CN111710759B - 一种shj太阳电池tco薄膜表面处理方法 - Google Patents
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Abstract
本发明公开了一种SHJ太阳电池TCO薄膜表面处理方法，用于解决现有技术中TCO薄膜与低温银浆接触不好的问题，涉及太阳电池技术领域，包括以下步骤：(1)在硅片的上下表面沉积本征非晶硅或非晶硅氧薄膜；(2)在步骤(1)所得硅片的上下表面分别沉积P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜，或者在其上下表面沉积非晶硅氧薄膜；(3)将步骤(2)所得硅片的上下表面沉积TCO薄膜；(4)采用等离子体对TCO薄膜进行表面处理，包括粗糙化处理和改性处理；本发明能够使低温银浆与TCO薄膜表面的接触更好，浆料边缘延展量低，浆料体系中的有机物延展小，使SHJ太阳电池的转化效率有效提高，有利于提高规模化生产SHJ太阳电池的稳定性和产品良率。
Description
技术领域
一种SHJ太阳电池TCO薄膜表面处理方法，属于太阳电池技术领域，尤其涉及TCO薄膜表面处理技术。
背景技术
太阳电池发电(光伏发电)作为可再生能源发展最快的技术之一，截至2018年底，全球累积装机量已超过400GW，成为新能源的主力军。中国作为世界上最大的太阳电池生产及装机国，近10年平均增速超过140％，累积装机总量接近200GW，成为名副其实的光伏大国。最近几年，随着光伏全产业链的快速规模化扩大发展、产业化技术创新及国家相关优惠政策扶持，相比10年前，中国光伏组件及系统价格分别下降了58％和65％，全国有超过三分之一省份光伏发电的度电成本(LCOE)接近甚至低于传统火力发电。尽管如此，开发下一代低成本/超高效太阳电池技术进一步降低光伏发电的LCOE，依然是科研院所和光伏企业不断创新的动力所在。
硅基异质结太阳电池(SHJ)因其超高转化效率、双面发电、低温度系数等诸多优点被认为是下一代量产超高效太阳电池的优选技术。日本松下作为SHJ太阳电池研发及产业化生产的鼻祖，其开发的SHJ太阳电池光电转化效率记录已接近25％，量产效率超过23％，年产能超过1GW。美国solar city，欧盟REC，俄罗斯Hevel，中国钧石、晋能、通威汉能、山煤国际、东方日升、爱康等也陆续布局SHJ太阳电池，全球规划产能已超过50GW。2019年，汉能成都研发中心报道了转化效率超过25.1％的双端子SHJ太阳电池世界记录，再次揭起了SHJ太阳电池产业化投资热潮。
硅异质结太阳电池是以晶体硅为基础，经过清洗制绒、在晶体硅正面第一受光面依次沉积本征非晶硅层和N型非晶硅层、在背面第二受光面依次沉积本征非晶硅层和P型非晶硅层、在第一受光面和第二受光面同时沉积透明导电氧化物(TransparentConductiveOxide：TCO)，最后在第一受光面和第二受光面，利用丝网印刷技术，采用热固型低温树脂浆料制备金属电极，得到硅异质结太阳电池。
TCO薄膜表面的金属电极对提高SHJ太阳电池的转化效率有很大影响，优异的金属电极高宽比可以提高电极的导电性和减少电极的遮光损失。低温银浆丝网印刷制备金属电极时，印刷电极的线形与低温浆料体系、网板设计及印刷参数有关；低温浆料体系中的银粉微结构、有机物体系、树脂体系等是决定浆料品质的关键因素；除此之外，电池表面状态是影响印刷电极的重要因素之一。然而，TCO薄膜表面由于包含有许多In、O、Sn、OH-、H+及表面C污染物，导致其表面浸润性差、表面能低、表面粗糙度小。因此，在TCO薄膜表面上印刷低温银浆时，TCO薄膜与低温银浆体系结合不够理想，导致在丝网印刷电极过程中工艺难以控制，有机物外延严重、银电极外延重要、银消耗量过多、高宽比低、拉力极差等一系列问题，使得SHJ太阳电池的成本、A品率、客诉率等远远比不上成熟PERC电池工艺的水平，影响了SHJ电池的大批量生产和产业化推广。
为了降低SHJ太阳电池的成本、提高A品率、提高拉力等的技术难题，很多企业和科研院所进行了大量的研究，尝试通过引进先进的金属化技术和浆料体系以期达到提效降本，如银包铜低温浆料、电镀铜技术(Plate-Cu)、智能网栅连接技术(SWCT)等。然而，与成熟、低成本的丝网印刷技术相比，电镀铜技术面临污水排放及掩膜成本问题，智能网栅连接技术面临独家供应商和专利技术问题，银包铜低温浆料印刷性及产品成本尚不满足产业化推广。因此，如何解决上述问题对于SHJ太阳电池产业大规模推广具有重要的现实意义。
发明内容
本发明的目的在于：提供一种SHJ太阳电池TCO薄膜表面处理方法，能够使低温银浆与TCO薄膜表面的接触更好，浆料边缘延展量低，浆料体系中的有机物延展小，使SHJ太阳电池的转化效率有效提高，有利于提高规模化生产SHJ太阳电池的稳定性和产品良率。
本发明采用的技术方案如下：
为实现上述目的，本发明提供一种SHJ太阳电池TCO薄膜表面处理方法，包括以下步骤：
(4)在硅片的上下表面沉积本征非晶硅或非晶硅氧薄膜；
(5)在步骤(1)所得硅片的上下表面分别沉积P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜，或者在其上下表面沉积非晶硅氧薄膜；
(6)将步骤(2)所得硅片的上下表面沉积TCO薄膜；
(4)采用等离子体对TCO薄膜进行表面处理，包括粗糙化处理和改性处理。
作为优选，所述等离子体气源包括SiCl4、CCl4、CH4、HBr、H2、Cl2、Ar、O2、SF6中的任意一种或多种组合。
作为优选，所述粗糙化处理所用的等离子体气源为SiCl4、CCl4、CH4、HBr、H2、Cl2、Ar中的任意一种或多种组合。
作为优选，所述改性处理所用的等离子体气源为H2、Cl2、Ar、O2、SF6中的任意一种或多种组合。
作为优选，所述粗糙化处理中，刻蚀时间为10-100s，功率密度为1-10KW/m 2，刻蚀气压为1-100mTorr，粗化后的TCO薄膜表面粗糙度>1.5nm。
作为优选，所述改性处理中，处理时间为10-100s，功率密度为1-10KW/m2，刻蚀气压为1-100mTorr，改性后的TCO薄膜表面能>0.1J/m2。
作为优选，所述TCO薄膜材料为锡掺杂氧化铟、钨掺杂氧化铟、钛掺杂氧化铟、钼掺杂氧化铟、镓掺杂氧化铟、氢掺杂氧化铟、铝掺杂氧化锌、镓掺杂氧化锌和硼掺杂氧化锌中的任意一种或多种。
作为优选，所述TCO薄膜厚度为70-100nm，所述TCO薄膜微结构为非晶、微晶、晶体的一种或者是多种组合。
作为优选，所述TCO薄膜的方块电阻在30-150ohm/sq之间，平均光学透过率大于90％，所述硅片上表面的TCO薄膜平均光学反射率小于3.5％。
综上所述，由于采用了上述技术方案，本发明的有益效果是：
1.本发明通过采用等离子体对TCO薄膜进行粗糙化处理和改性处理，TCO薄膜表面处理后形成了丰富的化学健、表面能更高、粗糙度更大，使得在制备电极时，低温银浆与TCO薄膜表面的接触更好，浆料边缘延展量低，浆料体系中的有机物延展小，从而有利于提高SHJ太阳电池的转化效率(提高了0.3-0.5％)，有利于提高规模化生产SHJ太阳电池的稳定性和产品良率。
2.本发明通过对TCO薄膜进行粗糙化处理和改性处理，使得在制备电极时，低温银浆与TCO薄膜表面的接触更好，印刷电极的工艺过程更容易控制，可有效降低银浆的消耗量，降低生产成本产品，解决了产品效率对低温银浆和印刷工艺稳定性的依赖性，同时电池的电极拉力得到明显改善，为SHJ电池的大批量生产和产业化推广增加了可靠性。
附图说明
本发明将通过例子并参照附图的方式说明，其中：
图1是SHJ太阳电池的结构示意图；
图2是TCO薄膜表面处理前后Ag电极线型对比图；
图3是对TCO薄膜表面做不同处理后Ag电极的结构对比图。
图中标记为：100-单晶硅片，101-本征非晶薄膜，102-P型掺杂非晶硅薄膜，103-N型掺杂非晶硅薄膜，104-TCO薄膜，105-Ag电极，301-有机物，302-金属电极外延。
具体实施方式
下面将结合附图对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例以PECVE镀膜技术为例，提供一种SHJ太阳电池TCO薄膜表面处理方法，包括以下步骤：
(1)用n型单晶硅片100为衬底，首先对硅片进行表面制绒和化学清洗，使表面形成可提高光吸收的金字塔凹凸结构，再次经过化学清洗后形成超清洁的表面，然后利用PECVD方法在硅片上下表面分别沉积本征非晶硅薄膜101，在下表面本征非晶硅薄膜101上沉积P型掺杂硅薄膜102叠层，在上表面本征非晶硅薄膜101上沉积N型掺杂非晶硅薄膜103叠层，然后在两面分别沉积TCO薄膜104。
(2)TCO薄膜104沉积完成后，采用等离子体对TCO薄膜104进行粗糙化处理和改性处理。设置刻蚀功率密度2-8KW/m2之间、刻蚀气压在10-80mTorr之间、刻蚀时间30-80s之间，以SiCl4和Ar为等离子气源，对TCO薄膜104表面进行粗糙化处理，粗化处理结束后以O2和Ar为等离子气源进行改性处理，使得处理后的TCO薄膜104表面粗糙度>1.5nm，表面能>0.1J/m2。
在本实施例处理后的TCO薄膜104表面进行低温银浆丝网印刷，在170-200℃空气环境下烧结后形成金属电极105，制得具有完美对称性结构的太阳电池。
实施例2
本实施例与实施例1的不同之处在于，以O2作为等离子气源对TCO薄膜表面进行改性处理，但省略粗糙化处理，其余步骤相同。
实施例3
本实施例与实施例1的不同之处在于，以CCl4和Ar为等离子气源，对TCO薄膜表面进行粗糙化处理，粗化处理结束后以O2和SF6为等离子气源进行改性处理，其余步骤相同。
实施例4
本实施例与实施例1的不同之处在于，以CH4、HBr为等离子气源，对TCO薄膜表面进行粗糙化处理，粗化处理结束后以Cl2为等离子气源进行改性处理，其余步骤相同。
实施例5
本实施例与实施例1的不同之处在于，以Cl2、Ar为等离子气源，对TCO薄膜表面进行粗糙化处理，粗化处理结束后以O2、Cl2为等离子气源进行改性处理，其余步骤相同。
实施例6
本实施例与实施例1的不同之处在于，以SiCl4为等离子气源，对TCO薄膜表面进行粗糙化处理，粗化处理结束后以O2、H2为等离子气源进行改性处理，其余步骤相同。
实施例7
本实施例与实施例1的不同之处在于，以SiCl4、Ar为等离子气源，对TCO薄膜表面进行粗糙化处理，粗化处理结束后以SF6为等离子气源进行改性处理，其余步骤相同。
实施例8
本实施例与实施例1的不同之处在于，以CCl4、HBr为等离子气源，对TCO薄膜表面进行粗糙化处理，粗化处理结束后以O2为等离子气源进行改性处理。
针对不同的TCO薄膜表面处理工艺，对TCO表面上的电极和有机延展情况进行检测，检测结果如表一所示。
表一、不同处理工艺下的电极和有机延展情况
此外，针对不同的TCO薄膜表面处理工艺，对SHJ太阳电池输出表现及银浆消耗量进行检测，检测结果如表二所示。
表二、不同处理工艺下的SHJ太阳电池输出表现及银浆消耗量
从表一、表二、图2和图3可以看出，经过等离子体粗糙化处理和改性处理后，TCO/Ag电极接触界面有机物横向延展消失、电极边缘延展减小，使得电极光学遮挡减小，使得SHJ太阳电池效率提高了0.3-0.5％，同时银浆的消耗量明显降低，电池的电极拉力也得到明显改善，有利于SHJ电池的大批量生产和产业化推广。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明实施例技术方案的范围，其均应涵盖在本发明的权利要求和说明书的范围当中。
Claims (7)
1.一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，包括以下步骤：
(1)在硅片的上下表面沉积本征非晶硅或非晶硅氧薄膜；
(2)在步骤(1)所得硅片的上下表面分别沉积P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜，或者在其上下表面沉积非晶硅氧薄膜；
(3)将步骤(2)所得硅片的上下表面沉积TCO薄膜；
(4)采用等离子体对TCO薄膜进行表面处理，包括先进行粗糙化处理、再进行改性处理；
所述粗糙化处理所用的等离子体气源为SiCl4、CCl4、CH4、HBr、H2、Cl2、Ar中的任意一种或多种组合；
所述改性处理所用的等离子体气源为H2、Cl2、Ar、O2、SF6中的任意一种或多种组合；
所述粗糙化处理中，刻蚀时间为10-100s，功率密度为1-10KW/m2，刻蚀气压为1-100mTorr，粗化后的TCO薄膜表面粗糙度>1.5nm；
所述改性处理中，处理时间为10-100s，功率密度为1-10KW/m2，刻蚀气压为1-100mTorr，改性后的TCO薄膜表面能>0.1J/m2。
2.根据权利要求1所述的一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，所述TCO薄膜材料为锡掺杂氧化铟、钨掺杂氧化铟、钛掺杂氧化铟、钼掺杂氧化铟、镓掺杂氧化铟、氢掺杂氧化铟、铝掺杂氧化锌、镓掺杂氧化锌和硼掺杂氧化锌中的任意一种或多种。
3.根据权利要求1所述的一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，所述TCO薄膜厚度为70-100nm。
4.根据权利要求1所述的一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，所述TCO薄膜微结构为非晶、微晶、晶体的一种或者是多种组合。
5.根据权利要求1所述的一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，所述TCO薄膜的方块电阻在30-150ohm/sq之间。
6.根据权利要求1所述的一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，所述TCO薄膜的平均光学透过率大于90％。
7.根据权利要求1所述的一种SHJ太阳电池TCO薄膜表面处理方法，其特征在于，所述硅片上表面的TCO薄膜平均光学反射率小于3.5％。
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