CN110797417A - 一种太阳能电池的制备方法 - Google Patents

一种太阳能电池的制备方法 Download PDF

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CN110797417A
CN110797417A CN201810875144.XA CN201810875144A CN110797417A CN 110797417 A CN110797417 A CN 110797417A CN 201810875144 A CN201810875144 A CN 201810875144A CN 110797417 A CN110797417 A CN 110797417A
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辛科
杨立红
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Shanghai zuqiang Energy Co.,Ltd.
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Abstract

本发明实施例涉及光伏领域，公开了一种太阳能电池的制备方法。本发明中，太阳能电池的制备方法包括以下步骤：(1)提供耐温度≥600℃的耐高温玻璃基板；(2)在耐高温玻璃基板上设置背电极层；(3)划刻并贯穿背电极层，划刻线为P1划刻线；(4)在背电极层上设置光电转换层，光电转换层包括光吸收层和过渡层；(5)划刻并贯穿光电转换层，划刻线为P2划刻线；(6)在光电转换层上设置透明前电极层；(7)划刻并贯穿光电转换层与透明前电极层组成的复合层，划刻线为P3划刻线；其中，P1划刻线，P2划刻线，P3划刻线错位设置。本发明提供的太阳能电池的制备方法，能够减小玻璃基板的翘曲度，提高太阳能电池的良品率。

Description

一种太阳能电池的制备方法
技术领域
本发明涉及光伏领域，特别涉及一种太阳能电池的制备方法。
背景技术
当今全球光伏市场是以晶体硅太阳能电池为主，但高能耗的生产工艺导致能源资源的快速消耗将使社会无法承受，也必将制约着光伏产业更大规模的发展。因此，发展低成本、新型薄膜太阳能电池是未来国际光伏产业的必然趋势。CIGS(CuInxGa(1-x)Se2的简称)薄膜太阳能电池，是由Cu(铜)、In(铟)、Ga(镓)、Se(硒)四种元素构成最佳比例的黄铜矿结晶薄膜太阳能电池，是在玻璃或其它廉价衬底上沉积多层化合物半导体和金属薄膜料，薄膜总厚度约3～4微米。该电池成本低、性能稳定、抗辐射能力强，其光电转换效率目前是各种薄膜太阳能电池之首，光谱响应范围宽，在阴雨天光强下输出功率高于其它任何种类太阳能电池，被国际上称为下一时代最有前途的廉价太阳能电池之一。
目前国内外的CIGS薄膜太阳能电池的制备流程为在Na/Ca浮法玻璃基板上形成SiN阻挡层、在SiN阻挡层上形成背电极层、刻划背电极层、在刻划后的背电极层上形成CIGS吸收层、在CIGS吸收层上形成CdS(硫化镉)过渡层、刻划CdS过渡层和CIGS层、在刻划后的CdS过渡层上溅射透明前电极层、刻划透明前电极层、CdS过渡层和CIGS吸收层。
发明人发现现有技术中至少存在如下问题：由于CIGS的镀膜温度较高，Na/Ca浮法玻璃基板在CIGS镀膜时会软化下沉而造成玻璃基板的翘曲度较大，导致后续沉积CdS层、沉积TCO层、以及层压工艺的破片几率大，太阳能电池的良品率低。
发明内容
本发明实施方式的目的在于提供一种太阳能电池的制备方法，能够减小玻璃基板的翘曲度，提高太阳能电池的良品率。
为解决上述技术问题，本发明的实施方式提供了一种太阳能电池的制备方法，包括以下步骤：(1)提供耐温度≥600℃的耐高温玻璃基板；(2)在所述耐高温玻璃基板上设置背电极层；(3)划刻并贯穿所述背电极层、以使所述背电极层均匀分割为多个相互绝缘的背电极层单元，所述划刻并贯穿所述背电极层的划刻线为P1划刻线；(4)在所述背电极层上设置光电转换层，所述光电转换层包括光吸收层和过渡层；(5)划刻并贯穿所述光电转换层、以使所述光电转换层均匀分割为多个相互绝缘的光电转换层单元，所述划刻并贯穿所述光电转换层的划刻线为P2划刻线；(6)在所述光电转换层上设置透明前电极层；(7)划刻并贯穿所述光电转换层与所述透明前电极层组成的复合层，以使所述复合层均匀分割为多个相互绝缘的复合层单元，所述划刻并贯穿所述光电转换层与所述透明前电极层组成的复合层的划刻线为P3划刻线；其中，所述P1划刻线，所述P2划刻线，所述P3划刻线错位设置。
本发明实施方式相对于现有技术而言，由于耐高温玻璃基板的主要成分为Si和O(即硅和氧)，其中Na元素的含量很低、甚至几乎为零，从而无需设置SiN阻挡层来阻止玻璃中的Na元素扩散到背电极层和光电转换层中，进而节省设置SiN阻挡层带来的设备成本、生产成本以及原料成本，具有成本优势；同时，由于耐高温玻璃基板能够耐受更高的温度，因此，在沉积光吸收层的过程中，耐高温玻璃基板不会发生软化下沉的现象，减小了玻璃基板的翘曲度，进而减小了后续沉积过渡层、沉积前电极层、以及层压工艺的破片几率，从而提高了太阳能电池的良品率；并且，由于耐高温玻璃基板能够耐受更高的温度，从而能够进一步提高沉积光吸收层的工艺温度，使得光吸收层的晶型尺寸更大，减小晶界缺陷，提高太阳能电池的转换效率。
可选的，所述光吸收层为铜铟镓硒，铜铟镓，锑化镉中的一种，所述过渡层为CdS，ZnS中的一种。
可选的，所述在所述耐高温玻璃基板上设置背电极层，具体包括：在所述耐高温玻璃基板上设置疏松钼层；在所述疏松钼层上设置致密钼层。由于疏松钼层与玻璃基板的结合能力较好，而致密钼层的导电性能较好，如此设置，能够在保证背电极层的导电性的前提下，提高背电极层与玻璃基板的结合力。
可选的，所述在所述耐高温玻璃基板上设置疏松钼层，具体包括：在0.02-0.05mbar的气压下，在所述耐高温玻璃基板上设置疏松钼层；
所述在所述疏松钼层上设置致密钼层，具体包括：
在0.002-0.008mbar的气压下，在所述疏松钼层上设置致密钼层。
可选的，所述疏松钼层的厚度为15nm～25nm，所述致密钼层的厚度为250nm～350nm。
可选的，所述划刻并贯穿所述背电极层，具体为：通过纳秒脉冲光纤激光器划刻并贯穿所述背电极层。如此设置，能够在保证划刻线的宽度的前提下，降低设备成本。
可选的，所述光吸收层为CIGS时，所述设置光吸收层的步骤，具体为：在预设温度下设置CIGS层，其中，所述预设温度为T，且600℃≤T≤700℃。
可选的，所述背电极层包括依次设置在所述耐高温玻璃基板上的疏松钼层，设置在所述疏松钼层上的致密钼层，所述光电转换层设置在所述致密钼层上。
附图说明
图1是本发明第一实施方式提供的太阳能电池的制备方法的流程图；
图2(a至g)是本发明第一实施方式提供的太阳能电池的制备方法中各步骤对应的太阳能电池的结构示意图；
图3是本发明第二实施方式提供的太阳能电池的结构示意图；
图4是多个本发明第二实施方式提供的太阳能电池串联而成的电池组件的结构示意图。
附图标记：太阳能电池100、耐高温玻璃基板11、背电极层12、光吸收层13、过渡层14、透明前电极层15、P1划刻线16、P2划刻线17、P3划刻线18、疏松钼层121、致密钼层122。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合附图对本发明的各实施方式进行详细的阐述。然而，本领域的普通技术人员可以理解，在本发明各实施方式中，为了使读者更好地理解本发明而提出了许多技术细节。但是，即使没有这些技术细节和基于以下各实施方式的种种变化和修改，也可以实现本发明所要求保护的技术方案。
本发明的第一实施方式涉及一种太阳能电池100的制备方法，如图1，图2所示，包括以下步骤：
S101:提供耐温度≥600℃的耐高温玻璃基板11。
如图2中的图a所示，具体的说，在步骤S101中，耐高温玻璃基板11可耐700℃左右的高温，且其主要成分为Si和O(即硅和氧)，其中，硅元素的质量占比为38-42％，氧元素的质量占比为50-54％，Na元素的含量很低、甚至几乎为零。
S102:在所述耐高温玻璃基板11上设置背电极层12。
如图2中的图b所示，具体的说，在步骤S102中，所述背电极层12的材质为Mo，首先在所述耐高温玻璃基板11上沉积一层疏松钼层121，然后在所述疏松钼层121上沉积致密钼层122。具体的，通过双层Mo沉积工艺沉积背电极层12的步骤，可以参照以下两步执行：第一，在较低的真空度条件，例如0.02-0.05mbar(毫巴)，进一步地，真空度可优选为0.03-0.04mbar(毫巴)，通过磁控溅射法在10KW溅射功率下，沉积一层厚度为10-20nm的种子层，因为高气压沉积，所以沉积得到的Mo种子层略为疏松，但与玻璃基板的结合力非常好，进而提高了背电极层12与玻璃基板的结合力；第二，在较高的真空度条件，例如0.002-0.008mbar(毫巴)，进一步的，真空度可优选为0.005或0.006mbr(毫巴)，通过磁控溅射法在20KW的溅射功率下，在Mo种子层上再沉积一层厚度为270nm～330nm的Mo层，因为低气压沉积，所以沉积得到的Mo层很致密，从而保证了背电极层12的导电性。本实施方式中，所述疏松钼层121的厚度小于所述致密钼层122的厚度，具体的说，所述疏松钼层121的厚度可为15nm～25nm，所述致密钼层122的厚度可为250nm～350nm。优选的，在本实施方案中，所述疏松钼层121的厚度为20nm，所述致密钼层122的厚度为300nm。如此设置，能够更好的保证背电极层12的导电性以及背电极层12与玻璃基板的结合力，同时保证了钼层具有较好的沉积速度。
S103:划刻并贯穿背电极层12、以使背电极层12均匀分割为多个相互绝缘的背电极层单元，划刻并贯穿背电极层的划刻线为P1划刻线16。
如图2中的图c所示，具体的说，在步骤S103中，首先通过ns-second(纳秒脉冲光纤)激光器划刻所述背电极层12形成P1划刻线16。由于没有SiN阻挡层，在划刻背电极层12时也就无需透过SiN层，从而可以选用激光频率更低的激光器，例如ns-second。ns-second激光器所划刻的线宽为40um(微米)，与ps-second激光器相当，因此，使用ns-second激光器能够保证P1划刻线16的刻划宽度基本不受影响；同时，ns-second激光器的工作功率为8瓦左右，由于其激光频率为10-9s，相比于激光频率为10-12s的ps-second激光器，其设备成本要低很多，从而在保证划刻线宽的前提下，降低了设备成本。
S104:在背电极层12上设置光电转换层。
如图2中的图d所示，具体的说，在步骤S104中，光电转换层(图未示)包括光吸收层13和过渡层14，在所述背电极层12上以及所述P1划刻线16中沉积光吸收层13，然后在光吸收层12上沉积过渡层14。过渡层14与光吸收层13共同构成用于发电的pn结，CIGS膜层为pn结的p层，CdS膜层为pn结的n层。
具体的说，光吸收层13为铜铟镓硒，铜铟镓，锑化镉中的一种。本实施方式中，光吸收层13为铜铟镓硒，通过多点源共蒸发沉积工艺沉积制得，采用Cu，In，Ga，Se的各种金属点源，在各个加热装置中分别填充各个金属，在600℃至700℃下，加热各种加热装置使其内部填充的金属融化后形成出各种元素的蒸汽，另外，引入NaF蒸汽作为蒸渡源来提供Na元素，Na作为类似催化剂的作用来促进晶粒生长，同时，镀好Mo的耐高温玻璃基板11在CIGSCoater设备的加热腔室中，从室温逐步加热到沉积CIGS薄膜工艺所需的温度，最终在加热的耐高温玻璃基板11上沉积形成CIGS薄膜，即光吸收层13。优选的，在650℃的工艺温度下，沉积光吸收层13。通过采用耐高温玻璃基板11，该玻璃基板可以耐700℃的高温而不发生软化变形，因此，在保证耐高温玻璃基板11不变形的前提下，在沉积光吸收层13的过程中工艺温度能够达到600℃至700℃，从而光吸收层13更容易在Mo表面形核生长，得到的CIGS膜层晶体尺寸更大，晶界缺陷更小，太阳能电池100的转换效率更高。另外，过渡层14为CdS，ZnS中的一种，优选的，过渡层14的材质为CdS(即硫化镉)，本实施方式中，过渡层14通过水浴沉积法制得。
因为耐高温玻基板璃中几乎没有Na元素且沉积CIGS层13的工艺温度更高，因此CIGS膜层的表面和性能会产生变化，本实施方式中，通过优化CIGS和CdS的工艺匹配，找到匹配CIGS层的最优化的CdS的厚度，从而更好的保证CIGS和CdS所形成的pn具有很好的光伏发电性能。例如：1，在耐高温玻璃基板11上沉积形成CIGS膜层后，还包括在CIGS膜层上蒸镀KF，对CIGS进行表面改性(或者称为后处理)的步骤，即通过改变KF的沉积速率来对CIGS的表面的化学状态进行改性，本实施方式中KF沉积速率为0.04nm/s，从而有利于后续沉积CdS层；2，由于更高的CIGS沉积温度会使得CIGS层的表面比较粗糙，本实施方式中通过沉积更厚的CdS膜层，保证了CdS将CIGS表面全部覆盖；3，调整Na的蒸发量与后处理碱金属的蒸发量，其中，Na的蒸发速率为0.018-0.024nm/s，后处理碱金属KF的蒸发速率为0.038-0.044nm/s，从而改善CIGS层性能和PN结性能；3，本实施方式中，在沉积CdS层过程中，通过调整氨水在4种反应物(硫脲、硫酸镉、氨水和去离子水)中的体积分数，具体为氨水浓度为9-11mol/L，从而提高了CdS层的性能。
S105:划刻并贯穿光电转换层、以使光电转换层均匀分割为多个相互绝缘的光电转换层单元，划刻并贯穿光电转换层的划刻线为P2划刻线17。
如图2中的图e所示，具体的说，在步骤S105中，机械划刻所述光吸收层13和所述过渡层14形成贯穿所述光吸收层13和所述过渡层14的P2划刻线17。其中，机械划刻可以采用针头直径为几十个微米的探针来对对应的膜层进行划刻。
S106:在光电转换层上设置透明前电极层15。
如图2中的图f所示，具体的说，在步骤S106中，通过磁控溅射技术，在所述过渡层14上以及所述P2划刻线17中沉积透明前电极层15，透明前电极层15的材质为透明导电氧化物薄膜(例如，掺铝氧化锌)，透明前电极层15作为太阳能电池100的正极，将太阳能电池100发出的电引出。
S107:划刻并贯穿光电转换层与透明前电极层15组成的复合层，以使复合层均匀分割为多个相互绝缘的复合层单元，划刻并贯穿光电转换层与透明前电极层15组成的复合层的划刻线为P3划刻线18。
如图2中的图g所示，具体的说，在步骤S107中，划刻所述透明前电极层15、所述过渡层14和所述光吸收层13，形成贯穿三者的P3划刻线18。值得一提的是，P1划刻线16和P2划刻线17和P3划刻线18错位设置，三者共同实现了各子电池之间的串联。
本发明实施方式相对于现有技术而言，由于耐高温玻璃基板11的软化温度高于沉积光吸收层13时的工艺温度，因此，在沉积光吸收层13的过程中，耐高温玻璃基板11不会发生软化下沉的现象，减小了玻璃基板的翘曲度，进而减小了后续沉积过渡层14、沉积前电极层、以及层压工艺的破片几率，从而提高了太阳能电池100的良品率；同时，由于耐高温玻璃基板11能够耐受更高的温度，从而能够进一步提高沉积光吸收层13的工艺温度，因此，在沉积光吸收层13的过程中，玻璃基板的温度更高，进而得到尺寸更大的CIGS膜层晶体，减小晶界缺陷，提高太阳能电池100的转换效率。
值得一提的是，现有技术中，虽然在采用共蒸发工艺蒸镀CIGS膜层的时候是需要Na作为类似催化剂的作用来促进晶粒生长，得到性能更好的CIGS膜层，提升太阳能电池100的转换效率，但是，一般会引入NaF蒸汽作为蒸渡源来提供Na元素，而钠钙玻璃中的钠的扩散反而会影响Na的添加量的精度，因此需要采用SiN阻挡层来阻挡钠钙玻璃中的Na元素扩散到Mo层和CIGS膜层中。而在本实施方式中，由于耐高温玻璃基板11的主要成分为Si和O(即硅和氧)，其中Na元素的含量很低、甚至几乎为零，从而无需设置SiN阻挡层来阻止玻璃中的Na元素扩散到背电极层12和光吸收层13中，进而节省设置SiN阻挡层带来的设备成本、生产成本以及原料成本，具有成本优势。
本发明的第二实施方式提供了一种太阳能电池100，如图3所示，包括：耐温度≥600℃的耐高温玻璃基板11、设置在所述耐高温玻璃基板11上的背电极层12、设置在所述背电极层12上的光电转换层、设置在所述过渡层14上的透明前电极层15，以及贯穿背电极层12的P1划刻线16、贯穿光电转换层的P2划刻线17，以及贯穿透明前电极层15和光电转换层的P3划刻线18，其中，光电转换层包括光吸收层13和过渡层14，所述P1划刻线16、所述P2划刻线17和所述P3划刻线18错位设置。
本发明实施方式相对于现有技术而言，由于耐高温玻璃基板11的软化温度高于沉积光吸收层13时的工艺温度，因此，在沉积光吸收层13的过程中，耐高温玻璃基板11不会发生软化下沉的现象，减小了玻璃基板的翘曲度，进而减小了后续沉积过渡层14、沉积前电极层、以及层压工艺的破片几率，从而提高了太阳能电池100的良品率；同时，由于耐高温玻璃基板11能够耐受更高的温度，从而使得沉积光吸收层13的工艺温度能够进一步提高，因此，在沉积光吸收层13的过程中，玻璃基板的温度更高，CIGS膜层更容易在Mo表面形核生长，得到的CIGS膜层晶体尺寸更大，晶界缺陷更小，太阳能电池100的转换效率更高。同时，由于耐高温玻璃基板11的主要成分为Si和O(即硅和氧)，其中Na元素的含量很低、甚至几乎为零，从而无需设置SiN阻挡层来阻止玻璃中的Na元素扩散到背电极层12和光吸收层13中，进而节省设置SiN阻挡层带来的设备成本、生产成本以及原料成本，具有成本优势。
本实施方式中，耐高温玻璃基板11可耐700℃左右的高温，且其主要成分为Si和O(即硅和氧)，Na元素的含量很低、甚至几乎为零。
具体的说，所述光吸收层13经由所述P1划刻线16局部嵌入所述背电极层12中，所述透明前电极层15经由所述P2划刻线17局部嵌入所述光吸收层13和所述过渡层14中，其中，P1划刻线16和P3划刻线18分别位于P2划刻线17的两侧、且三者错位设置，P1划刻线16、P2划刻线17和P3划刻线18共同实现了各子电池之间的串联，具体如图4所示。
值得一提的是，所述背电极层12的材质为Mo，所述背电极层12包括依次设置在所述耐高温玻璃基板11上的疏松钼层121，设置在所述疏松钼层121上的致密钼层122，所述光电转换层设置在所述致密钼层122上。由于疏松钼层121与玻璃基板的结合能力较好，而致密钼层122的导电性能较好，如此设置，能够在保证背电极层12的导电性的前提下，提高背电极层12与玻璃基板的结合力。
本实施方式中，所述疏松钼层121的厚度小于所述致密钼层122的厚度，具体的说，所述疏松钼层121的厚度可为15nm～25nm，所述致密钼层122的厚度可为250nm～350nm。优选的，在本实施方案中，所述疏松钼层121的厚度为20nm，所述致密钼层122的厚度为300nm。如此设置，能够更好的保证背电极层12的导电性以及背电极层12与玻璃基板的结合力。
具体的说，过渡层14的材质为CdS(即硫化镉)，CdS层与光吸收层13共同构成用于发电的pn结，CIGS膜层为pn结的p层，CdS膜层为pn结的n层，透明前电极层15的材质为透明导电氧化物薄膜(例如，掺铝氧化锌)，透明前电极层15作为太阳能电池100的正极，将太阳能电池100发出的电引出。
本领域的普通技术人员可以理解，上述各实施方式是实现本发明的具体实施例，而在实际应用中，可以在形式上和细节上对其作各种改变，而不偏离本发明的精神和范围。

Claims (10)

1.一种太阳能电池的制备方法，其特征在于，包括：
(1)提供耐温度≥600℃的耐高温玻璃基板；
(2)在所述耐高温玻璃基板上设置背电极层；
(3)划刻并贯穿所述背电极层、以使所述背电极层均匀分割为多个相互绝缘的背电极层单元，所述划刻并贯穿所述背电极层的划刻线为P1划刻线；
(4)在所述背电极层上设置光电转换层，所述光电转换层包括光吸收层和过渡层；
(5)划刻并贯穿所述光电转换层、以使所述光电转换层均匀分割为多个相互绝缘的光电转换层单元，所述划刻并贯穿所述光电转换层的划刻线为P2划刻线；
(6)在所述光电转换层上设置透明前电极层；
(7)划刻并贯穿所述光电转换层与所述透明前电极层组成的复合层，以使所述复合层均匀分割为多个相互绝缘的复合层单元，所述划刻并贯穿所述光电转换层与所述透明前电极层组成的复合层的划刻线为P3划刻线；
其中，所述P1划刻线，所述P2划刻线，所述P3划刻线错位设置。
2.根据权利要求1所述的太阳能电池的制备方法，其特征于，所述光吸收层为铜铟镓硒，铜铟镓，锑化镉中的一种，所述过渡层为CdS，ZnS中的一种。
3.根据权利要求2所述的太阳能电池的制备方法，其特征在于，所述在所述耐高温玻璃基板上设置背电极层，具体包括：
在所述耐高温玻璃基板上设置疏松钼层；
在所述疏松钼层上设置致密钼层。
4.根据权利要求3所述的太阳能电池的制备方法，其特征在于，所述在所述耐高温玻璃基板上设置疏松钼层，具体包括：
在0.02-0.05毫巴mbar的气压下，在所述耐高温玻璃基板上设置疏松钼层；
所述在所述疏松钼层上设置致密钼层，具体包括：
在0.002-0.008毫巴mbar的气压下，在所述疏松钼层上设置致密钼层。
5.根据权利要求4所述的太阳能电池的制备方法，其特征在于，所述疏松钼层的厚度为15nm～25nm，所述致密钼层的厚度为250nm～350nm。
6.根据权利要求1所述的太阳能电池的制备方法，其特征在于，所述划刻并贯穿所述背电极层，具体为：
通过纳秒脉冲光纤激光器划刻并贯穿所述背电极层。
7.根据权利要求2所述的太阳能电池的制备方法，其特征在于，所述光吸收层为CIGS时，所述设置CIGS层步骤，具体为：
在预设温度下设置CIGS层，其中，所述预设温度为T，且600℃≤T≤700℃。
8.一种太阳能电池，其特征在于，包括：耐温度≥600℃的耐高温玻璃基板、设置在所述耐高温玻璃基板上的背电极层、设置在所述背电极层上的光电转换层、设置在所述光电转换层上的透明前电极层，以及贯穿所述背电极层的P1划刻线、贯穿所述光电转换层的P2划刻线，以及贯穿所述透明前电极层和所述光电转换层的P3划刻线，其中，光电转换层包括光吸收层和过渡层，所述P1划刻线、所述P2划刻线和所述P3划刻线错位设置。
9.根据权利要求8所述的太阳能电池，其特征在于，所述背电极层包括依次设置在所述耐高温玻璃基板上的疏松钼层，设置在所述疏松钼层上的致密钼层，所述光电转换层设置在所述致密钼层上。
10.根据权利要求9所述的太阳能电池，其特征在于，所述疏松钼层的厚度为15nm～25nm，所述致密钼层的厚度为250nm～350nm。
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