CN111960828A - 冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法 - Google Patents
冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法 Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 150
- 239000010703 silicon Substances 0.000 title claims abstract description 150
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000919 ceramic Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000010453 quartz Substances 0.000 title claims abstract description 40
- 238000003723 Smelting Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 35
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- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000003349 gelling agent Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 34
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 27
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
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- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
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- 239000004310 lactic acid Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
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- 235000019698 starch Nutrition 0.000 claims description 3
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- 229920000084 Gum arabic Polymers 0.000 claims description 2
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- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims 1
- 229910002790 Si2N2O Inorganic materials 0.000 claims 1
- -1 perhydropolysilazane Chemical compound 0.000 claims 1
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- 238000009736 wetting Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
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- 239000000463 material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 240000007472 Leucaena leucocephala Species 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。其技术方案是：将70～85质量份的氮氧化硅前驱体和15～30质量份的熔融石英粉体混合，在混合气氛和1400～1700℃条件下保温2～10h，冷却，研磨，制得氮氧化硅粉体；将50～100质量份的氮氧化硅粉体、0～50质量份的熔融石英粉体、0.3～1质量份的分散剂、0.1～2质量份的胶凝剂和30～70质量份的去离子水置入球磨罐中混合，再注入模具，在30～90℃水浴条件下保温0.5～3h，脱模，在80～110℃条件下烘干，于1100～1400℃条件下保温2～10h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。本发明制备的所述复合陶瓷坩埚具有不开裂和与硅锭不粘连的特点，使用性能良好。
Description
技术领域
本发明属于氮氧化硅/石英复合陶瓷坩埚技术领域。尤其涉及一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。
背景技术
光伏级硅是当前太阳能电池用关键光电转换材料，其熔炼和生长主要在具有氮化硅涂层的熔融石英坩埚中开展。在实际生产中，现有的熔融石英坩埚普遍存在以下突出问题。首先，熔融石英坩埚极易开裂，原因在于熔融石英坩埚在高温下不可避免发生析晶转变，产生2～5％的体积变化，从而导致坩埚开裂。其次，凝固过程中硅锭与熔融石英坩埚粘连，导致脱模困难，重要原因之一是高温下硅熔体极易渗透过氮化硅涂层与熔融石英坩埚直接接触，而硅熔体与熔融石英的接触角为～83°，二者之间润湿而粘连。由于粘连问题，随之会造成光伏级硅破裂和生成大量缺陷，不利于硅锭品质以及产量的提高，也增加了生产成本。
为了解决上述问题，调整坩埚材质是目前普遍采用的有效途径，目前被认可的坩埚材质主要是氧化硅和氮化硅。其中，氮化硅本身不会有析晶问题，能够通过高温烧结提高强度，使用过程中不会开裂。例如，“一种氮化硅坩埚的制作方法”(CN104744051B)专利技术以氮化硅粉体为原料，采用等静压成型方式，制备了氮化硅坩埚，既避免了对硅锭的污染，又提高了生产安全性。另外，氮化硅对石英陶瓷具有抑制析晶效果。因此，将氮化硅引入石英陶瓷中，制备氮化硅结合石英坩埚，也能降低因析晶带来的坩埚开裂风险。如“光伏级硅铸锭用氮化硅结合熔融石英坩埚的制备方法”(CN105541311B)专利技术通过硅粉原位氮化，制得氮化硅结合石英复合陶瓷坩埚，降低了生产成本，且可以重复使用。然而，氮化硅与硅熔体的接触角为～49°，两者润湿，极易导致坩埚与硅锭的粘连。而根据Cassie方程(cosθ＝αSiO2cosθSiO2+(1-αSiO2)cosθSi3N4)预测，硅熔体与氮化硅结合熔融石英的接触角介于49°和83°之间，会发生润湿和粘连。显然，氮化硅坩埚和氮化硅结合熔融石英坩埚难以解决硅锭与坩埚粘连问题。
综上所述，现有技术所制备的坩埚难以在保证不开裂的基础上解决硅锭与坩埚粘连问题。
发明内容
本发明旨在克服现有技术缺陷，目的在于提供一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，用该方法所制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚在保证不开裂的基础上能实现凝固后硅锭与所制坩埚之间分离，避免粘连。
为实现本发明，本发明采用的技术方案的步骤是：
步骤一、将70～85质量份的氮氧化硅前驱体和15～30质量份的熔融石英粉体混合，在混合气氛和1400～1700℃条件下保温2～10h，自然冷却，研磨，制得氮氧化硅粉体。
步骤二、将50～100质量份的所述氮氧化硅粉体、0～50质量份的熔融石英粉体、0.3～1质量份的分散剂、0.1～2质量份的胶凝剂和30～70质量份的去离子水置入球磨罐中，混合16～24h，制得陶瓷料浆。
步骤三、将所述陶瓷料浆注入模具中，在30～90℃水浴条件下保温0.5～3h，脱模，制得复合陶瓷坯体。
步骤四、将所述复合陶瓷坯体于80～110℃条件下烘干，然后在空气或惰性气氛中，于1100～1400℃条件下保温2～10h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
所述氮氧化硅前驱体为氮化硅、单质硅、全氢聚硅氮烷、氮氧化硅中的一种以上。
所述混合气氛中的O∶N的体积比为1∶5～30。
所述分散剂为乳酸、丙烯酸与2-丙烯酰胺-2-甲基丙磺酸共聚物、聚丙烯酸铵中的一种。
所述胶凝剂为淀粉、阿拉伯胶、明胶、异丁烯与马来酸酐共聚物中的一种。
所述熔融石英粉体的SiO2≥99.9wt％；所述熔融石英粉体的平均粒径≤10μm。
所述氮化硅为α-Si3N4或为β-Si3N4，所述氮化硅的Si3N4≥99wt％；所述氮化硅的平均粒径≤5μm。
所述单质硅的Si≥99.99wt％；所述单质硅的平均粒径≤45μm。
所述全氢聚硅氮烷的固含量≤20wt％。
所述氮氧化硅的Si2N2O≥99wt％；所述氮氧化硅的平均粒径≤5μm。
由于采用以上技术方案，本发明与现有技术相比具有如下积极效果：
本发明在制备过程中充分利用Si2N2O与硅熔体不润湿的特性，通过调整氮氧化硅和熔融石英的比例使硅熔体与坩埚材质之间的接触角>90°，保证二者之间不润湿，从而实现凝固后硅锭与制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的有效分离，避免粘连。
本发明制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚与现有技术相比，在减少析晶、保证使用过程中不开裂的基础上，实现了所制坩埚与硅熔体之间不润湿，从而保证硅锭凝固后与光伏级硅冶炼用氮氧化硅/石英复合陶瓷坩埚分离，避免粘连。
本发明制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚经检测：高温处理后析晶度<5％；润湿角>90°。
因此，本发明制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚高温处理后析晶度低，不会开裂；实现了所制坩埚与硅熔体之间不润湿，解决了现有技术中存在的粘连问题。本发明同时解决了坩埚开裂以和粘连问题，具备良好的使用性能。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对本发明的保护范围的限制。
本具体实施方式中：
所述熔融石英粉体的SiO2≥99.9wt％；所述熔融石英粉体的平均粒径≤10μm。
所述氮化硅的Si3N4≥99wt％；所述氮化硅的平均粒径≤5μm。
所述单质硅的Si≥99.99wt％；所述单质硅的平均粒径≤45μm。
所述全氢聚硅氮烷的固含量≤20wt％。
所述氮氧化硅的Si2N2O≥99wt％；所述氮氧化硅的平均粒径≤5μm。
实施例中不再赘述。
实施例1
一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。本实施例所述制备方法的具体步骤是：
步骤一、将76质量份的氮氧化硅前驱体和24质量份的熔融石英粉体混合，在混合气氛和1600℃条件下保温10h，自然冷却，研磨，制得氮氧化硅粉体。
步骤二、将100质量份的所述氮氧化硅粉体、0.3质量份的分散剂、0.2质量份的胶凝剂和57质量份的去离子水置入球磨罐中，混合18h，制得陶瓷料浆。
步骤三、将所述陶瓷料浆注入模具中，在70℃水浴条件下保温0.5h，脱模，制得复合陶瓷坯体。
步骤四、将所述复合陶瓷坯体于110℃条件下烘干，然后在空气气氛中，于1200℃条件下保温5h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
所述混合气氛中的O∶N的体积比为1∶30。
所述氮氧化硅前驱体为氮化硅；所述氮化硅为α-Si3N4。
所述分散剂为乳酸。
所述胶凝剂为异丁烯与马来酸酐共聚物。
实施例2
一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。本实施例所述制备方法的具体步骤是：
步骤一、将71质量份的氮氧化硅前驱体和29质量份的熔融石英粉体混合，在混合气氛和1500℃条件下保温8h，自然冷却，研磨，制得氮氧化硅粉体。
步骤二、将85质量份的所述氮氧化硅粉体、15质量份的熔融石英粉体、0.8质量份的分散剂、1.9质量份的胶凝剂和44质量份的去离子水置入球磨罐中，混合16h，制得陶瓷料浆。
步骤三、将所述陶瓷料浆注入模具中，在30℃水浴条件下保温3h，脱模，制得复合陶瓷坯体。
步骤四、将所述复合陶瓷坯体于90℃条件下烘干，然后在惰性气氛中，于1100℃条件下保温10h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
所述混合气氛中的O∶N的体积比为1∶22。
所述氮氧化硅前驱体为单质硅。
所述分散剂为丙烯酸与2-丙烯酰胺-2-甲基丙磺酸共聚物。
所述胶凝剂为阿拉伯胶。
实施例3
一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。本实施例所述制备方法的具体步骤是：
步骤一、将85质量份的氮氧化硅前驱体和15质量份的熔融石英粉体混合，在混合气氛和1400℃条件下保温3h，自然冷却，研磨，制得氮氧化硅粉体。
步骤二、将70质量份的所述氮氧化硅粉体、30质量份的熔融石英粉体、0.6质量份的分散剂、0.9质量份的胶凝剂和69质量份的去离子水置入球磨罐中，混合24h，制得陶瓷料浆。
步骤三、将所述陶瓷料浆注入模具中，在50℃水浴条件下保温2h，脱模，制得复合陶瓷坯体。
步骤四、将所述复合陶瓷坯体于100℃条件下烘干，然后在惰性气氛中，于1300℃条件下保温7h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
所述混合气氛中的O∶N的体积比为1∶5。
所述氮氧化硅前驱体为全氢聚硅氮烷。
所述分散剂为聚丙烯酸铵。
所述胶凝剂为明胶。
实施例4
一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。本实施例所述制备方法的具体步骤是：
步骤一、将81质量份的氮氧化硅前驱体和19质量份的熔融石英粉体混合，在混合气氛和1700℃条件下保温5h，自然冷却，研磨，制得氮氧化硅粉体。
步骤二、将52质量份的所述氮氧化硅粉体、48质量份的熔融石英粉体、1质量份的分散剂、1.4质量份的胶凝剂和30质量份的去离子水置入球磨罐中，混合20h，制得陶瓷料浆。
步骤三、将所述陶瓷料浆注入模具中，在90℃水浴条件下保温1h，脱模，制得复合陶瓷坯体。
步骤四、将所述复合陶瓷坯体于80℃条件下烘干，然后在空气气氛中，于1400℃条件下保温2h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
所述混合气氛中的O∶N的体积比为1∶13。
所述氮氧化硅前驱体为氮氧化硅。
所述分散剂为丙烯酸与2-丙烯酰胺-2-甲基丙磺酸共聚物。
所述胶凝剂为淀粉。
实施例5
一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚及其制备方法。除下述外，其余同实施例1：
所述氮氧化硅前驱体为氮化硅；所述氮化硅为β-Si3N4。
本具体实施方式与现有技术相比具有如下积极效果：
本具体实施方式在制备过程中充分利用Si2N2O与硅熔体不润湿的特性，通过调整氮氧化硅和熔融石英的比例使硅熔体与坩埚材质之间的接触角>90°，保证二者之间不润湿，从而实现凝固后硅锭与制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的有效分离，避免粘连。
本具体实施方式制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚与现有技术相比，在减少析晶、保证使用过程中不开裂的基础上，实现了所制坩埚与硅熔体之间不润湿，从而保证硅锭凝固后与光伏级硅冶炼用氮氧化硅/石英复合陶瓷坩埚分离，避免粘连。
本具体实施方式制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚经检测：高温处理后析晶度<5％；润湿角>90°。
因此，本具体实施方式制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚高温处理后析晶度低，不会开裂；实现了所制坩埚与硅熔体之间不润湿，解决了现有技术中存在的粘连问题。本具体实施方式同时解决了坩埚开裂以和粘连问题，具备良好的使用性能。
Claims (11)
1.一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述制备方法的步骤是：
步骤一、将70～85质量份的氮氧化硅前驱体和15～30质量份的熔融石英粉体混合，在混合气氛和1400～1700℃条件下保温2～10h，自然冷却，研磨，制得氮氧化硅粉体；
步骤二、将50～100质量份的所述氮氧化硅粉体、0～50质量份的熔融石英粉体、0.3～1质量份的分散剂、0.1～2质量份的胶凝剂和30～70质量份的去离子水置入球磨罐中，混合16～24h，制得陶瓷料浆；
步骤三、将所述陶瓷料浆注入模具中，在30～90℃水浴条件下保温0.5～3h，脱模，制得复合陶瓷坯体；
步骤四、将所述复合陶瓷坯体于80～110℃条件下烘干，然后在空气或惰性气氛中，于1100～1400℃条件下保温2～10h，制得冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
2.如权利要求1所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述氮氧化硅前驱体为氮化硅、单质硅、全氢聚硅氮烷、氮氧化硅中的一种。
3.如权利要求1所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述混合气氛中的O∶N的体积比为1∶5～30。
4.如权利要求1所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述分散剂为乳酸、丙烯酸与2-丙烯酰胺-2-甲基丙磺酸共聚物、聚丙烯酸铵中的一种。
5.如权利要求1所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述胶凝剂为淀粉、阿拉伯胶、明胶、异丁烯与马来酸酐共聚物中的一种。
6.如权利要求1所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述熔融石英粉体的SiO2≥99.9wt％；所述熔融石英粉体的平均粒径≤10μm。
7.如权利要求2所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述氮化硅为α-Si3N4或为β-Si3N4，所述氮化硅的Si3N4≥99wt％；所述氮化硅的平均粒径≤5μm。
8.如权利要求2所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述单质硅的Si≥99.99wt％；所述单质硅的平均粒径≤45μm。
9.如权利要求2所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述全氢聚硅氮烷的固含量≤20wt％。
10.如权利要求2所述的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法，其特征在于所述氮氧化硅的Si2N2O≥99wt％；所述氮氧化硅的平均粒径≤5μm。
11.一种冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚，其特征在于所述冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚是根据权利要求1～10中任一项所述冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚的制备方法所制备的冶炼光伏级硅用氮氧化硅/石英复合陶瓷坩埚。
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