CN105140345A - 一种异质结电池及其制备方法 - Google Patents
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Abstract
本发明涉及一种异质结电池的制备方法,其特征在于,包括如下步骤:a)在硅晶片上沉积铜,形成电极层;b)光刻;c)湿法及电镀。本发明提供的铜电极异质结电池具有以下有益技术效果:1.既解决了银储量有限和未来银价格上涨的问题,又满足了光伏产业未来发展的需求;2.铜异质结电池相对目前的传统晶硅电池具有成本更低,而效率更高的优势,尤其是可提高单位面积发电量,更适宜分布式发电;3.铜电极技术研发的成功将突破我国光伏产业低水平重复投资和技术创新性不够的困境。
Description
技术领域
本发明涉及一种太阳能电池及其制备方法,尤其涉及一种异质结电池及其制备方法。
背景技术
传统晶硅电池工艺中普遍采用的丝网印刷银浆工艺,由于银的成本较高和资源有限,并不能满足未来太阳能电池的生产需求。而且丝网印刷过程需要对硅片施加一定的压力,容易导致碎片的问题。传统晶硅电池的产品存在边缘漏电、化学镀锡后ITO发白、栅线断线、栅线线宽不均匀、栅线脱落等技术缺陷。
本发明提供新型的铜电极化技术,这种技术对硅片施加外部压力很微小或可实现非接触式工艺,可实现低碎片率生产,并且电池制造成本更低而转换效率更高。本发明以异质结电池为基础进行铜电极技术研发,其中包括光刻、湿法腐蚀和电镀等主要工艺技术,最后进行工艺集成和产业化解决方案的研究。
发明内容
本发明要解决的技术问题是以异质结电池为基础进行铜电极技术研发,提供一种太阳能电池及其制备方法,制备方法包括光刻、湿法腐蚀和电镀等主要工艺技术,研发出铜电极的异质结太阳能电池,克服了边缘漏电、化学镀锡后ITO发白、栅线断线、栅线线宽不均匀、栅线脱落等技术问题。
为了解决上述技术问题,本发明采取的技术方案如下:
(1)一种异质结电池的制备方法,包括如下步骤:
a)在硅晶片上沉积铜,形成电极层;
b)光刻;
c)湿法及电镀。
(2)根据(1)所述的异质结电池的制备方法,所述硅晶片的结构依次包括ITO层、P-Si层、i-Si层、Si衬底、N-Si层、i-Si层和ITO层。
(3)根据(1)或(2)所述的异质结电池的制备方法,所述a)步骤中,在硅晶片双面沉积铜,形成电极层;采用射频方式进行沉淀,射频频率为12-16MHz,工作气体为氩气,靶材为铜。所述沉积的工艺条件如下,本底真空为5X10-5Pa,工作气压为0.1-0.5Pa,溅射功率为200-400W,溅射时间为200-280S,硅晶片温度为90-110℃。
(4)根据(1)-(3)任一项所述的方法异质结电池的制备方法,所述b)光刻步骤包括,激光光绘绘制图形、冲片显影菲林片、压膜和曝光。
(5)根据(1)-(4)任一项所述的方法异质结电池的制备方法,在所述冲片显影菲林片步骤中,定影、显影液以浓度20-30%的比例配置,冲片温度为30-50℃,传送速度恒定。
(6)根据(1)-(5)任一项所述的方法异质结电池的制备方法,所述压膜步骤如下,所述压膜步骤如下,压膜轮滚轴上表面温度90-110℃,压膜轮滚轴下表面温度90-100℃,传输速率0.4-0.6m/min。
(7)根据(1)-(6)任一项所述的方法异质结电池的制备方法,所述曝光的能量强度为80-90mv/cm2。
(8)根据(1)-(7)任一项所述的方法异质结电池的制备方法,所述湿法包括显影、水洗和稀硫酸清洗。
(9)根据(1)-(8)任一项所述的方法异质结电池的制备方法,在所述显影中,碳酸钠浓度为0.5-2%,温度为20-40℃,时间为0.5-4min;所述水洗步骤为水洗2次,每次水洗时间为1-2min,温度为室温-45℃;所述稀硫酸清洗步骤在室温中进行,硫酸浓度为10%,清洗时间为0.2-1min。
(10)根据(1)-(9)任一项所述的方法异质结电池的制备方法,所述电镀步骤中电镀溶液的配方为,水硫酸铜67.5-90g/l,硫酸100-130ml/l,氯离子50-80ppm,陶氏添加剂451#2-4ml/l,陶氏452#10-30ml/l。
(11)根据(1)-(10)任一项所述的方法异质结电池的制备方法,所述电镀的工艺条件为,18-35℃,1-6A/dm2,12-40min。
(12)根据(1)-(11)任一项所述的方法异质结电池的制备方法,在电镀步骤之后还依次包括如下步骤:水洗、去膜、水洗、去除种子铜、水洗、稀硫酸清洗、化学镀锡、水洗和干燥。
(13)根据(1)-(12)任一项所述的方法异质结电池的制备方法,在电镀之后水洗、去膜之前的水洗步骤为洗3次,每次1-2min,温度范围为室温-45℃。
(14)根据(1)-(13)任一项所述的方法异质结电池的制备方法,所述去膜步骤使用1-3%氢氧化钠,温度为20-55℃,时间为1-5min。
(15)根据(1)-(14)任一项所述的方法异质结电池的制备方法,在去膜之后、去除种子铜之前的水洗步骤为洗2次,每次1-2min,温度范围为室温-45℃。
(16)根据(1)-(15)任一项所述的方法异质结电池的制备方法,所述去除种子铜的配方为SPS:100~120g/l,H2SO4:1%~3%;工艺条件为:室温-40℃,0.5-5min。
(17)根据(1)-(16)任一项所述的方法异质结电池的制备方法,在去除种子铜之后、稀硫酸清洗之前的水洗步骤为洗2次,每次1-2min,温度范围为室温-45℃。
(18)根据(1)-(17)任一项所述的方法异质结电池的制备方法,所述稀硫酸清洗使用5%-10%硫酸,在室温下清洗1-3min。
(19)根据(1)-(18)任一项所述的方法异质结电池的制备方法,所述化学镀锡的配方为乐思SN100A90%v/v,乐思SN100B10%v/v,工艺条件为63-72℃,1-5min。
(20)根据(1)-(19)任一项所述的方法异质结电池的制备方法,在化学镀锡之后、干燥之前的水洗步骤为洗3次,每次1-2min,温度范围为40-45℃。
(21)根据(1)-(20)任一项所述的方法异质结电池的制备方法,所述干燥在N2氛围中,干燥温度为30-40℃,干燥时间为4-6min。
(22)根据(1)-(21)任一项所述的方法异质结电池的制备方法,电池正面主栅宽度为1-2cm共三根,细栅宽度60-80um共73-75根,电池背面主栅宽度为1-2cm共三根,细栅宽度60-80um共140-150根。
(23)根据(1)-(22)任一项所述的方法异质结电池的制备方法,沉淀载板边缘宽度为2-4mm,正面全部溅射,背面用载板支撑并作为边缘隔离;预留的干膜比硅片大,防止从侧边上铜;PVD前将硅片四周用高温胶带包裹起来,起到隔离的作用。
(24)根据(1)-(23)任一项所述的方法异质结电池的制备方法,,在ITO过程中,化锡温度为20-30℃,PH值为0.9-1.1,即减少酸度,以减轻酸的腐蚀。
(25)一种异质结电池,所述异质结电池的电极为铜电极,在硅晶片上下表面设有铜电极层;所述硅晶片的结构依次包括ITO层、P-Si层、i-Si层、Si衬底、N-Si层、i-Si层和ITO层。
针对边缘漏电问题,本发明提供以下解决方案:
(1)PVD载板边缘宽度由原来的1-2mm变为2-4mm。正面全部溅射,背面用载板支撑并作为边缘隔离。ITO镀膜也是同样的过程,但ITO载板边缘无法限位,导致隔离区ITO据硅片边缘位置波动性大,铜有可能进入隔离区P层和N层。
(2)预留的干膜比硅片大,防止从侧边上铜
(3)PVD前将硅片四周用高温胶带包裹起来,起到隔离的作用。
其中(2)是改善边缘,(1),(3)是核心的因数。
针对镀锡后ITO发白的技术问题,本发明提供以下解决方案:通过一些调研和送样给药水厂家测试,对化锡药水做如下调整:化锡温度由40-60℃降到20-30℃,PH值由0.25-0.35升高到0.95-1.05,即减少酸度,以减轻酸的腐蚀。药水调整后ITO表面发白的问题基本解决。
针对栅线断线的技术问题,本发明提供以下解决方案:把电镀时的工作电流从3-4A/片调整到6-8A/片,并增加铜离子浓度。
针对栅线线宽不均匀的技术问题,本发明提供以下解决方案:电镀槽体加高2-4cm,阳极(钛篮)上提1-1.5cm,阳极(钛篮)底部用塑料条遮挡;钛篮脱焊处用捆扎带捆绑。
本发明提供的一种异质结电池的制备方法具体的工艺条件如下表:
本发明提供的一种铜电极异质结电池外观良好,最高效率21.29%,小批次平均效率20.65%,测试数据如下表下:
本发明提供的铜电极异质结电池平均转换效率已达20.65%,通过对工艺流程的优化,电池效率还有进一步提升的潜能。电池正面拉脱力平均值为5.28N/mm,背面拉脱力平均值为5N/mm,按照晶硅电池标准拉脱力>2.5N/mm的标准,拉脱力测试全部合格。
本发明具有以下有益技术效果:
1.既解决了银储量有限和未来银价格上涨的问题,又满足了光伏产业未来发展的需求;
2.铜异质结电池相对目前的传统晶硅电池具有成本更低,而效率更高的优势,尤其是可提高单位面积发电量,更适宜分布式发电;
3.铜电极技术研发的成功将突破我国光伏产业低水平重复投资和技术创新性不够的困境。
附图说明
图1为一种异质结电池制备方法的工艺流程示意图。
图2为现有技术的电解槽体。
图3为本发明的电解槽体。
图4为硅晶片的结构示意图。
图中,1为阳极,2为阴极,3为塑料条。
具体实施方式
现将参考附图来介绍实施例。
实施例1
一种异质结电池的制备方法,包括如下步骤:
a)在硅晶片上沉积铜,形成电极层;
b)光刻;
c)湿法及电镀。
所述a)步骤中,所述硅晶片的结构依次包括ITO层、P-Si层、i-Si层、Si衬底、N-Si层、i-Si层和ITO层(如图4所示)。在硅晶片双面沉积铜,形成电极层;采用射频方式进行沉淀,射频频率为12-16MHz,工作气体为氩气,靶材为铜。所述a)步骤中沉积的工艺条件如下,本底真空为5X10-5Pa,工作气压为0.1-0.5Pa,溅射功率为200-400W,溅射时间为200-280S,硅晶片温度为90-110℃。
所述b)光刻步骤包括,激光光绘绘制图形、冲片显影菲林片、压膜和曝光。在所述冲片显影菲林片步骤中,定影、显影液以浓度20-30%的比例配置,冲片温度为30-50℃,传送速度恒定。所述压膜步骤如下,压膜轮滚轴上表面温度90-110℃,压膜轮滚轴下表面温度90-100℃,传输速率0.4-0.6m/min。所述曝光的能量强度为80-90mv/cm2。
所述湿法包括显影、水洗和稀硫酸清洗。在所述显影中,碳酸钠浓度为0.5-2%,温度为20-40℃,时间为0.5-4min;所述水洗步骤为水洗2次,每次水洗时间为1-2min,温度为室温-45℃;所述稀硫酸清洗步骤在室温中进行,硫酸浓度为10%,清洗时间为0.2-1min。
所述电镀步骤中电镀溶液的配方为,水硫酸铜67.5-90g/l,硫酸100-130ml/l,氯离子50-80ppm,陶氏添加剂451#2-4ml/l,陶氏452#10-30ml/l。所述电镀的工艺条件为,18-35℃,1-6A/dm2,12-40min。
在电镀步骤之后还依次包括如下步骤:水洗、去膜、水洗、去除种子铜、水洗、稀硫酸清洗、化学镀锡、水洗和干燥。
在电镀之后水洗、去膜之前的水洗步骤为洗3次,每次1-2min,温度范围为室温-45℃。
所述去膜步骤使用1-3%氢氧化钠,温度为20-55℃,时间为1-5min。
在去膜之后、去除种子铜之前的水洗步骤为洗2次,每次1-2min,温度范围为室温-45℃。
所述去除种子铜的配方为SPS:100~120g/l,H2SO4:1%~3%;工艺条件为:室温-40℃,0.5-5min。
在去除种子铜之后、稀硫酸清洗之前的水洗步骤为洗2次,每次1-2min,温度范围为室温-45℃。
所述稀硫酸清洗使用5%-10%硫酸,在室温下清洗1-3min。
所述化学镀锡的配方为乐思SN100A90%v/v,乐思SN100B10%v/v,工艺条件为63-72℃,1-5min。
在化学镀锡之后、干燥之前的水洗步骤为洗3次,每次1-2min,温度范围为40-45℃。
所述干燥在N2氛围中,干燥温度为30-40℃,干燥时间为4-6min。
电池正面主栅宽度为1-2cm共三根,细栅宽度60-80um共73-75根,电池背面主栅宽度为1-2cm共三根,细栅宽度60-80um共140-150根。
沉淀载板边缘宽度为3mm,正面全部溅射,背面用载板支撑并作为边缘隔离;预留的干膜比硅片大,防止从侧边上铜;PVD前将硅片四周用高温胶带包裹起来,起到隔离的作用。
在ITO过程中,化锡温度为20-30℃,PH值为0.9-1.1,即减少酸度,以减轻酸的腐蚀。
实施例2
一种异质结电池,一种异质结电池,所述异质结电池的电极为铜电极,在硅晶片上下表面设有铜电极层;所述硅晶片的结构依次包括ITO层、P-Si层、i-Si层、Si衬底、N-Si层、i-Si层和ITO层。
实施例3
现有技术的电镀槽体(如图2所示),阳极1深度比阴极3深,导致底部电力线密集;阳极1底部无遮挡,也会产生电力线;阳极1变型,导致阴阳极间距不固定;液面据阴极上端太近,离子交换不足。
本发明的电镀槽体(如图3所示)与现有技术的电镀槽体(如图2所示)相比,槽体加高2-4cm,阳极1上提1-1.5cm,阳极1底部用塑料条遮挡;阳极1脱焊处用捆扎带捆绑。中间线宽在60-80um,边缘线宽在80-90um左右。
上述实施例并非具体实施方式的穷举,还可有其他的实施例,上述实施例目的在于说明本发明,而非限制本发明的保护范围,所有由本发明简单变化而来的应用均落在本发明的保护范围内。
此专利说明书使用实例去展示本发明,其中包括最佳模式,并且使熟悉本领域的技术人员制造和使用此项发明。此发明可授权的范围包括权利要求书的内容和说明书内的具体实施方式和其它实施例的内容。这些其它实例也应该属于本发明专利权要求的范围,只要它们含有权利要求相同书面语言所描述的技术特征,或者它们包含有与权利要求无实质差异的类似字面语言所描述的技术特征。
所有专利,专利申请和其它参考文献的全部内容应通过引用并入本申请文件。但是如果本申请中的一个术语和已纳入参考文献的术语相冲突,以本申请的术语优先。
本文中公开的所有范围都包括端点,并且端点之间是彼此独立地组合。
需要注意的是,“第一”,“第二”或者类似词汇并不表示任何顺序,质量或重要性,只是用来区分不同的技术特征。结合数量使用的修饰词“大约”包含所述值和内容上下文指定的含义。(例如:它包含有测量特定数量时的误差)
Claims (12)
1.一种异质结电池的制备方法,其特征在于,包括如下步骤:
a)在硅晶片上沉积铜,形成电极层;
b)光刻;
c)湿法及电镀。
2.根据权利要求1所述的异质结电池的制备方法,其特征在于:所述硅晶片的结构依次包括ITO层、P-Si层、i-Si层、Si衬底、N-Si层、i-Si层和ITO层。
3.根据权利要求1所述的异质结电池的制备方法,其特征在于:所述a)步骤中,在硅晶片上双面沉积铜,形成电极层;采用射频方式进行沉淀,射频频率为12-16MHz,工作气体为氩气,靶材为铜;所述沉积的工艺条件如下,本底真空为5X10-5Pa,工作气压为0.1-0.5Pa,溅射功率为200-400W,溅射时间为200-280S,硅晶片温度为90-110℃。
4.根据权利要求1所述的方法异质结电池的制备方法,其特征在于:所述b)光刻步骤包括,激光光绘绘制图形、冲片显影菲林片、压膜和曝光;在所述冲片显影菲林片步骤中,定影、显影液以浓度20-30%%的比例配置,冲片温度为30-50℃,传送速度恒定;所述压膜步骤如下,压膜轮滚轴上表面温度90-110℃,压膜轮滚轴下表面温度90-100℃,传输速率0.4-0.6m/min;所述曝光的能量强度为80-90mv/cm2。
5.根据权利要求1所述的异质结电池的制备方法,其特征在于:所述湿法包括显影、水洗和稀硫酸清洗;在所述显影中,碳酸钠浓度为0.5-2%,温度为20-40℃,时间为0.5-4min;所述水洗步骤为水洗2次,每次水洗时间为1-2min,温度为室温-45℃;所述稀硫酸清洗步骤在室温中进行,硫酸浓度为10%,清洗时间为0.2-1min。
6.根据权利要求1所述的异质结电池的制备方法,其特征在于:所述电镀步骤中电镀溶液的配方为,水硫酸铜67.5-90g/l,硫酸100-130ml/l,氯离子50-80ppm,陶氏添加剂451#2-4ml/l,陶氏452#10-30ml/l;所述电镀的工艺条件为,18-35℃,1-6A/dm2,12-40min。
7.根据权利要求1-6任一项所述的异质结电池的制备方法,其特征在于,在电镀步骤之后还依次包括如下步骤:水洗、去膜、水洗、去除种子铜、水洗、稀硫酸清洗、化学镀锡、水洗和干燥。
8.根据权利要求7所述的异质结电池的制备方法,其特征在于:在电镀之后水洗、去膜之前的水洗步骤为洗3次,每次1-2min,温度范围为室温-45℃;所述去膜步骤使用1-3%氢氧化钠,温度为20-55℃,时间为1-5min;在去膜之后、去除种子铜之前的水洗步骤为洗2次,每次1-2min,温度范围为室温-45℃;所述去除种子铜的配方为SPS:100~120g/l,H2SO4:1%~3%;工艺条件为:室温-40℃,0.5-5min;在去除种子铜之后、稀硫酸清洗之前的水洗步骤为洗2次,每次1-2min,温度范围为室温-45℃;所述稀硫酸清洗使用5%-10%硫酸,在室温下清洗1-3min;所述化学镀锡的配方为乐思SN100A90%v/v,乐思SN100B10%v/v,工艺条件为63-72℃,1-5min;在化学镀锡之后、干燥之前的水洗步骤为洗3次,每次1-2min,温度范围为40-45℃;所述干燥在N2氛围中,干燥温度为30-40℃,干燥时间为4-6min。
9.根据权利要求7所述的异质结电池的制备方法,其特征在于:电池正面主栅宽度为1-2cm共三根,细栅宽度60-80um共73-75根,电池背面主栅宽度为1-2cm共三根,细栅宽度60-80um共140-150根。
10.根据权利要求7所述的异质结电池的制备方法,其特征在于:沉淀载板边缘宽度为2-4mm,正面全部溅射,背面用载板支撑并作为边缘隔离;预留的干膜比硅片大,防止从侧边上铜;PVD前将硅片四周用高温胶带包裹起来,起到隔离的作用。
11.根据权利要求10所述的异质结电池的制备方法,其特征在于:,在ITO过程中,化锡温度为20-30℃,PH值为0.9-1.1,即减少酸度,以减轻酸的腐蚀。
12.一种异质结电池,其特征在于,所述异质结电池的电极为铜电极,在硅晶片上下表面设有铜电极层;所述硅晶片的结构依次包括ITO层、P-Si层、i-Si层、Si衬底、N-Si层、i-Si层和ITO层。
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