CN114368975B - 一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚 - Google Patents

一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚 Download PDF

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CN114368975B
CN114368975B CN202111681954.XA CN202111681954A CN114368975B CN 114368975 B CN114368975 B CN 114368975B CN 202111681954 A CN202111681954 A CN 202111681954A CN 114368975 B CN114368975 B CN 114368975B
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程皓
张永辉
白鸽
郁荣
康媛媛
程凯峰
候雯菲
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Xi'an Chaoma Technology Co ltd
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Abstract

本发明涉及一种含有α‑Al2O3涂层的低密度C/C‑SiC复合材料坩埚，属于单晶硅拉制炉用热场部件技术领域。所述复合材料坩埚包括坩埚本体以及涂覆在坩埚本体内表面的α‑Al2O3涂层，坩埚本体是通过化学气相渗透工艺依次对炭纤维预制体进行热解炭以及碳化硅增密处理获得的C/C‑SiC复合材料，炭纤维预制体的体积密度为0.5g/cm3～0.7g/cm3，热解炭增密至1.0g/cm3～1.2g/cm3，碳化硅增密至1.4g/cm3～1.6g/cm3。所述复合材料坩埚既具有支撑作用又可保证熔融硅纯度，避免使用石英坩埚，而且复合材料坩埚使用寿命显著提高，有效降低单晶硅拉制成本，解决了现有技术中必须同时使用石英坩埚和炭/炭复合材料坩埚拉制单晶硅所带来的问题。

Description

一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚
技术领域
本发明涉及一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，属于单晶硅拉制炉用热场部件技术领域。
背景技术
利用直拉法生产单晶硅过程中，目前普遍采用“炭/炭复合材料坩埚+石英坩埚”共同作用的方式进行拉制，如图1所示，石英坩埚嵌套于炭/炭复合材料坩埚中，石英坩埚用来承载硅料，保证硅料的纯度，炭/炭复合材料坩埚用来承载石英坩埚，提供强度支撑。在单晶硅拉制过程中，硅蒸气及含硅气体(SiO)和石英坩埚(主要成分为SiO2)均会和炭/炭复合材料坩埚发生化学反应，导致炭/ 炭坩埚被侵蚀，直至失效。同时在单晶硅拉制过程中，每炉次将消耗1件石英坩埚，故石英坩埚需求量将持续增加，然而随着生产石英坩埚的原材料高纯石英砂的日益短缺，石英坩埚的制造成本也将持续增加。因此解决石英坩埚和炭/ 炭坩埚所存在的问题是单晶硅生产过程中的关键所在。
专利CN 113200765A公开了一种采用CVD方法在碳陶坩埚表面制备形成一层Si3N4和BN的复合涂层，以达到提升坩埚的高温稳定性能和抗硅蚀能力，但Si3N4涂层对硅有一定的润湿性，且碳陶坩埚密度过高会导致成本增加，抗热震性差，缩短坩埚的使用寿命；专利CN 103102170 A公开了一种新型炭/炭复合材料坩埚，包括涂于炭/炭复合材料坩埚基体上的SiC涂层和和涂覆于炭/炭/碳化硅坩埚表面的Si3N4涂层，使坩埚可利用次数显著上升，寿命明显提高，但是由于熔融硅对Si3N4涂层具有一定的润湿性，存在Si3N4涂层被破坏的风险，降低坩埚的使用寿命。
发明内容
针对现有技术中存在的问题，本发明提供一种含有α-Al2O3涂层的低密度 C/C-SiC复合材料坩埚，所述复合材料坩埚既具有支撑作用又可保证熔融硅纯度，满足单晶硅制备的需求，避免石英坩埚的使用，而且延长了所述复合材料坩埚的使用寿命，解决了现有技术中必须同时使用石英坩埚和炭/炭复合材料坩埚拉制单晶硅所带来的问题。
本发明的目的是通过以下技术方案实现的。
一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，所述复合材料坩埚包括坩埚本体以及涂覆在坩埚本体内表面的α-Al2O3涂层；
所述坩埚本体是通过化学气相渗透(CVI)工艺依次对炭纤维预制体进行热解炭以及碳化硅增密处理获得的体积密度为1.4g/cm3～1.6g/cm3的C/C-SiC复合材料；其中，炭纤维预制体的体积密度为0.5g/cm3～0.7g/cm3，热解炭增密至1.0 g/cm3～1.2g/cm3，碳化硅增密至1.4g/cm3～1.6g/cm3。
进一步地，炭纤维预制体为轴向炭纤维无纬布/炭网胎复合铺层与环向炭纤维连续缠绕层交替叠加针刺形成的；其中，优选炭纤维无纬布/炭网胎复合铺层中含有一层炭纤维无纬布和一层炭网胎，炭纤维无纬布/炭网胎复合铺层与一层炭纤维连续缠绕层交替叠加。
进一步地，采用CVI工艺进行热解炭增密过程中，碳源气体采用天然气或丙烯。
进一步地，采用CVI工艺进行碳化硅增密过程中，硅源气体采用三氯甲基硅烷；硅源气体的流量优选10L/min～50L/min，化学气相沉积的温度优选 1100℃～1300℃。
进一步地，α-Al2O3涂层的厚度为200μm～500μm。
进一步地，采用等离子喷涂法制备α-Al2O3涂层，优选等离子喷涂的工艺参数如下：载气(优选氮气)压力为0.2MPa～2.0MPa，辅气(优选氢气)压力为 0.1MPa～1.0MPa，电流为500A～800A，电压为60V～100V，喷涂距离为50 mm～100mm。
进一步地，等离子喷涂所采用的氧化铝粉体的纯度大于等于99.50％，优选粒径10μm～100μm。
有益效果：
(1)本发明所述复合材料坩埚，在单晶硅拉制过程中，取代了传统的石英坩埚结合炭/炭复合材料坩埚的生产模式，避免了石英坩埚的大量使用，降低了单晶硅生产的成本。
(2)本发明所述复合材料坩埚，通过调控炭纤维、热解炭以及碳化硅的含量，一方面，引入的热解炭为坩埚本体提供强度支撑；另一方面，引入的碳化硅提高了坩埚本体的抗侵蚀性能。
(3)本发明采用CVI工艺制备得到热解炭和SiC复合基体，相对于传统的 CVI工艺制备的纯SiC基体，进一步缩短了制备周期，降低了生产成本；同时， CVI工艺生成的立方晶型结构的β-SiC，结晶性能好，具有耐高温、耐热震、耐腐蚀等优良性能，与热解炭匹配形成的复合基体致密性高，承载能力强，在1.40 g/cm3～1.60g/cm3的体积密度下能够满足坩埚的使用要求。
(4)本发明在坩埚本体上制备晶相稳定的α-Al2O3涂层，一方面，α-Al2O3与β-SiC具有良好的适配性，能够有效填充炭陶基体内部孔隙，且与炭陶基体的结合强度高，进而实现对炭陶基体的充分保护；另一方面，α-Al2O3涂层在单晶硅拉制过程中不会引入杂质成分，保证了拉制单晶硅过程中熔融硅的纯度；同时，利用优化的等离子喷涂工艺参数获得厚度为200μm～500μm的α-Al2O3涂层，在一定含量的热解炭和碳化硅基体的共同作用下，满足单晶硅拉制的需求。
(5)本发明所述复合材料坩埚中，选用轴向炭纤维无纬布/炭网胎复合铺层与环向炭纤维连续缠绕层交替叠加针刺形成的炭纤维预制体，相对于其他编织形式的预制体，环向连续纤维的引入，提高了复合材料的环向拉伸强度，进一步提高了复合材料坩埚的使用寿命。
附图说明
图1为现有技术中炭/炭复合材料坩埚与石英坩埚共同作用下拉制单晶硅时的结构示意图。
图2为实施例中制备的含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚的结构示意图。
图3为实施例1中制备的坩埚本体表面的X射线衍射(XRD)谱图。
图4为实施例1中制备的含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚内表面的X射线衍射(XRD)谱图。
其中，1-坩埚本体，2-α-Al2O3涂层。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步阐述，其中，所述方法如无特别说明均为常规方法，所述原材料如无特别说明均能从公开商业途径获得。
实施例1
一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，所述复合材料坩埚包括坩埚本体1以及涂覆在坩埚本体1内表面的α-Al2O3涂层2，如图2所示；所述复合材料坩埚的具体制备步骤如下：
(1)采用轴向炭纤维无纬布/炭网胎复合铺层与环向炭纤维连续缠绕层交替叠加针刺的形式制备体积密度为0.5g/cm3的炭纤维预制体；
其中，炭纤维无纬布/炭网胎复合铺层中含有一层炭纤维无纬布和一层炭网胎，炭纤维无纬布/炭网胎复合铺层与一层炭纤维连续缠绕层交替叠加；
(2)采用化学气相渗透工艺对炭纤维预制体进行热解炭增密处理且增密至 1.0g/cm3，之后进行机械加工，即得到炭/炭基体；
化学气相渗透工艺的参数如下：以丙烯为碳源气体，碳源气体的流量为20 L/min，沉积温度为900℃，总沉积时间为300h；
(3)采用化学气相渗透工艺对炭/炭基体进行碳化硅增密处理且增密至1.4 g/cm3，得到C/C-SiC基体，即得到坩埚本体1；
化学气相渗透工艺的参数如下：以三氯甲基硅烷为硅源气体，硅源气体的流量为10L/min，化学气相沉积温度为1100℃，总沉积时间为300h；
(4)选用粒度为10μm以及质量纯度≥99.50％的氧化铝，载气氮气压力为 0.2MPa，辅气氢气压力为0.1MPa，电压为60V，电流为500A，喷涂距离为 100mm，通过等离子喷涂将氧化铝粉体喷涂在坩埚本体1的内表面，在其内表面形成一层厚度为200μm的α-Al2O3涂层2，即得到所述复合材料坩埚。
对步骤(3)制备的坩埚本体1分别进行拉伸强度测试以及XRD测试，测得拉伸强度为90MPa(根据GB/T 33501-2017标准测试)；根据图3的XRD图谱可知，通过CVI工艺引入的是β-SiC。
对步骤(4)所制备的含有α-Al2O3涂层的C/C-SiC复合材料坩埚的内表面进行XRD测试，根据图4的测试结果可知，坩埚本体1内表面的涂层成分为α-Al2O3。
实施例2
一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，所述复合材料坩埚包括坩埚本体1以及涂覆在坩埚本体1内表面的α-Al2O3涂层2，如图2所示；所述复合材料坩埚的具体制备步骤如下：
(1)采用轴向炭纤维无纬布/炭网胎复合铺层与环向炭纤维连续缠绕层交替叠加针刺的形式制备体积密度为0.6g/cm3的炭纤维预制体；
其中，炭纤维无纬布/炭网胎复合铺层中含有一层炭纤维无纬布和一层炭网胎，炭纤维无纬布/炭网胎复合铺层与一层炭纤维连续缠绕层交替叠加；
(2)采用化学气相渗透工艺对炭纤维预制体进行热解炭增密处理且增密至 1.1g/cm3，之后进行机械加工，即得到炭/炭基体；
化学气相渗透工艺的参数如下：以丙烯为碳源气体，碳源气体的流量为60 L/min，沉积温度为1000℃，总沉积时间为200h；
(3)采用化学气相渗透工艺对炭/炭基体进行碳化硅增密处理且增密至1.5 g/cm3，得到C/C-SiC基体，即得到坩埚本体1；
化学气相渗透工艺的参数如下：以三氯甲基硅烷为硅源气体，硅源气体的流量为30L/min，化学气相沉积温度为1200℃，总沉积时间为200h；
(4)选用粒度为50μm以及质量纯度≥99.50％的氧化铝，载气氮气压力为 1.0MPa，辅气氢气压力为0.5MPa，电压为80V，电流为600A，喷涂距离为 80mm，通过等离子喷涂将氧化铝粉体喷涂在坩埚本体1的内表面，在其内表面形成一层厚度为350μm的α-Al2O3涂层2，即得到所述复合材料坩埚。
对步骤(3)制备的坩埚本体1分别进行拉伸强度测试以及XRD测试，测得拉伸强度为95MPa(根据GB/T 33501-2017标准测试)；根据XRD的表征结果可知，通过CVI工艺引入的是β-SiC。
对步骤(4)所制备的含有α-Al2O3涂层的C/C-SiC复合材料坩埚的内表面进行XRD测试，根据测试结果可知，坩埚本体1内表面的涂层成分为α-Al2O3。
实施例3
一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，所述复合材料坩埚包括坩埚本体1以及涂覆在坩埚本体1内表面的α-Al2O3涂层2，如图2所示；所述复合材料坩埚的具体制备步骤如下：
(1)采用轴向炭纤维无纬布/炭网胎复合铺层与环向炭纤维连续缠绕层交替叠加针刺的形式制备体积密度为0.7g/cm3的炭纤维预制体；
其中，炭纤维无纬布/炭网胎复合铺层中含有一层炭纤维无纬布和一层炭网胎，炭纤维无纬布/炭网胎复合铺层与一层炭纤维连续缠绕层交替叠加；
(2)采用化学气相渗透工艺对炭纤维预制体进行热解炭增密处理且增密至 1.2g/cm3，之后进行机械加工，即得到炭/炭基体；
化学气相渗透工艺的参数如下：以天然气为碳源气体，碳源气体的流量为100L/min，沉积温度为1100℃，总沉积时间为100h；
(3)采用化学气相渗透工艺对炭/炭基体进行碳化硅增密处理且增密至1.6 g/cm3，得到C/C-SiC基体，即得到坩埚本体1；
化学气相渗透工艺的参数如下：以三氯甲基硅烷为硅源气体，硅源气体的流量为50L/min，化学气相沉积温度为1300℃，总沉积时间为100h；
(4)选用粒度为100μm以及质量纯度≥99.50％的氧化铝，载气氮气压力为2.0MPa，辅气氢气压力为1.0MPa，电压为100V，电流为800A，喷涂距离为50mm，通过等离子喷涂将氧化铝粉体喷涂在坩埚本体1的内表面，在其内表面形成一层厚度为500μm的α-Al2O3涂层2，即得到所述复合材料坩埚。
对步骤(3)制备的坩埚本体1分别进行拉伸强度测试以及XRD测试，测得拉伸强度为100MPa(根据GB/T 33501-2017标准测试)；根据XRD的表征结果可知，通过CVI工艺引入的是β-SiC。
对步骤(4)所制备的含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚的内表面进行XRD测试，根据测试结果可知，坩埚本体1内表面的涂层成分为α-Al2O3。
对本发明实施例1～3所制备的含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚与目前西安超码科技有限公司现有的“石英坩埚+炭/炭复合材料坩埚”生产模式下石英坩埚损耗量进行对比，结果见表1。
表1
Figure BDA0003447200510000061
对本发明实施例1～3所制备的含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚中的C/C-SiC复合材料坩埚本体1与目前西安超码科技有限公司现有的“石英坩埚+炭/炭复合材料坩埚”组合中的炭/炭复合材料坩埚力学性能进行对比，结果见表2。
表2
材料 拉伸强度(MPa)
炭/炭复合材料坩埚 60～80
C/C-SiC复合材料坩埚本体1 90～100 
对本发明实施例1～3所制备的含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚与目前西安超码科技有限公司现有的“石英坩埚+炭/炭复合材料坩埚”组合中的炭/炭复合材料坩埚使用寿命进行对比，结果见表3。
表3
材料 使用寿命(月)
炭/炭复合材料坩埚 6～9
<![CDATA[含有α-Al<sub>2</sub>O<sub>3</sub>涂层的低密度C/C-SiC复合材料坩埚]]> 10～12 
综上所述，以上仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：所述复合材料坩埚包括坩埚本体以及涂覆在坩埚本体内表面的α-Al2O3涂层；
所述坩埚本体是通过化学气相渗透工艺依次对炭纤维预制体进行热解炭以及碳化硅增密处理获得的体积密度为1.4g/cm3～1.6g/cm3的C/C-SiC复合材料；其中，炭纤维预制体的体积密度为0.5g/cm3～0.7g/cm3，热解炭增密至1.0g/cm3～1.2g/cm3，碳化硅增密至1.4g/cm3～1.6g/cm3，且碳化硅为β-SiC；
炭纤维预制体为轴向炭纤维无纬布/炭网胎复合铺层与环向炭纤维连续缠绕层交替叠加针刺形成的；
α-Al2O3涂层的厚度为200μm～500μm。
2.根据权利要求1所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：炭纤维无纬布/炭网胎复合铺层中含有一层炭纤维无纬布和一层炭网胎，炭纤维无纬布/炭网胎复合铺层与一层炭纤维连续缠绕层交替叠加。
3.根据权利要求1所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：采用化学气相渗透工艺进行热解炭增密过程中，碳源气体采用天然气或丙烯。
4.根据权利要求1所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：采用化学气相渗透工艺进行碳化硅增密过程中，硅源气体采用三氯甲基硅烷。
5.根据权利要求 4所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：采用化学气相渗透工艺进行碳化硅增密过程中，硅源气体的流量为10L/min～50L/min，化学气相沉积的温度为1100℃～1300℃。
6.根据权利要求1至5任一项所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：采用等离子喷涂法制备α-Al2O3涂层。
7.根据权利要求6所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：离子喷涂的工艺参数如下：载气压力为0.2MPa～2.0MPa，辅气压力为0.1MPa～1.0MPa，电流为500A～800A，电压为60V～100V，喷涂距离为50mm～100mm。
8.根据权利要求7所述的一种含有α-Al2O3涂层的低密度C/C-SiC复合材料坩埚，其特征在于：等离子喷涂所采用的氧化铝粉体的纯度大于等于99.50％，粒径为10μm～100μm。
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