CN114464700A - N型晶硅电池的选择性硼掺杂方法及其应用 - Google Patents
N型晶硅电池的选择性硼掺杂方法及其应用 Download PDFInfo
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 71
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 238000009792 diffusion process Methods 0.000 claims abstract description 20
- 238000007581 slurry coating method Methods 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000007639 printing Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
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- 238000004140 cleaning Methods 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 7
- 238000005215 recombination Methods 0.000 claims description 6
- 229910004205 SiNX Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002161 passivation Methods 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229910017107 AlOx Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000013083 solar photovoltaic technology Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明公开了一种N型晶硅电池的选择性硼掺杂方法,包括如下步骤:对制绒后的N型硅片进行硼扩散,形成硼的浅掺杂,且硼扩面上形成BSG;然后按照金属电极图形,在硼扩面上印刷能与BSG反应的腐蚀浆料,形成覆浆区域;然后通过加热使腐蚀浆料与覆浆区域的BSG发生反应,将覆浆区域的BSG转变为硼硅化合物;然后对覆浆区域进行激光推进,使覆浆区域形成硼的重掺杂。本发明还提供一种N型晶硅电池的制备工艺,其应用上述的选择性硼掺杂方法。本发明利用腐蚀浆料与BSG发生反应,降低了硼源进入硅基底中所需的激光能量,保护硅片表面的金字塔绒面不受到激光破坏,形成高表面浓度深结的重掺杂区,达到选择性硼掺杂的目的。
Description
技术领域
本发明涉及光伏领域,具体涉及一种N型晶硅电池的选择性硼掺杂方法及其应用。
背景技术
随着太阳能光伏技术的研究和发展,以晶硅为衬底的光伏技术已然占据了市场主流位置。晶硅分为P型和N型硅两种,随着P型晶硅电池量产化转换效率逐渐趋于理论上限,而N型晶硅电池由于其硅片特性,具有更高的少子寿命,适合更为复杂的电池工艺并得到更高的电池转换效率。
N型晶硅电池技术中,通过硼掺杂形成发射极,而选择性硼掺杂有利于在浅掺杂区域保持良好的表面复合,以及在重掺杂区域保持良好的欧姆接触、降低金属复合。而基于P型晶硅电池量产技术方案,采用先磷扩散形成PSG再激光得到重掺杂的技术路线无法直接应用于N型硼掺杂,这是由于BSG作为扩散硼源具有完全不同于PSG作为磷源的特性,直接将已经非常成熟的选择性激光磷扩散技术显然是无法实现的。申请号为201910017046.7的中国专利公开了一种旋涂硼源激光掺杂制作N型选择性发射极双面电池的方法,其正面的重掺杂发射极采用BSG激光掺杂法完成,选用的激光波长为355nm或532nm,光斑采用方形光斑,激光功率在20W-50W之间,基频为100KHz-360KHz;该专利忽视了激光在晶硅金字塔绒面造成的不可逆转的损伤,随着N型晶硅电池效率不断提高,由于激光损伤导致复合增加的问题逐渐凸显,选择性硼掺杂带来的提效也会大打折扣。申请号为201910578339.2的中国专利公开了一种激光硼掺杂选择性发射极TOPCon结构电池及其制备方法,其先形成高硼表面浓度的P++层,不进行氧化,再采用激光对所需区域进行掺杂推进,经过清洗后放回扩散炉进行氧化以达到形成选择性发射极的目的;该专利需要经过两次高温,两次高温均控制在700℃~1200℃,且时间长,无疑此种操作会降低部分硅片体少子寿命,而激光先掺杂虽然可以达到不同掺杂深度的目的,但共氧化会缩小重掺杂和轻掺杂之间近表面浓度的差异,这不利于降低金属电极与重掺杂区域的欧姆接触。
发明内容
为解决现有技术的缺陷,本发明提供一种N型晶硅电池的选择性硼掺杂方法,包括如下步骤:
对制绒后的N型硅片进行硼扩散,形成硼的浅掺杂,且硼扩面上形成BSG;
然后按照金属电极图形,在硼扩面上印刷能与BSG反应并将BSG反应转变为硼硅化合物的腐蚀浆料,形成与金属电极图形一致的覆浆区域;
然后通过加热使腐蚀浆料与覆浆区域的BSG发生反应,将覆浆区域的BSG转变为硼硅化合物;
然后对覆浆区域进行激光推进,使覆浆区域形成硼的重掺杂。
优选的,硼扩散形成的浅掺杂区,其方阻为100~300Ω/□,表面复合J0<30fA/cm2。
优选的,腐蚀浆料为含硼腐蚀浆料或不含硼腐蚀浆料。
优选的,加热腐蚀浆料的温度为50~700℃,时间为1~60min。
优选的,激光推进采用脉冲激光或连续激光。
优选的,激光推进所用激光的能量密度为0.05~50J/cm2,光束为圆形或方形,光束内激光能量均匀分布。
本发明还提供一种N型晶硅电池的制备工艺,其应用上述的选择性硼掺杂方法。
优选的,所述N型晶硅电池的制备工艺,其包括如下步骤:
1)N型硅片制绒、清洗;
2)硼扩散,形成低复合的浅掺杂区,且硼扩面上形成BSG;
3)按照金属电极图形,在硼扩面上印刷能与BSG反应的腐蚀浆料,形成与金属电极图形一致的覆浆区域;然后通过加热使腐蚀浆料与覆浆区域的BSG发生反应,将覆浆区域的BSG转变为硼硅化合物;
4)对覆浆区域进行激光推进,使覆浆区域形成硼的重掺杂;
5)沉积绝缘介质层;
6)清洗背面,去除BSG,磷扩散形成背场;
7)清洗,去除PSG和绝缘介质层;
8)双面沉积减反射钝化膜;
9)印刷金属电极,烧结。
优选的,绝缘介质层为SiNx层、SiOx层、SiONx层、AlOx层中的一层或几层叠加。
优选的,绝缘介质层的厚度为2~200nm。
本发明的优点和有益效果在于:提供一种N型晶硅电池的选择性硼掺杂方法及其应用,本发明利用腐蚀浆料与BSG发生反应,降低了硼源进入硅基底中所需的激光能量,保护硅片表面的金字塔绒面不受到激光破坏,形成高表面浓度深结的重掺杂区,达到选择性硼掺杂的目的。
本发明采用能与BSG反应的腐蚀浆料,该浆料可以与含硼氧化硅发生反应,但不与硅反应,该浆料常温下不具有化学活性,便于储存和印刷,经加温后材料激活与BSG反应可生成含硼硅化物,浆料中含有的有机/无机溶剂以及反应生产的副产物经加热后挥发,以保证激光作用区域仅为硼硅化合物。
腐蚀浆料常温下不与BSG反应,升温激活后腐蚀BSG,与BSG(含硼氧化硅)发生反应但不与Si发生反应,从而将BSG转变为硼硅化合物,且对硅基底表面绒面不产生破坏和腐蚀。
对于SiO2/Si界面硼的分凝系数>1,在高温情况下,硼元素受热推进的过程中,一部分硼也会向SiO2层中扩散,导致硅基表面的硼浓度进一步下降,这就是常规激光硼掺杂无法或者很难达到高表面浓度的原因。本发明中,硼硅化合物与硅基底(近表面已掺硼区域)的材料属性基本一致,受热影响后硼元素从高浓度(硼硅化合物)向低浓度(硅基底中掺硼区域)扩散,从而达到高表面浓度以及深结的目的。
本发明还具有如下特点:
1)本发明由于硼硅化合物与硅基底材料特性基本一致,因此可大大降低硼元素推进所需的能量,即作用其表面的激光能量,从而最大程度地减小因激光损伤产生的复合;
2)本发明的高表面硼浓度与金属电极接触,有利于降低金属接触电阻,减小金属复合。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
本发明提供一种N型晶硅电池的制备工艺,其包括如下步骤:
1)N型硅片制绒、清洗;
2)对制绒后的N型硅片进行硼扩散,形成硼的浅掺杂,且硼扩面上形成BSG;硼扩散形成的浅掺杂区,其方阻为100~300Ω/□,表面复合J0<30fA/cm2;
3)按照金属电极图形,在硼扩面上印刷能与BSG反应并将BSG反应转变为硼硅化合物的含硼或不含硼腐蚀浆料,形成与金属电极图形一致的覆浆区域;然后通过加热使腐蚀浆料与覆浆区域的BSG发生反应,将覆浆区域的BSG转变为硼硅化合物;加热腐蚀浆料的温度为50~700℃,时间为1~60min;
4)对覆浆区域进行激光推进,使覆浆区域形成硼的重掺杂;激光推进采用脉冲激光或连续激光;激光推进所用激光的能量密度为0.05~50J/cm2,光束为圆形或方形,光束内激光能量均匀分布;
5)沉积绝缘介质层;绝缘介质层为SiNx层、SiOx层、SiONx层、AlOx层中的一层或几层叠加;绝缘介质层的厚度为2~200nm;
6)清洗背面,去除BSG,磷扩散形成背场;
7)清洗,去除PSG和绝缘介质层;
8)双面沉积减反射钝化膜;
9)印刷金属电极,烧结。
本发明的具体实施例如下:
实施例1
N型硅片制绒后硼扩散,扩散方阻为200Ω/□;然后在扩散面按照金属化电极印刷不含硼元素的腐蚀浆料;然后将硅片置于加热台烘干,烘干温度250℃,烘干时间2.5min;然后激光作用于浆料上,扫描速度10m/s,功率30W,激光作用后方阻90Ω/□;然后沉积SiNx膜50nm;然后清洗背面,去除BSG,磷扩散形成背场;然后双面清洗并覆盖减反射钝化膜;然后印刷电极、烧结制备得到N型电池。
经测试,实施例1的硼浅掺杂区域表面浓度为9.8E18 atoms/cm3,结深为0.4 μm;激光后硼重掺杂区域表面浓度6.5E+19 atoms/cm3,结深0.8 μm。
实施例2
N型硅片制绒后硼扩散,扩散方阻为250Ω/□;然后在扩散面按照金属化电极印刷含硼元素的腐蚀浆料(浆料中硼含量为10wt%);然后将硅片置于加热台烘干,烘干温度300℃,烘干时间10min,然后激光作用于浆料上,扫描速度15m/s,功率20W,激光作用后方阻75Ω/□;然后沉积SiNx膜50nm;然后清洗背面,去除BSG,磷扩散形成背场;然后双面清洗并覆盖减反射钝化膜;然后印刷电极、烧结制备得到N型电池。
经测试,实施例2的硼浅掺杂区域表面浓度为8.3E18 atoms/cm3,结深为0.35 μm,激光后硼重掺杂区域表面浓度9.2E+19 atoms/cm3,结深0.76 μm。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.N型晶硅电池的选择性硼掺杂方法,其特征在于,包括如下步骤:
对制绒后的N型硅片进行硼扩散,形成硼的浅掺杂,且硼扩面上形成BSG;
然后按照金属电极图形,在硼扩面上印刷能与BSG反应的腐蚀浆料,形成覆浆区域;
然后通过加热使腐蚀浆料与覆浆区域的BSG发生反应,将覆浆区域的BSG转变为硼硅化合物;
然后对覆浆区域进行激光推进,使覆浆区域形成硼的重掺杂。
2.根据权利要求1所述的N型晶硅电池的选择性硼掺杂方法,其特征在于,硼扩散形成的浅掺杂区,其方阻为100~300Ω/□,表面复合J0<30fA/cm2。
3.根据权利要求1所述的N型晶硅电池的选择性硼掺杂方法,其特征在于,腐蚀浆料为含硼腐蚀浆料或不含硼腐蚀浆料。
4.根据权利要求1所述的N型晶硅电池的选择性硼掺杂方法,其特征在于,加热腐蚀浆料的温度为50~700℃,时间为1~60min。
5.根据权利要求1所述的N型晶硅电池的选择性硼掺杂方法,其特征在于,激光推进采用脉冲激光或连续激光。
6.根据权利要求1所述的N型晶硅电池的选择性硼掺杂方法,其特征在于,激光推进所用激光的能量密度为0.05~50J/cm2,光束为圆形或方形,光束内激光能量均匀分布。
7.N型晶硅电池的制备工艺,其特征在于,其应用权利要求1至6中任一项所述的选择性硼掺杂方法。
8.根据权利要求7所述的N型晶硅电池的制备工艺,其特征在于,其包括如下步骤:
1)N型硅片制绒、清洗;
2)硼扩散,形成低复合的浅掺杂区;
3)按照金属电极图形,在硼扩面上印刷能与BSG反应的腐蚀浆料,形成覆浆区域;然后通过加热使腐蚀浆料与覆浆区域的BSG发生反应,将覆浆区域的BSG转变为硼硅化合物;
4)对覆浆区域进行激光推进,使覆浆区域形成硼的重掺杂;
5)沉积绝缘介质层;
6)清洗背面,去除BSG,磷扩散形成背场;
7)清洗,去除PSG和绝缘介质层;
8)双面沉积减反射钝化膜;
9)印刷金属电极,烧结。
9.根据权利要求8所述的N型晶硅电池的制备工艺,其特征在于,绝缘介质层为SiNx层、SiOx层、SiONx层、AlOx层中的一层或几层叠加。
10.根据权利要求8所述的N型晶硅电池的制备工艺,其特征在于,绝缘介质层的厚度为2~200nm。
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