CN107863415B - 一种热氧化结合pecvd提升太阳能电池片转化效率的方法 - Google Patents
一种热氧化结合pecvd提升太阳能电池片转化效率的方法 Download PDFInfo
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Abstract
本发明涉及太阳能电池领域，公开了一种热氧化结合PECVD提升太阳能电池片转化效率的方法，包括：1）硅片预清洗、制绒及酸清洗；2）高温磷扩散、湿法刻蚀；3）热氧化处理：方阻控制在95‑120 ohm/squ，二氧化硅层厚度控制在10‑20nm；4）PECVD镀膜：依次沉积SixNy膜、SixNyO膜和SiOx膜；三步镀膜后膜厚控制在50‑70nm；且热氧化处理和PECVD镀膜后总膜厚控制在60‑90nm，折射率控制在1.9‑2.1；5）背电极和正电极丝网印刷及烧结。本发明方法独创性地将PECVD镀膜工艺与热氧化工艺匹配结合，并且进一步在热氧化基础上提升电池片的转化效率0.1%以上。
Description
技术领域
本发明涉及太阳能电池领域，尤其涉及一种热氧化结合PECVD提升太阳能电池片转化效率的方法。
背景技术
表面钝化就是降低半导体的表面活性，使表面的复合速率降低，其主要的方式是饱和半导体表面处的悬挂键，降低表面活性，增加表面的清洁程度，避免由于杂质在表面层的引入而形成复合中心，以此来降低少数载流子的表面复合速率，使器件稳定工作。适用于太阳电池表面钝化的措施一般有以下四个方面：表面悬挂键饱和钝化、发射结钝化、发射结氧化钝化和场钝化。包括氢化钝化和氧化钝化等多种方法。氧化钝化方法就是在硅片表面热氧化生长SiO2钝化膜以达到表面钝化的效果。SiO2膜是通过硅氧化形成，具有一个不规则多面体网络的非晶态结构。氧化反应在SiO2/Si界面发生，在生长氧化层时硅不断消耗，整个SiO2/Si界面逐渐向硅片内部侵入，而SiO2/Si界面的电荷主要有界面态、固定电荷、可动正离子三种类型。
这三种电荷都会造成晶体表层晶格缺陷增多、悬挂键增加，进而影响增加载流子的复合速率，降低少子寿命，所以如何控制热氧化过程中氧化层的生长速度和SiO2/Si界面特性显得尤为重要。
另外行业现有制备PECVD工艺只是简单在硅片表面镀一层减反射膜，用于减少电池片表面的反射率，增加对光的吸收，但是电池片对于长波范围光吸收还是较少。并且PECVD工艺与热氧化工艺都是表面生长一层膜，虽然两种生长膜的折射率不同，但是可以相互匹配进一步优化电池片的电性能，而行业现有的制备工艺没能将二者很好的结合起来，所以如何将热氧化工艺所形成的SiO2膜与PECVD工艺所形成的减反射膜结合起来变得非常关键。
发明内容
为了解决上述技术问题，本发明提供了一种热氧化结合PECVD提升太阳能电池片转化效率的方法。本发明方法独创性地将PECVD镀膜工艺与热氧化工艺匹配结合，并且进一步在热氧化基础上提升电池片的转化效率0.1％以上(在本领域中，在转化效率上能够取得0.1％以上提高已经属于非常显著的进步)。
本发明的具体技术方案为：一种热氧化结合PECVD提升太阳能电池片转化效率的方法，包括以下步骤：
1)原始硅片预清洗、制绒及酸清洗。
2)高温磷扩散、湿法刻蚀。
3)热氧化处理：热氧化后方阻控制在95-120ohm/squ，二氧化硅层厚度控制在10-20nm。
4)PECVD镀膜：第一步，沉积SixNy膜；第二步，沉积SixNyO膜；第三步，沉积SiOx膜；三步镀膜后膜厚控制在50-70nm；且热氧化处理和PECVD镀膜后总膜厚控制在60-90nm，折射率控制在1.9-2.1。
5)背电极和正电极丝网印刷及烧结，完成电池片制备。
1、本发明在热氧化处理方面，本发明通过对各项参数调节来控制氧化层的生长速度，以控制SiO2膜的厚度(厚度为10nm-20nm)以使其具有良好的钝化效果，同时还能够控制以及Si/SiO2界面特性，从而减少硅片表面的缺陷态密度，减少载流子复合，提高少子寿命，有利于提升电池片的开路电压。
2、本发明的PECVD镀膜工艺采用三步工艺，即在硅片表面镀三层膜，然后通过对各层膜厚调节，可以很好地把减反射膜厚控制在50nm-70nm，热氧化处理和PECVD镀膜后总膜厚控制在60-90nm。本发明的PECVD镀膜工艺能够控制减反射膜的厚度和均匀性，并且可以很好匹配热氧化工艺所形成的SiO2膜，可以起到多层减反射膜的效果，使得硅片表面有较低折射率、反射率以及较高的外量子效率，从而增强对光的吸收，有利于提高电池片的短路电流。
作为优选，步骤1)中，所述硅片制绒后绒面尺寸控制在2～4μm，反射率大于13％。
作为优选，步骤2)中，高温磷扩散形成发射区后进行湿法刻蚀，发射区方阻控制在85-105ohm/squ。
作为优选，步骤3)中，热氧化处理具体为：初始温度为710-730℃，经450-550s升温至770-790℃；保温氧化10-25min，氧气流量为3000-5000sccm，氮气流量10000-14000sccm，炉管压力为正压状态；然后经750-850s降温至690-710℃，氮气流量13000-15000sccm。
作为优选，步骤4)的第一步中，炉管温度控制在420-480℃，时间450-650s，NH3流量5000-6000sccm，SiH4流量400-600sccm，压力1500-1900mtorr，功率3500-4500W，占空比3/40。
作为优选，步骤4)的第二步中，炉管温度控制在420-480℃，时间100-200s，N2O流量2000-3000sccm，SiH4流量300-500sccm，NH3流量1500-2500sccm，压力1200-1600mtorr，功率2500-3500W，占空比3/40。
作为优选，步骤4)的第三步中，炉管温度控制在420-480℃，时间100-200s，硅烷SiH4流量300-500sccm，笑气N2O流量3000-5000sccm，压力1200-1600mtorr，功率2500-3500W，占空比3/40。
本发明的技术原理依据：
1.热氧化层的生长速度主要受氧分子在SiO2层中的迁移速度和SiO2/Si界面处氧分子与硅原子的反应速率影响。而这两个速率主要受氧化时间、氧气流量、氮气流量、炉管温度和炉内气体压力控制。
2.PECVD镀膜工艺是直接在热氧化的SiO2氧化层上面镀SixNy膜，SixNy膜与SiO2膜的晶格系数更加匹配，折射率形成高低搭配，从而可以达到更好的光学参数匹配，从而降低了硅片表面整体的反射率和折射率。
通过对上述各步骤工艺的调整、配合，能够更好地提升电池片转化效率。
与现有技术对比，本发明的有益效果是：
本发明可提升单晶硅电池片开路电压、短路电流，从而提升转换效率，该热氧化工艺能够很好的控制SiO2层厚度，膜厚控制在10-20nm，且能够保证优异的SiO2/Si界面特性。采用该PECVD工艺能够很好地与热氧化工艺进行匹配，使硅片表面整体的膜厚可以控制在60-90nm，起到多层减反射膜的效果，并且可以确保硅片表面膜厚均匀性以及降低表面折射率和反射率，(用SE400adv-PV椭偏仪测得折射率1.9-2.1，D8积分反射仪测得反射率1.8-2.3)增强了对光的吸收，提高短路电流；另外PECVD过程所形成的减反射层还可以有效地提高热氧化过成所形成SiO2/Si界面的特性，降低了光生载流子复合，提高少子寿命，进而提高开路电压。采用该技术方案，单晶电池片开路电压Uoc提升1.5-3mV，短路电流Ise提高10-30mA，效率可以提升0.1％以上。
具体实施方式
下面结合实施例对本发明作进一步的描述。
实施例1
一种热氧化结合PECVD提升太阳能电池片转化效率的方法，包括以下步骤：
1)原始硅片预清洗、制绒及酸清洗，硅片制绒后绒面尺寸控制在3μm，反射率大于13％。
2)高温磷扩散形成发射区后进行湿法刻蚀，发射区方阻控制在89-96ohm/squ(详见表2)。
3)热氧化处理：初始温度为720℃，经500s升温至780℃；保温氧化1200s，氧气流量为4000sccm，氮气流量10000sccm，炉管压力为正压状态；然后经800s降温至700℃，氮气流量14000sccm。热氧化后方阻控制在98-105ohm/squ(详见表2)，二氧化硅层厚度控制在13-17nm。
4)PECVD镀膜：
第一步，沉积SixNy膜：炉管温度控制在450℃，时间520s，氨气NH3流量5500sccm，硅烷SiH4流量500sccm，压力1700mtorr，功率4000W，占空比3/40。
第二步，沉积SixNyO膜：炉管温度控制在450℃，时间120s，氨气NH3流量2000sccm，硅烷SiH4流量400sccm，笑气N2O流量2500sccm，压力1300mtorr，功率3000W，占空比3/40。
第三步，沉积SiOx膜：炉管温度控制在450℃，时间150s，硅烷SiH4流量400sccm，笑气N2O流量4500sccm，压力1300mtorr，功率3000W，占空比3/40。
三步镀膜后膜厚控制在60-64nm；且热氧化处理和PECVD镀膜后总膜厚控制在77.5-80.1nm(详见表3)，折射率控制在2.021-2.025(详见表3)。
5)背电极和正电极丝网印刷及烧结，完成电池片制备。
表1：常规工艺方案与发明实施例1的热氧化/PECVD结合工艺方案的效率对比
由上表可知，实施例1的电池与常规工艺制得的电池，在各项性能上均更为出色，特别是在转化效率上，取得了0.12％的提升，在本领域中，在转化效率上能够取得0.1％以上提高已经属于非常显著的进步。
表2典型的扩散方阻与氧化方阻
表3典型的热氧化/PECVD结合工艺的膜厚与折射率
| 常规工艺膜厚/nm | 72.5 | 72.1 | 73.8 | 75.5 | 71.2 | 74.3 |
| 常规工艺折射率 | 2.071 | 2.075 | 2.062 | 2.052 | 2.054 | 2.052 |
| 实施例1膜厚/nm | 80.1 | 79.6 | 77.5 | 78.3 | 78.8 | 79.5 |
| 实施例1折射率 | 2.021 | 2.022 | 2.023 | 2.025 | 2.025 | 2.023 |
实施例2
一种热氧化结合PECVD提升太阳能电池片转化效率的方法，包括以下步骤：
1)原始硅片预清洗、制绒及酸清洗，硅片制绒后绒面尺寸控制在2μm，反射率大于13％。
2)高温磷扩散形成发射区后进行湿法刻蚀，发射区方阻控制在85ohm/squ。
3)热氧化处理：初始温度为710℃，经450s升温至770℃；保温氧化10min，氧气流量为3000sccm，氮气流量12000sccm，炉管压力为正压状态；然后经750s降温至690℃，氮气流量13000sccm。热氧化后方阻控制在85-105ohm/squ，二氧化硅层厚度控制在10nm左右。
4)PECVD镀膜：
第一步，沉积SixNy膜：炉管温度控制在420℃，时间450s，NH3流量5000sccm，SiH4流量400sccm，压力1500mtorr，功率3500W，占空比3/40。
第二步，沉积SixNyO膜：炉管温度控制在420℃，时间100s，N2O流量2000sccm，SiH4流量300sccm，NH3流量1500sccm，压力1200mtorr，功率2500W，占空比3/40。
第三步，沉积SiOx膜：炉管温度控制在420℃，时间100s，硅烷SiH4流量300sccm，笑气N2O流量3000sccm，压力1200mtorr，功率2500W，占空比3/40。
三步镀膜后膜厚控制在50nm左右；且热氧化处理和PECVD镀膜后总膜厚控制在60nm左右，折射率控制在2.02左右。
5)背电极和正电极丝网印刷及烧结，完成电池片制备。
实施例3
一种热氧化结合PECVD提升太阳能电池片转化效率的方法，包括以下步骤：
1)原始硅片预清洗、制绒及酸清洗，硅片制绒后绒面尺寸控制在4μm，反射率大于13％。
2)高温磷扩散形成发射区后进行湿法刻蚀，发射区方阻控制在105ohm/squ。
3)热氧化处理：初始温度为730℃，经550s升温至790℃；保温氧化25min，氧气流量为5000sccm，氮气流量14000sccm，炉管压力为正压状态；然后经850s降温至710℃，氮气流量15000sccm。热氧化后方阻控制在120ohm/squ，二氧化硅层厚度控制在20nm左右。
4)PECVD镀膜：
第一步，沉积SixNy膜：炉管温度控制在480℃，时间650s，NH3流量6000sccm，SiH4流量600sccm，压力1900mtorr，功率4500W，占空比3/40。
第二步，沉积SixNyO膜：炉管温度控制在480℃，时间200s，N2O流量3000sccm，SiH4流量500sccm，NH3流量2500sccm，压力1600mtorr，功率3500W，占空比3/40。
第三步，沉积SiOx膜：炉管温度控制在480℃，时间200s，硅烷SiH4流量500sccm，笑气N2O流量5000sccm，压力1600mtorr，功率3500W，占空比3/40。
三步镀膜后膜厚控制在70nm左右；且热氧化处理和PECVD镀膜后总膜厚控制在90nm左右，折射率控制在1.9-2.1。
5)背电极和正电极丝网印刷及烧结，完成电池片制备。
本发明中所用原料、设备，若无特别说明，均为本领域的常用原料、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换，均仍属于本发明技术方案的保护范围。
Claims (6)
1.一种热氧化结合PECVD提升太阳能电池片转化效率的方法，其特征在于包括以下步骤：
1）原始硅片预清洗、制绒及酸清洗；
2）高温磷扩散、湿法刻蚀；
3）热氧化处理：热氧化处理具体为：初始温度为710-730℃，经450-550s升温至770-790℃；保温氧化10-25min，氧气流量为3000-5000sccm，氮气流量10000-14000sccm，炉管压力为正压状态；然后经750-850s降温至690-710℃，氮气流量13000-15000sccm；热氧化后方阻控制在95-120 ohm/squ，二氧化硅层厚度控制在10-20nm；
4）PECVD镀膜：第一步，沉积SixNy膜；第二步，沉积SixNyO膜；第三步，沉积SiOx膜；三步镀膜后膜厚控制在50-70nm；且热氧化处理和PECVD镀膜后总膜厚控制在60-90nm，折射率控制在1.9-2.1；
5）背电极和正电极丝网印刷及烧结，完成电池片制备。
2.如权利要求1所述的一种热氧化结合PECVD提升太阳能电池片转化效率的方法，其特征在于，步骤1）中，所述硅片制绒后绒面尺寸控制在2~4μm，反射率大于13%。
3.如权利要求1所述的一种热氧化结合PECVD提升太阳能电池片转化效率的方法，其特征在于，步骤2）中，高温磷扩散形成发射区后进行湿法刻蚀，发射区方阻控制在85-105ohm/squ。
4.如权利要求1所述的一种热氧化结合PECVD提升太阳能电池片转化效率的方法，其特征在于，步骤4）的第一步中，炉管温度控制在420-480℃，时间450-650s，NH3流量5000-6000sccm，SiH4流量400-600sccm，压力1500-1900mtorr，功率3500-4500W，占空比3/40。
5.如权利要求4所述的一种热氧化结合PECVD提升太阳能电池片转化效率的方法，其特征在于，步骤4）的第二步中，炉管温度控制在420-480℃，时间100-200s，N2O流量2000-3000sccm，SiH4流量300-500sccm，NH3流量1500-2500sccm，压力1200-1600mtorr，功率2500-3500W，占空比3/40。
6.如权利要求5所述的一种热氧化结合PECVD提升太阳能电池片转化效率的方法，其特征在于，步骤4）的第三步中，炉管温度控制在420-480℃，时间100-200s，硅烷SiH4流量300-500sccm，笑气N2O流量3000-5000sccm，压力1200-1600mtorr，功率2500-3500W，占空比3/40。
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