CN116462520A - 一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法 - Google Patents
一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法 Download PDFInfo
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 55
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 229920001709 polysilazane Polymers 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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Abstract
本发明公开了一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法,属于单晶硅熔炼提纯的技术领域,包括:S1、将高纯氮化硅粉体与聚硅氮烷(PSZ)充分混合,加入易挥发性有机溶剂,充分搅拌均匀后,制得混合浆料;S2、将混合好的浆料在球磨机上进行球磨处理,之后将浆料静置一段时间;S3、将S2中的浆料注入提前预制好的坩埚模具中,注浆过程缓慢平稳,完成后,持续加压一定时间,开模取出坩埚坯体,在室温下干燥烘干去除溶剂;S4、将处理好的坩埚坯体放置于烧结炉中,在氮气氛围下,维持正压,升温至熔融状态,在熔融态下保温一定时间,随炉冷却制得不含氧氮化硅坩埚,本发明工艺简单,制得的无氧氮化硅坩埚是理想的单晶硅的熔炼提纯用坩埚。
Description
技术领域
本申请涉及单晶硅冶炼提纯的技术领域,尤其涉及一种新型的无氧氮化硅坩埚的制备方法。
背景技术
目前,光伏行业所用的拉单晶的坩埚大多为石英坩埚,其中的氧元素在高温熔炼的过程中,分解脱离坩埚本体,进入熔融的硅溶液当中,制得的单晶硅内部含有氧元素,影响光电转换效率,对于商业化生产的进一步发展起到了阻碍作用,于是人们进一步研究了不含氧的可替代的坩埚,氮化硅坩埚理论上不仅是力学性能优异,同时有着较好的化学特性。
但是现阶段氮化硅坩埚在制作的过程中存在着诸多困难,氮化硅的粉体在高温时极易气化,不能够形成有效的熔区,难于烧结,一些方法通过添加常用的烧结剂如Al2O3、Y2O3、ZrO等,但氧化物都会引入氧,并且高温稳定性差,这就使得不含氧的氮化硅坩埚的制备一直处于技术瓶颈之中
聚硅氮烷类聚合物,其中只含有Si、N、H、C等元素,在高温时可以与Si反应生成氮化硅,或者碳化硅,这些都是理想的熔炼硅晶体的坩埚材料,因此,本发明采用这类聚硅氮烷的聚合物作为氮化硅坩埚制作过程中的烧结剂,能够有效突破这一技术瓶颈。
发明内容
本申请实施例的目的是提供一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法,以解决相关技术中存在的氮化硅坩埚制备过程中烧结剂脱氧的问题,进一步解决单晶硅制备过程中氧污染的问题
本发明采用以下的技术方案:
一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法,包括以下步骤:
S1、将高纯氮化硅粉体与聚硅氮烷(PSZ)充分混合,加入易挥发性有机溶剂,充分搅拌均匀后,制得混合浆料;
S2、将混合好的浆料在球磨机上进行球磨处理,之后将浆料静置一段时间;
S3、将S2中的浆料注入提前预制好的坩埚模具中,注浆过程缓慢平稳,完成后,持续加压,开模取出坩埚坯体,在室温下干燥烘干去除溶剂;
S4、将处理好的坩埚坯体放置于烧结炉中,在氮气氛围下,维持正压,升温至熔融状态,在熔融态下保温一定时间,随炉冷却制得不含氧氮化硅坩埚。
可选的,S1中所述的氮化硅采用高纯氮化硅,纯度≥95%,状态为高纯氮化硅粉体材料,颗粒直径在1-3um,较小的粒径可以与烧结剂更加充分的混合,从而提高烧结强度;
可选地,S1中所述的硅氮烷类的聚合物应具备仅含有Si、N、H、C这几种元素,尤其是不能含有氧元素。
可选地,S1中所述的氮化硅粉体与聚硅氮烷(PSZ)的质量比为100:80-95,最后加入易挥发性有机溶剂配置成固含量在55-60%左右的浆料。
可选地,所述易挥发性有机溶剂选自有机胺、丙酮、无水乙醇。
可选地,S2中所述的球磨机选用行星球磨机,研磨参数优选为转速为50-80转/分钟,处理时长为3-5小时,这样可避免氮化硅粉体团聚成块,影响与烧结剂的充分混合。
可选的,S3中的模具尽可能的选用不含氧或者含氧量低的模具,优选为石墨模具,若使用含氧模具,则其内腔要做光滑处理,优选为8k级别。
可选的,S3中的模具具备密封性良好,要能满足5-15MPa的压力,完成注浆后要对模具进行加压处理,压力在5-15MPa,目的是让氮化硅基的浆料在模具内充分贴合并致密化。
可选的,S3中所述的烘干干燥处理可选择在60-80℃的环境下烘干处理30-45小时左右,目的是去除氮化硅坯体中的少量的有机溶剂,尤其是含氧溶剂。
可选的,S4中所述的烧结炉要密封性良好,内部可承受正压5-10MPa,抽真空后,充入氮气或者氨气中的一种或者多种。
可选的,混合充入的时候,按照氮气:氨气体积分数为1:1充入。
可选的,S4中所述的烧结炉采用电加热炉,温度能够精确控制,炉子升温方式为梯度温升,温升速率为1-30℃/min,在达到1300℃时保温1-2小时,达到1500℃时,保温2-5小时,最后升温至1900℃,保温60小时,待烧结完成且炉内温度稳定后断电,降温处理,随炉冷却制得不含氧氮化硅坩埚。
本申请的实施中例提供的技术方案可以包括以下有益效果:
本发明采用的高纯氮化硅粉体配合聚硅氮烷类的聚合物作为烧结剂,制得的氮化硅坩埚具有无氧坩埚的优秀特质,在单晶硅拉制的过程中,不会引入氧元素,能够完全控制后续单晶片中B-O对的形成,这种B-O对对光电转换具有抑制作用,也就能很好的解决太阳能电池光电转换效率的问题,大大提高商业应用价值;传统使用的时石英坩埚其中SiO2中的氧高温易裂解脱氧进入硅溶液中,并且现阶段的氮化硅坩埚,采用的烧结剂为常规的Al2O3、Y2O3、ZrO等金属氧化物和稀土元素氧化物,同样引入氧元素,大大影响光电转换效率,本发明恰好能解决这一问题,氮化硅配合聚硅氮烷的烧结剂,原料和烧结剂均只含有Si、N、H、C这几种元素,且高温下生成的SiN、SiC都是高温机械性能和化学性能优质的熔炼单晶硅的坩埚材料,不会引入任何氧元素,完美地突破了现有技术瓶颈。
应当理解的是,以上的一般描述和后文的细节描述仅是示例性和解释性的,并不能限制本申请。
具体实施方式
这里将详细地对示例性实施例进行说明,以下示例性实施例中所描述的实施方式并不代表与本申请相一致的所有实施方式。相反,它们仅是与如所附权利要求书中所详述的、本申请的一些方面相一致的装置和方法的例子。
在本申请使用的术语是仅仅出于描述特定实施例的目的,而非旨在限制本申请。在本申请和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式,除非上下文清楚地表示其他含义。还应当理解,本文中使用的术语“和/或”是指并包含一个或多个相关联的列出项目的任何或所有可能组合。
本发明所述的一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法,包括以下步骤:
S1、将高纯氮化硅粉体与聚硅氮烷(PSZ)充分混合,加入易挥发性有机溶剂,充分搅拌均匀后,制得混合浆料;
S2、将混合好的浆料在球磨机上进行球磨处理,之后将浆料静置一段时间;
S3、将S2中的浆料注入提前预制好的坩埚模具中,注浆过程缓慢平稳,完成后,持续加压一定时间,开模取出坩埚坯体,在室温下干燥烘干去除溶剂;
S4、将处理好的坩埚坯体放置于烧结炉中,在氮气氛围下,维持正压,升温至熔融状态,在熔融态下保温一定时间,随炉冷却制得不含氧氮化硅坩埚。
由以上技术方案可知,本申请提供了一种无氧氮化硅坩埚的制作方法,采用高纯氮化硅粉体配合聚硅氮烷类的聚合物作为烧结剂,制得的氮化硅坩埚。该坩埚在微观结构上由致密排列的氮化硅单元体组成,由于氮化硅的熔点高于聚硅氮烷(PSZ),各氮化硅分子之间的空隙,高温下形成所示的熔区,该区发生的一系列化学反应均没有氧元素的参与,摆脱了传统烧结剂的含氧问题,该氮化硅坩埚在单晶硅拉制的过程中,不会引入氧元素,能够完全控制后续单晶片中B-O对的形成,这种B-O对对光电转换具有抑制作用,也就能很好的解决太阳能电池光电转换效率的问题,大大提高商业应用价值;相比于传统使用的石英坩埚,不会导致SiO2中的氧高温易裂解脱氧进入硅溶液中,并且现阶段的氮化硅坩埚,采用的烧结剂为常规的Al2O3、Y2O3、ZrO等金属氧化物和稀土元素氧化物,同样引入氧元素,大大影响光电转换效率,本发明恰好能解决这一问题,氮化硅配合聚硅氮烷的烧结剂,原料和烧结剂均只含有Si、N、H、C这几种元素,且高温下生成的SiN、SiC都是机械性能,高温化学性能优质的熔炼单晶硅的坩埚材料,不会引入任何氧元素,完美地突破了现有技术瓶颈,是一种创造性的技术方案。
实例1
S1、将粒径1um,纯度≥95%的高纯氮化硅粉体100质量份与聚硅氮烷(PSZ)80质量份充分混合,加入适量有机胺,充分搅拌均匀后,制得氮化硅基的浆料,浆料固含量为55%;
S2、将混合好的浆料在行星球磨机上进行球磨处理,转速为50/分钟,处理时长为3小时,之后将浆料静置一段时间;
S3、将步骤2中的浆料注入提前预制好的石墨坩埚模具中,注浆过程缓慢平稳,完成后,持续加压5MPa,开模取出坩埚坯体,在60℃的环境下烘干处理30小时左右;
S4、将处理好的坩埚坯体放置于烧结炉中,抽真空,充入氮气,维持正压5MPa,缓慢升温至1400℃,温升速率为30℃/min,在达到1300℃时保温1小时,达到1500℃时,保温2小时,最后升温至1900℃左右,保温60小时,待烧结完成且炉内温度稳定后断电,降温处理,随炉冷却制得不含氧氮化硅坩埚。
实例2
S1、将粒径3um,纯度≥95%的高纯氮化硅粉体100质量份与聚硅氮烷(PSZ)1:1混合物共85质量份充分混合,加入适量无水乙醇,充分搅拌均匀后,制得氮化硅基的浆料,浆料固含量为60%;
S2、将混合好的浆料在行星球磨机上进行球磨处理,转速为80/分钟,处理时长为5小时,之后将浆料静置一段时间;
S3、将步骤2中的浆料注入提前预制好的石墨坩埚模具中,注浆过程缓慢平稳,完成后,持续加压10MPa,开模取出坩埚坯体,在70℃的环境下烘干处理40小时左右;
S4、将处理好的坩埚坯体放置于烧结炉中,抽真空,充入氨气,维持正压8MPa,缓慢升温至1400℃,温升速率为30℃/min,在达到1300℃时保温2小时,达到1500℃时,保温3小时,最后升温至1900℃左右,保温60小时,待烧结完成且炉内温度稳定后断电,降温处理,随炉冷却制得不含氧氮化硅坩埚。
实例3
S1、将粒径2um,纯度≥95%的高纯氮化硅粉体100质量份与聚硅氮烷(PSZ)85质量份充分混合,加入适量丙酮,充分搅拌均匀后,制得氮化硅基的浆料,浆料固含量为60%;
S2、将混合好的浆料在行星球磨机上进行球磨处理,转速为80/分钟,处理时长为5小时,之后将浆料静置一段时间;
S3、将步骤2中的浆料注入提前预制好的石墨坩埚模具中,注浆过程缓慢平稳,完成后,持续加压15MPa,开模取出坩埚坯体,在80℃的环境下烘干处理45小时左右;
S4、将处理好的坩埚坯体放置于烧结炉中,抽真空,按照N2:NH3=1:1充入炉内,维持正压10MPa,缓慢升温至1400℃,温升速率为30℃/min,在达到1300℃时保温2小时,达到1500℃时,保温5小时,最后升温至1900℃左右,保温60小时,待烧结完成且炉内温度稳定后断电,降温处理,随炉冷却制得不含氧氮化硅坩埚。
本申请旨在涵盖本申请的任何变型、用途或者适应性变化,这些变型、用途或者适应性变化遵循本申请的一般性原理并包括本申请未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的,本申请的真正范围和精神由权利要求指出。
应当理解的是,本申请并不局限于上面已经描述中示出的精确结构,并且可以在不脱离其范围进行各种修改和改变。本申请的范围仅由所附的权利要求来限制。
Claims (10)
1.一种用于单晶硅拉制的无氧氮化硅坩埚的制作方法,其包括:
S1、将高纯氮化硅粉体与聚硅氮烷(PSZ)充分混合,加入易挥发性有机溶剂,充分搅拌均匀后,制得混合浆料;
S2、将混合好的浆料在球磨机上进行球磨处理,之后将浆料静置一段时间;
S3、将S2中的浆料注入提前预制好的坩埚模具中,注浆过程缓慢平稳,完成后,持续加压一定时间,开模取出坩埚坯体,在室温下干燥烘干去除溶剂;
S4、将处理好的坩埚坯体放置于烧结炉中,在氮气氛围下,维持正压,升温至熔融状态,在熔融态下保温一定时间,随炉冷却制得不含氧氮化硅坩埚。
2.根据权利要求1所述的方法,其特征在于,S1中的高纯氮化硅粉体纯度达到95%以上,粒径1-3um。
3.根据权利要求1所述的方法,其特征在于,S1中加入聚硅氮烷(PSZ)之类的仅含有C、H、N、Si且熔点低于氮化硅气化临界点的聚合物,浆料固含量维持在55-60%。
4.根据权利要求1所述的方法,其特征在于,所述易挥发性有机溶剂选自有机胺、丙酮、无水乙醇。
5.根据权利要求1所述的方法,其特征在于,S2的球磨机选取行星球磨机,球磨混合参数选择:转速为50-80转/分钟,处理时长为3-5小时。
6.根据权利要求1所述的方法,其特征在于,S2中对浆料的球磨处理时间为5-10小时,静置时间为6-8小时。
7.根据权利要求1所述的方法,其特征在于,S3中的坩埚模具内腔表面做光滑处理,不能存在毛面,注浆完成后加压5-15MPa,持续时间为6-8小时,在60-80℃的环境下烘干处理30-45小时。
8.根据权利要求1所述的方法,其特征在于,S4中真空炉充入的氮气或者氨气中的一种或者多种。
9.根据权利要求1所述的方法,其特征在于,混合充入的时候,按照氮气:氨气体积分数为1:1充入。
10.根据权利要求1所述的方法,其特征在于,S4中烧结炉,气密性良好,炉内氮气或者氨气的正压维持在5-10MPa,温升方式为梯度温升,温升速率为1-30℃/min,在达到1300℃时保温1-2小时,达到1500℃时,保温2-5小时,最后升温至1900℃,保温60小时后,随炉冷却。
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