本相同。
上述碳源气可选用乙炔、乙烯、甲烷等化学性质较活泼的碳氢化合物，本实施例优选的碳源气为乙炔；保护气体为氮气或惰性气体，本实施例优选的保护气体为氩气。
可以理解，本实施例提供的碳纳米管阵列不限于上述制备方法，也可为石墨电极恒流电弧放电沉积法、激光蒸发沉积法等。
其次，采用一拉伸工具拉取上述碳纳米管阵列从而获得一碳纳米管薄膜163。
本实施例中，采用一拉伸工具拉取上述碳纳米管阵列从而获得一碳纳米管薄膜163的方法包括以下步骤：(a)从上述碳纳米管阵列中选定一定宽度的多个碳纳米管束片断；(b)沿基本垂直于碳纳米管阵列生长方向拉伸该多个碳纳米管束片断，获得一连续的碳纳米管薄膜163，该碳纳米管薄膜163中的碳纳米管的排列方向平行于碳纳米管薄膜163的拉伸方向。
在上述拉伸过程中，该多个碳纳米管束片断在拉力作用下沿拉伸方向逐渐脱离基底的同时，由于范德华力作用，该选定的多个碳纳米管束片断分别与其他碳纳米管束片断首尾相连地连续地被拉出，从而形成一碳纳米管薄膜163。
所述有序碳纳米管薄膜163是由碳纳米管阵列经进一步处理得到的，其长度和宽度可以较准确地控制。该有序碳纳米管薄膜163中碳纳米管首尾相连，且长度相等并均匀、有序分布、相邻的碳纳米管之间具有空隙，从而使得所述碳纳米管结构具有均匀的阻值分布和透光特性。故，采用该碳纳米管结构作上电极，可以相应提高所述太阳能电池的光电转换效率。进一步，所述碳纳米管结构的制备方法简单、容易实现，适于批量生产。
可以理解，所述碳纳米管结构16也可是其他的碳纳米管结构，如多个碳纳米管长线互相平行铺设于所述单晶硅衬底14表面，形成一碳纳米管结构16；或者所述碳纳米管结构为一层状结构，每一层包括多个互相平行铺设于所述单晶硅衬底14表面的碳纳米管长线，相邻两层中的碳纳米管长线之间具有一交叉角度β，且0度≤β≤90度；或者多个碳纳米管长线互相平行铺设于一碳纳米管薄膜表面，形成一碳纳米管结构16；或者碳纳米管粉末与金属混合形成的复合材料涂覆于所述单晶硅衬底14表面，形成一碳纳米管结构16等，只需具有良好的吸光性、导电性及耐用性等特性即可。
请参阅表1，为以所述有序碳纳米管薄膜163制成的太阳能电池10的各项参数指标列表。其中n-Si表示所述单晶硅衬底14为n型单晶硅片，p-Si表示所述单晶硅衬底14为p型单晶硅片。所述交叉铺设表示至少两层有序碳纳米管薄膜163交叉铺设形成一碳纳米管结构16，该有序碳纳米管薄膜163中的碳纳米管之间的交叉角度为90度。从图5中可以看出，本实施例中以n型单晶硅片和p型单晶硅片制成的太阳能电池10都有光生伏特现象，其中以四个有序碳纳米管薄膜163交叉铺设所制得的太阳能电池10的光电转换效率最高，为0.84％。以n型单晶硅片制成的太阳能电池10的光电转换效率比以p型单晶硅片制成的太阳能电池10的光电转换效率高。
表1太阳能电池的各项参数指标列表
Figure GSB00000401036800071
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。

Claims (9)

1.一种太阳能电池，其包括：
一单晶硅衬底；
一背电极，该背电极设置于所述单晶硅衬底的下表面，且与该单晶硅衬底的下表面欧姆接触；
一碳纳米管结构，该碳纳米管结构设置于所述单晶硅衬底的上表面，且与该单晶硅衬底的上表面接触；
其特征在于，所述碳纳米管结构包括至少两个重叠设置的有序碳纳米管薄膜，每一有序碳纳米管薄膜包括多个首尾相连且长度相等的碳纳米管束，该碳纳米管束的两端通过范德华力相互连接，所述碳纳米管薄膜中碳纳米管沿固定方向择优取向排列，相邻的两个有序碳纳米管薄膜中的碳纳米管具有一交叉角度α，且0度＜α≤90度。
2.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管结构中碳纳米管薄膜的层数为二层至八层。
3.如权利要求2所述的太阳能电池，其特征在于，所述碳纳米管结构中碳纳米管薄膜的层数为四层。
4.如权利要求2或3所述的太阳能电池，其特征在于，所述相邻的两层碳纳米管薄膜中的碳纳米管的交叉角度α为90度。
5.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管薄膜中的碳纳米管平行于所述碳纳米管结构的表面排列。
6.如权利要求1所述的太阳能电池，其特征在于，所述单晶硅衬底为n型单晶硅片或者p型单晶硅片，该单晶硅衬底的厚度为200微米～300微米。
7.如权利要求1所述的太阳能电池，其特征在于，所述背电极的材料为铝、镁或者银，该背电极的厚度为10微米～300微米。
8.如权利要求1所述的太阳能电池，其特征在于，该太阳能电池进一步包括至少一钝化层，该钝化层设置于所述单晶硅衬底和碳纳米管结构之间。
9.如权利要求8所述的太阳能电池，其特征在于，所述钝化层的材料为二氧化硅或者四氮化三硅。
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