CN113130669B - 一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池 - Google Patents

一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池 Download PDF

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CN113130669B
CN113130669B CN202110425023.7A CN202110425023A CN113130669B CN 113130669 B CN113130669 B CN 113130669B CN 202110425023 A CN202110425023 A CN 202110425023A CN 113130669 B CN113130669 B CN 113130669B
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黄仕华
李林华
林娜
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Chuzhou Jietai New Energy Technology Co ltd
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Abstract

本发明公开了一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池，硅片前表面制绒；硅片前表面磷扩散；硅片前表面生长氮化硅作为钝化层和抗反层；硅片背面形成自然氧化层；硅片背面蒸镀金属铝；采用磁控溅射法沉积氧化硅，氧化硅薄膜生长结束以后，进行退火处理；背面铝电极以及前面银电极生长。本发明采用原生氧化硅/超薄金属铝/溅射氧化硅结构，可以有效地控制氧化硅的针孔尺寸及密度，使得该结构对硅片具有良好的钝化接触功能，提升钝化接触硅太阳能电池的效率，降低电池的制造成本，具有重要的产业化应用前景。

Description

一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池
技术领域
本发明属于晶体硅太阳能电池领域，涉及一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池。
背景技术
钝化发射极及背面接触(PERC)电池是目前晶体硅电池的主流产品，但背面金属电极与硅片局部存在直接接触，引起较大载流子复合损失，导致电池量产效率被限制在23％左右。隧穿氧化硅钝化接触(TOPCon)电池在金属电极与硅片之间插入超薄氧化硅和掺杂多晶硅，消除金属与硅片的直接接触，可以把电池量产效率提升至24％以上。然而，人们对氧化硅中纳米针孔缺陷的形成机理及其对载流子输运的影响还缺乏深刻理解，导致在开发TOPCon电池量产技术过程中遇到诸多问题。
对于相同的局部接触电阻率，当针孔尺寸从PERC电池中的～10微米减小到TOPCon电池中氧化硅针孔的～10纳米时，可以把含有针孔的超薄氧化硅钝化接触看成nano-PERC接触，接触因子(金属和硅片的局部接触面积与整个介电层钝化硅片面积之比)可降低近3个数量级，接触因子越小，复合损失越低。纳米针孔不但可以进行足够的电流传导，而且这些局部针孔接触区域产生饱和电流密度也很低。TOPCon电池中的氧化硅针孔是在后续高温(850～1050℃)处理过程中自然形成的，因此，人们不能精确地控制针孔尺寸及密度，很难进一步调控其钝化接触性能。
在硅衬底上利用高温热氧化、低压气相沉积(LPCVD)、等离子体气相沉积(PECVD)等方法生长的氧化硅，具有针孔缺陷少、致密性好等特点，对硅片具有良好的钝化作用，同时可以阻挡硼、磷、砷、锑等在二氧化硅中的扩散速度比在硅中慢得多的杂质扩散到硅衬底，但是铝、银、铟等杂质不能起到阻挡的作用，因为这些杂质在二氧化硅中的扩散速度比在硅中的大。硅片表面自然氧化形成氧化硅(原生氧化硅)，对硅片表面具有良好的钝化作用。在常温下利用溅射法在硅片表面生长的氧化硅(溅射氧化硅)，具有较大的针孔密度，薄膜的致密性也较差。原生氧化硅和溅射氧化硅一般具有非晶结构，在低温(200～600℃)退火过程中，非晶相结构逐渐转变为晶相结构，导致存在于薄膜中的针孔变大，铝、银、铟等金属可以通过针孔有效地扩散到硅片之中，形成一层共晶层，并在针孔周围扩散。
发明内容
本发明的目的是在PERC电池以及TOPCon电池的结构基础上，提供一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池。
为此，本发明采用的技术方案是这样的：一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池，其特征在于：通过以下步骤制备得到：
1)硅片前表面制绒；
2)硅片前表面磷扩散；
3)硅片前表面生长氮化硅作为钝化层和抗反层；
4)硅片背面形成自然氧化层；
5)硅片背面蒸镀金属铝；
6)采用磁控溅射法沉积氧化硅，氧化硅薄膜生长结束以后，在250～550℃温度和氢气氛围下进行退火处理5～10min；
7)背面铝电极以及前面银电极生长。
在具有原生氧化硅层的p型单晶硅片蒸镀一层超薄金属铝，然后采用磁控溅射沉积一层超薄氧化硅，随后在低温下进行退火处理。在200～600℃的低温退火过程中，原生氧化硅和溅射氧化硅由于非晶相结构逐渐转变为晶相结构，使得薄膜中针孔的尺寸变大。另一方面，退火使得金属铝膜收缩破裂，形成纳米团聚，这些铝纳米晶通过原生氧化硅扩散到硅片衬底，与硅形成合金，同时铝纳米晶也会通过溅射氧化硅中针孔扩散。因此，后续在溅射氧化硅上沉积的金属铝可以通过溅射氧化硅和原生氧化硅中的针孔与硅衬底形成导电通道，使得接触电阻率很低，原生氧化硅对硅片具有良好的钝化效果。采用原生氧化硅/超薄金属铝/溅射氧化硅结构，通过200～600℃的低温退火处理，可以有效地控制氧化硅的针孔尺寸及密度，使得该结构对硅片具有良好的钝化接触功能，提升钝化接触硅太阳能电池的效率，降低电池的制造成本，具有重要的产业化应用前景。
附图说明
以下结合附图和本发明的实施方式来作进一步详细说明。
图1为本发明的电池结构示意图。
具体实施方式
本实施例是太阳能电池，结构示意图如图1所示。依次具有如下结构层：铝电极1(500nm)、溅射氧化硅层2(2～5nm)、铝层3(2～5nm)、原生氧化硅层4(2～3nm)、p型硅片5、掺磷发射极6、氮化硅层7，其中掺磷发射极6上同时还有银电极8。
制备时：
1)硅片前表面制绒。首先，采用的20～30wt％的氢氧化钠溶液在80℃温度下水浴处理15min，去除p型金刚线切割的单晶硅片表面的损伤层；其次，采用硝酸、氢氟酸、冰醋酸(体积比为3:3:1)在常温下对硅片表面进行化学抛光；第三，采用等离子体增强化学气相沉积(PECVD)法，在硅片的背面生长厚度为200～300nm的氮化硅薄膜，阻挡后续工艺中的磷在硅片背面的扩散以及背面金字塔的形成；第四，采用1～2wt％的氢氧化钠、8～12vol％异丙醇的碱醇混合溶液，在80～85℃的水浴条件下处理10～20min，对硅片前表面进行制绒，获得表面金字塔结构。
2)硅片前表面磷扩散。采用75wt％偏磷酸与25wt％焦磷酸硅作为固态磷扩散源，扩散温度为1000-1050℃，扩散时间为5～15min，炉内通入氮气作为保护气体。磷扩散完成后，利用氢氟酸去除硅片表面残留的磷硅玻璃以及硅片背面的氮化硅保护层。最后，采用等离子体干法刻蚀，去除硅片边缘的磷扩散层。
3)硅片前表面生长氮化硅作为钝化层和抗反层。利用PECVD方法沉积氮化硅薄膜，以电子级氨气和硅烷分别为氮源和硅源，氨气和硅烷的流量比为1:2～6，生长温度为200～300℃，薄膜厚度为80～100nm。
4)硅片背面自然氧化层(原生氧化硅)的形成。依次采用三氯乙烯、丙酮、甲醇、异丙醇去除硅片背面的杂质，然后立即使用氢氟酸缓冲腐蚀液(BHF，氢氟酸与氟化铵的体积比为1:10～20，PH值5～6，室温)，刻蚀硅片背面自然形成的氧化膜。通过改变氢氟酸与氟化铵的混合比例、刻蚀时间，可以获得不同厚度的原生氧化物。氢氟酸与氟化铵的体积比为1:10，刻蚀时间为5s，获得的原生氧化硅厚度为2.0～2.5nm。对于相同的刻蚀溶液，刻蚀20s，原生氧化硅的厚度为1.0～1.5nm。
5)硅片背面蒸镀金属铝。首先采用真空蒸镀法在硅片背面原生氧化硅之上蒸镀一层超薄金属铝，厚度为2～5nm。蒸镀腔体的真空度优于5×10-5Pa，蒸镀积速率0.02～0.05nm/s。
6)采用磁控溅射法沉积氧化硅(溅射氧化硅)。利用磁控溅射法在硅片背面的原生氧化硅之上生长氧化硅薄膜(溅射氧化硅)，厚度为2-3nm。具体工艺为：溅射靶材为二氧化硅靶，氩气为工作气体，它们纯度均大于99.999％。溅射腔的本底真空优于1×10-4Pa，在薄膜生长之前，对靶材进行10min的预溅射，去除靶材表面氧化层和吸附的杂质。氩气的流量分别为30sccm，衬底温度为室温，工作气压为0.1～0.3Pa，溅射功率为2～5W。氧化硅薄膜生长结束以后，在250～550℃温度和氢气氛围下进行退火处理5～10min。
7)背面铝电极以及前面银电极生长。利用磁控溅射分别在硅片前表面和背表面生长厚度为500nm的银电极和铝电极。对于前表面，采用栅线掩膜板，形成银栅线电极。为了使硅片前表面的金属银与硅片的n型区形成良好的欧姆接触，以及硅片背面的铝通过氧化硅针孔的扩散在硅片背面形成铝背场效应，电池需要在750～850℃温度和氮气氛围下进行退火处理，时间为5～10min。

Claims (1)

1.一种针孔尺寸及密度可控的氧化硅钝化接触硅太阳能电池，其特征在于：通过以下步骤制备得到：
1)硅片前表面制绒；
2)硅片前表面磷扩散；
3)硅片前表面生长氮化硅作为钝化层和抗反层；
4)硅片背面形成自然氧化层；
5)硅片背面蒸镀金属铝：首先采用真空蒸镀法在硅片背面原生氧化硅之上蒸镀一层超薄金属铝，厚度为2～5nm；蒸镀腔体的真空度优于5×10-5Pa，蒸镀积速率0.02～0.05nm/s；
6)采用磁控溅射法沉积氧化硅：利用磁控溅射法在硅片背面的原生氧化硅之上生长氧化硅薄膜，厚度为2-3nm；具体工艺为：溅射靶材为二氧化硅靶，氩气为工作气体，它们纯度均大于99.999％； 溅射腔的本底真空优于1×10-4Pa，在薄膜生长之前，对靶材进行10min的预溅射，去除靶材表面氧化层和吸附的杂质；氩气的流量分别为30sccm，衬底温度为室温，工作气压为0.1～0.3Pa，溅射功率为2～5W； 氧化硅薄膜生长结束以后，在250～550℃温度和氢气氛围下进行退火处理5～10min；
7)背面铝电极以及前面银电极生长。
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