CN112117188A - 一种三合一硅片镀膜工艺 - Google Patents
一种三合一硅片镀膜工艺 Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 28
- 239000010703 silicon Substances 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 25
- 229910004205 SiNX Inorganic materials 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 14
- 238000010926 purge Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 22
- 238000000231 atomic layer deposition Methods 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 229910052681 coesite Inorganic materials 0.000 abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 12
- 238000002161 passivation Methods 0.000 description 9
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 5
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 5
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000010261 cell growth Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
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Abstract
本发明公开了一种三合一硅片镀膜工艺，涉及晶硅电池制造领域，采用O3+O2+H2O作为混合氧源氧化方式,可以在较低温度下生成氧化层，在Al2O3膜层生长采用原子层沉积技术（ALD）加等离子增强化学气相沉积(PECVD)方式，成膜既有原子层沉积技术的优良特性又具有等离子增强化学气相沉积(PECVD)方式的快速特点,在使用等离子增强化学气相沉积(PECVD)方式成膜之前,有热SiO2以及原子层沉积技术（ALD）生产的Al2O3保护表面，能够阻挡离子损伤，避免效率损失；Si02、AL2O3、SiNx三种不同特性的膜在同一炉管腔体内完成，减少硅片运输、插片卸片、存储等步骤，膜层界面也没有在空气中暴露污染的风险，成本更低、工艺步骤简单，适用于规模化生产。
Description
技术领域
本发明涉及晶硅电池制造领域，尤其涉及一种三合一硅片镀膜工艺。
背景技术
硅片表面钝化是高效电池工艺发展的必经之路，现有PERC电池使用氧化铝膜层对硅片表面钝化已经得到大规模的应用并表现出优异的性能。近年发展十分迅速并逐步对常规铝背场晶硅电池进行取代，各光伏企业也在持续进行PERC电池扩产。
现有P型PERC电池整个工艺过程包括：1.制绒—2.扩散—3.激光SE—4.刻蚀—5.氧化退火—6.背面镀AL2O3膜—7.背面镀SiNx膜—8.正面镀SiNx膜—9.激光开槽—10.丝网印刷—11.烧结。其中氧化、背面Al2O3、背面SiNx分三台设备完成，工艺流程多，不利于产线规模化生产成本的降低；（目前量产工艺中，氧化工序即在硅片表面制备二氧化硅会单独的用热氧化炉，在600度以上的氧气氛围下制备。背面AL2O3会采用管式/板式ALD原子层设备，或者板式PECVD设备沉积制备；而SiNx则会采用PECVD管式炉制备;而这些设备都是独立的，整个镀膜工序要三台设备才能完成）；
N型TOPCon电池也需要进行SiO2/AL2O3/SiNx叠层镀膜（其中的一道工序，在扩散后的硅片表面依次沉积SiO2、AL2O3、SiNx薄膜），现有PECVD方式制备的AL2O3膜（PECVD等离子增强化学气相沉积，高能等离子会损伤硅表面）因存在离子损伤，影响表面钝化效果，不适用于更高效的N型TOPCon电池，ALD方式生长的AL2O3膜层虽然可以用于N型TOPCon电池表面钝化，但是与氧化步骤以及背面镀SiNx膜（NH3、SiH4经过等离子激活产生化学反应在硅片表面形成SiNx薄膜）步骤分离，增加了工艺环节，在多次传输、插片过程中也容易造成破片、污染等良率损失，这些都限制了现有设备在未来高效TOPCon工艺中的应用。
主要存在下述缺点：
1.现有热生长二氧化硅方式温度高>600℃，生长速度慢，产能低；
2.现有PECVD方式生长Al2O3膜的过程中等离子对硅片表面的轰击会导致表面损伤，降低钝化效果；
3.现有ALD方式生长Al2O3膜的成膜质量好，但是生长周期较长，产能低；
4.目前Si02、AL2O3、SiNx三种膜是分机台完成；
5.分机台进行工艺设备投资大、占用空间大、设备运营维护高、额外增加运输、插片卸片、存储等步骤成本；
6.分机台进行工艺导致硅片不同膜层表面多次在空气中暴露，表面容易受到污染影响膜的质量和钝化效果，影响电池片效率和良率。
发明内容
本发明提出了实现SiO2/AL2O3/SiNx叠层镀膜方案，在同一管中实现Si02/AL2O3/SiNx三种膜沉积，解决了P型PERC电池需要多台设备，工艺流程多,不利于产线规模化生产的问题，解决了N型TOPCon电池采用PECVD方式制备的AL2O3膜因存在离子损伤问题，采用ALD方式氧化步骤以及背面镀SiNx膜步骤分离，增加了工艺环节，在多次传输、插片过程中也容易造成破片、污染等良率损问题。
专业术语介绍：
PERC电池：一种晶硅高效电池结构，通过对电池背面沉积钝化膜使电池拥有更高的电池效率。
TOPCon电池：隧穿氧化钝化接触电池，具有双面钝化特点，理论效率极限更高。
ALD：原子层沉积技术；
PECVD：等离子增强化学气相沉。
为了实现上述目的，本发明采用了如下技术方案：
1.一种三合一硅片镀膜工艺，包括如下步骤；
S1：使用自动插片装置将表面清洗干净的硅片插入石墨舟片上，由自动装载机构将石墨舟送入机台石英炉管内，升温并抽真空；
S2:通入强氧化性气体进行硅片表面氧化，氧化层厚度控制在1-5nm，其反应温度在200-500℃范围内，完成后通保护气体吹扫炉管并抽真空；
S3:通入铝源和氧源,使用原子沉积方式在二氧化硅表面生长AL2O3层厚度在0-10nm，完成后通保护气体吹扫炉管并抽真空；
S4：通入铝源和氧源，使用等离子增强化学气相沉积生成AL2O3层厚度在0-20nm，完成后通保护气体吹扫炉管并抽真空；
S5:升温并稳定至氮化硅沉积温度，同时进行氮化硅镀膜前的表面处理；
S6:通入氨气、硅烷、一氧化二氮，使用等离子增强化学气相沉积方式生长SiNxO+SiNx层厚度在50-120nm，完成后通保护气体吹扫炉管并抽真空；
S7:破真空、降温并出舟卸料。
进一步的技术方案，所述S1中石墨舟表面经过碳化硅镀膜处理，避免石墨舟被氧化。
进一步的技术方案，所述S2中强氧化性气体采用O3+O2+H2O混合通入，能在较低温度下生成氧化层。
进一步的技术方案，所述S3中铝源采用液态三甲基铝，通入流量为0-15SLM，通源时间0-60min，所述氧源优选水蒸汽，通源时间为0-60min，通入流量为0-10SLM。
进一步的技术方案，所述S4中铝源通入量0-20SLM，通源时间0-60min,所述氧源通源时间0-60，通入量0-15SLM。
进一步的技术方案，所述S5表面处理采用表面氮气吹扫，氮气通入流量为0-20SLM，吹扫时间为0-20min。
与现有技术相比，本发明的有益效果：
（1）使用O3+O2+H2O作为混合氧源氧化方式，可以在较低温度下生成氧化层,其特征厚度在1-5nm，其反应温度在200-500℃范围内，生长速度达1.5-2.5A/min，因此可以实现低温氧化层的快速生长，工艺步骤时间可控制在10min以内，提高设备产能；
（2）Al2O3膜层生长采用ALD加PECVD方式，先在底层使用ALD生长一层高质量的Al2O3膜，再使用PECVD方式快速生长Al2O3膜达到要求的厚度（0nm-20nm），其反应温度在150-400℃范围内，结合了ALD的方式，成膜既有ALD方式的优良特性又具有PECVD的快速特点；
（3）在使用PECVD方式成膜之前有热SiO2以及ALD生产的Al2O3保护表面，能够阻挡离子损伤，避免效率损失；
（4）Si02、AL2O3、SiNx三种不同特性的膜在同一炉管腔体内完成，减少硅片运输、插片卸片、存储等步骤，膜层界面也没有在空气中暴露污染的风险，成本更低、工艺步骤简单，适用于规模化生产。
具体实施方式
下面将结合本发明实施例中，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。
实施例1，使用自动插片装置将表面清洗干净的硅片插入石墨舟片上，由自动装载机构将石墨舟送入机台石英炉管内，升温并抽真空；所述石墨舟表面经过碳化硅镀膜处理，避免石墨舟被氧化，将O3+O2+H2O混合通入进行硅片表面氧化，氧化层厚度控制在1-5nm，其反应温度在200-500℃范围内，完成后通保护气体吹扫炉管并抽真空，通入液态三甲基铝，通入流量为0-15SLM，通源时间0-60min，通入水蒸汽，通源时间为0-60min，通入流量为0-10SLM和氧源,通过原子沉积方式在二氧化硅表面生长AL2O3层厚度在0-10nm，完成后通保护气体吹扫炉管并抽真空；通入液态三甲基铝，通入量0-20SLM，通源时间0-60min,通入水蒸气通源时间0-60，通入量0-15SLM，通过等离子增强化学气相沉积方式生成AL2O3层，厚度在0-20nm，完成后通保护气体吹扫炉管并抽真空；升温并稳定至氮化硅沉积温度，采用表面氮气吹扫，氮气通入流量为0-20SLM，吹扫时间为0-20min；通入氨气、硅烷、一氧化二氮，使用等离子增强化学气相沉积方式生长SiNxO+SiNx层厚度在50-120nm，完成后通保护气体吹扫炉管并抽真空，破真空、降温至200℃并出舟卸料。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (6)
1.一种三合一硅片镀膜工艺，其特征在于，包括如下步骤；
S1：将表面清洗干净的硅片插入石墨舟片上，将石墨舟送入石英炉管内，升温到200-500℃度并抽真空；
S2:通入强氧化性气体进行硅片表面氧化，氧化层厚度控制在1-5nm，其反应温度在200-500℃范围内，完成后通保护气体吹扫炉管并抽真空；
S3:通入铝源和氧源,使用原子沉积方式在二氧化硅表面生长AL2O3层厚度在0-10nm，完成后通保护气体吹扫炉管并抽真空；
S4：通入铝源和氧源，使用等离子增强化学气相沉积生成AL2O3层厚度在0-20nm，完成后通保护气体吹扫炉管并抽真空；
S5:升温到350-500℃并稳定至氮化硅沉积温度，同时进行氮化硅镀膜前的表面处理；
S6:通入氨气、硅烷、一氧化二氮，使用等离子增强化学气相沉积方式生长SiNxO和SiNx层，厚度在50-120nm，完成后通保护气体吹扫炉管并抽真空；
S7:破真空、降温到200℃并出舟卸料。
2.根据权利要求1所述的一种三合一硅片镀膜工艺，其特征在于，所述S1中石墨舟表面经过碳化硅镀膜处理，避免石墨舟被氧化。
3.根据权利要求1所述的一种三合一硅片镀膜工艺，其特征在于，所述S2中强氧化性气体采用O3+O2+H2O混合通入，能在较低温度下生成氧化层。
4.根据权利要求1所述的一种三合一硅片镀膜工艺，其特征在于，所述S3中铝源采用液态三甲基铝，通入流量为0-15SLM，通源时间0-60min，所述氧源优选水蒸汽，通源时间为0-60min，通入流量为0-10SLM。
5.根据权利要求1所述的一种三合一硅片镀膜工艺，其特征在于，所述S4中铝源通入量0-20SLM，通源时间0-60min,所述氧源通源时间0-60，通入量0-15SLM。
6.根据权利要求1所述的一种三合一硅片镀膜工艺，其特征在于，所述S5表面处理采用表面氮气吹扫，氮气通入流量为0-20SLM，吹扫时间为0-20min。
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