CN101552297A - 太阳能电池 - Google Patents

太阳能电池 Download PDF

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CN101552297A
CN101552297A CN200810066509.0A CN200810066509A CN101552297A CN 101552297 A CN101552297 A CN 101552297A CN 200810066509 A CN200810066509 A CN 200810066509A CN 101552297 A CN101552297 A CN 101552297A
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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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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、一多晶硅衬底和一碳纳米管结构。所述背电极设置于所述多晶硅衬底的下表面，且与该多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多晶硅衬底的上表面，且与该多晶硅衬底的上表面接触。

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(请参见太阳能电池及多晶硅的生产，材料与冶金学报，张明杰等，vol6，p33-38(2007))为主。在硅基太阳能电池中，以单晶硅和多晶硅作为光电转换的材料。通常用单晶硅片制造太阳能电池。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，导致单晶硅片非常昂贵，使得使用单晶硅片的太阳能电池也非常昂贵。近年来，具有多晶硅衬底的硅太阳能电池的成本日益跌落，其产量显著增加。
请参阅图1，为现有技术中的多晶硅太阳能电池30包含一背电极32、一多晶硅衬底34、一掺杂硅层36和一上电极38。所述多晶硅衬底34采用多晶硅制成。所述背电极32设置于所述多晶硅衬底34的下表面341，且与该多晶硅衬底34的下表面341欧姆接触。所述掺杂硅层36形成于所述多晶硅衬底34的上表面342，作为光电转换的材料。所述上电极38设置于所述掺杂硅层36的上表面361。所述多晶硅太阳能电池30中多晶硅衬底34和掺杂硅层36形成P-N结，所述P-N结在太阳光的激发下产生多个电子-空穴对(激子)，所述电子-空穴对在静电势能作用下分离并分别向所述背电极32和上电极38移动。如果在所述多晶硅太阳能电池30的背电极32与上电极38两端接上负载，就会有电流通过外电路中的负载。
然而，现有技术中的多晶硅太阳能电池30的结构复杂。而且，在多晶硅衬底的生长过程中，由于热应力的作用，会在晶粒中产生大量的缺陷(如悬挂键、晶界、位错、微缺陷等)。其中，悬挂键是多晶硅中的主要缺陷之一，存在于多晶硅的畴界处，成为载流子的俘获中心。晶粒间的杂质电离产生的载流子首先被悬挂键俘获。悬挂键在俘获载流子之前是电中性的，在俘获载流子之后悬挂键带电，在其周围形成一个多子势区，阻挡载流子从一个晶粒向另一个晶粒运动，导致载流子迁移率下降。且悬挂键的存在增加电子-空穴的复合损失，导致所制得的太阳能电池30的光电转换效率低。为了增加载流子的迁移率，提高光电转换效率。通常在所述多晶硅衬底34的上表面342沉积一磷或砷层，使其与所述多晶硅衬底34作用以形成掺杂硅层36。接着，在所述掺杂硅层36的上表面361通过丝网印刷形成金属电极。然而，形成掺杂硅层36需在高温条件下进行，工艺复杂，另外，丝网印刷所形成的金属电极宽度较大，造成遮光面积较大，导致所制得的太阳能电池30的光电转换效率低。
因此，确有必要提供一种光电转换效率较高且结构简单的太阳能电池及其制备方法，且该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、一多晶硅衬底和一碳纳米管结构。所述背电极设置于所述多晶硅衬底的下表面，且与该多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多晶硅衬底的上表面，且与该多晶硅衬底的上表面接触。
与现有技术相比较，所述太阳能电池及其制备方法具有以下优点：其一，由于采用碳纳米管结构作为光电转换材料，可以饱和部分悬挂键，降低悬挂键对载流子的俘获无需形成掺杂硅层，同时碳纳米管结构对太阳光具有很好的透光性，采用碳纳米管结构作为上电极，可以提高太阳能电池的光电转换效率；其二，碳纳米管结构在太阳能电池中起到光电转换及上电极的双重作用，且无需磷或砷层，因此结构简单。
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的俯视结构示意图。
图4是本技术方案实施例的太阳能电池中有序碳纳米管层的部分放大示意图。
图5是本技术方案实施例的太阳能电池的制备方法的流程示意图。
图6是本技术方案实施例的铺设碳纳米管结构前多晶硅衬底的结构示意图。
图7是本技术方案实施例的铺设碳纳米管结构后多晶硅衬底的结构示意图。
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及其制备方法。
请参阅图2，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、一多晶硅衬底14和一碳纳米管结构16。所述背电极12设置于所述多晶硅衬底14的下表面141，且与该多晶硅衬底14的下表面141欧姆接触。所述碳纳米管结构16设置于所述多晶硅衬底14的上表面142，且与该多晶硅衬底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。
所述多晶硅衬底14为p型多晶硅片。该多晶硅衬底14的厚度为200微米～300微米。所述多晶硅衬底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，包括多个均匀分布的碳纳米管。该碳纳米管结构具有良好的吸收太阳光能力，在所述太阳能电池10中起到光电转换材料及上电极的双重作用。该碳纳米管结构包括无序碳纳米管层或者有序碳纳米管层。
所述无序碳纳米管层包括多个无序排列的碳纳米管。该碳纳米管在无序碳纳米管层中相互缠绕或者各向同性。
所述有序碳纳米管层包括多个有序排列的碳纳米管，该碳纳米管沿固定方向择优取向排列。所述的多个碳纳米管在该有序碳纳米管层中平行于所述有序碳纳米管层的表面排列，且沿同一方向或者沿多个方向择优取向排列。
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多晶硅衬底14的表面。
请参阅图3及图4，本实施例采用的碳纳米管结构16包括一有序碳纳米管薄膜163。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，以使所述太阳能电池10具有均匀的电阻、良好导电性以及较高的光电转换效率。
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固定方向择优取向排列。
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多晶硅衬底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多晶硅衬底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多晶硅衬底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。
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，在所述多晶硅衬底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多晶硅衬底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、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，这样外电路就有电流通过。
请参阅图5，本技术方案实施例提供一种制备上述采用有序碳纳米管薄膜163的太阳能电池10的方法，其具体包括以下步骤：
步骤一：提供一多晶硅衬底14。
该多晶硅衬底12为P型多晶硅片，采用标准电子级清洗步骤清洗该P型多晶硅片。请参阅图6，所述多晶硅衬底14的晶粒间存在很多的畴界143，畴界143处是多晶硅缺陷最集中的地方，包括了大量的不饱和悬挂键。而这些不饱和悬挂键是载流子的俘获中心，会影响所述太阳能电池10的光电转换效率及载流子的迁移率。
步骤二：在该多晶硅衬底14一侧的表面上形成一背电极12。
以高纯铝作为蒸发源，采用热蒸发技术，在上述P型多晶硅片14一侧的表面上沉积形成厚度为10微米～300微米的金属铝作为背电极12；接着在充满惰性的气氛下，在300℃～500℃下退火20分钟～40分钟，在所述P型多晶硅片14一侧的表面形成与该述P型多晶硅片14欧姆接触的背电极12。
本技术方案实施例优选在上述P型多晶硅片14一侧的表面上沉积形成厚度为20微米的金属铝作为背电极12；接着在充满惰性的气氛下，在450℃下退火30分钟，在所述P型多晶硅片14一侧的表面形成与该述P型多晶硅片14欧姆接触的背电极12。
可以理解，也可在上述P型多晶硅片14一侧的表面涂覆一层导电胶，将一金属片粘附于所述P型多晶硅片14一侧的表面形成与该述P型多晶硅片14欧姆接触的背电极14。
步骤三：制备至少一有序碳纳米管薄膜163。
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有序碳纳米管薄膜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，获得一连续的有序碳纳米管薄膜163，该有序碳纳米管薄膜163中的碳纳米管的排列方向平行于有序碳纳米管薄膜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，从而形成一有序碳纳米管薄膜163。
步骤四：将所述至少一有序碳纳米管薄膜163铺设于所述多晶硅衬底14的上表面142，从而得到一太阳能电池10。
可以理解，可将一有序碳纳米管薄膜163直接铺设于所述硅晶衬底14的上表面142，或者将至少两个有序碳纳米管薄膜163重叠铺设于所述硅晶衬底14的上表面142。所述至少一有序碳纳米管薄膜163形成一碳纳米管结构16，作为所述太阳能电池10的光电转换材料及上电极。
请参阅图7，所述多晶硅衬底14中晶粒间的畴界143处存在着大量的不饱和悬挂键。所述碳纳米管结构16在不饱和悬挂键的作用下吸附于所述多晶硅衬底14的上表面142，饱和畴界143处的部分悬挂键，降低悬挂键对载流子的俘获，从而提高所述太阳能电池10的光电转换效率及载流子的迁移率。
所述太阳能电池及其制备方法具有以下优点：其一，由于采用碳纳米管结构作为光电转换材料，可以饱和部分悬挂键，降低悬挂键对载流子的俘获无需形成掺杂硅层，同时碳纳米管结构对太阳光具有很好的透光性，采用碳纳米管结构作为上电极，可以提高太阳能电池的光电转换效率；其二，碳纳米管结构在太阳能电池中起到光电转换及上电极的双重作用，且无需磷或砷层，因此结构简单。
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 (15)

1.一种太阳能电池，其包括：
一多晶硅衬底；
一背电极，该背电极设置于所述多晶硅衬底的下表面，且与该多晶硅衬底的下表面欧姆接触；
其特征在于，所述太阳能电池进一步包括一碳纳米管结构，该碳纳米管结构设置于所述多晶硅衬底的上表面，且与该多晶硅衬底的上表面接触。
2.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管结构包括均匀分布的碳纳米管。
3.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管结构包括无序碳纳米管层或者有序碳纳米管层。
4.如权利要求3所述的太阳能电池，其特征在于，所述无序碳纳米管层包括多个无序排列的碳纳米管。
5.如权利要求3所述的太阳能电池，其特征在于，所述有序碳纳米管层包括多个有序排列的碳纳米管。
6.如权利要求3所述的太阳能电池，其特征在于，所述有序碳纳米管层包括至少一有序碳纳米管薄膜，该有序碳纳米管薄膜通过直接拉伸一碳纳米管阵列获得，且包括沿拉伸方向择优取向排列的碳纳米管。
7.如权利要求6所述的太阳能电池，其特征在于，所述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，每个碳纳米管束包括多个长度相等且平行排列的碳纳米管。
8.如权利要求6所述的太阳能电池，其特征在于，所述有序碳纳米管层包括至少两个重叠设置的有序碳纳米管薄膜。
9.如权利要求8所述的太阳能电池，其特征在于，所述相邻两个有序碳纳米管薄膜中的碳纳米管之间具有一交叉角度α，且0度≤α≤90度。
10.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管结构包括多个互相平行铺设的碳纳米管长线。
11.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管结构为一层状结构，每一层包括多个互相平行铺设的碳纳米管长线，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。
12.如权利要求1所述的太阳能电池，其特征在于，所述碳纳米管结构包括一碳纳米管薄膜和多个碳纳米管长线，该多个碳纳米管长线互相平行铺设于所述碳纳米管薄膜表面。
13.如权利要求1所述的太阳能电池，其特征在于，所述多晶硅衬底为n型多晶硅片，其厚度为200微米～300微米。
14.如权利要求1所述的太阳能电池，其特征在于，所述背电极的材料可为铝、镁或者银，且该背电极的厚度为10微米～300微米。
15.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电极，该电极与所述碳纳米管结构的上表面电接触。
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CN104953944A (zh) * 2014-12-13 2015-09-30 襄阳精圣科技信息咨询有限公司 一种使用推挽变换器的太阳能电池

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