CN114455963B - 一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚 - Google Patents

一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚 Download PDF

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CN114455963B
CN114455963B CN202111658795.1A CN202111658795A CN114455963B CN 114455963 B CN114455963 B CN 114455963B CN 202111658795 A CN202111658795 A CN 202111658795A CN 114455963 B CN114455963 B CN 114455963B
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张永辉
程皓
郁荣
白鸽
康媛媛
候雯菲
程凯峰
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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涂层的炭/炭‑碳化硅复合材料坩埚，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CVI工艺、树脂浸渍炭化工艺以及CVI工艺依次对炭纤维预制体进行热解炭、树脂炭以及碳化硅增密处理获得的体积密度为1.6g/cm3～1.8g/cm3的C/C‑SiC复合材料；其中，炭纤维预制体的体积密度为0.3g/cm3～0.6g/cm3，热解炭增密至1.0g/cm3～1.2g/cm3，树脂炭增密至1.4g/cm3～1.6g/cm3，碳化硅增密至1.6g/cm3～1.8g/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，避免石英坩埚的使用，而且使用寿命显著提高，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。

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一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚
技术领域
本发明涉及一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，属于单晶硅拉制炉用热场部件技术领域。
背景技术
目前，利用直拉法生产单晶硅过程中，盛装多晶硅的石英坩埚安放在炭/炭复合材料坩埚内(如图1所示)，其中石英坩埚用来承载硅料以保证硅料的纯度；炭/炭复合材料坩埚用来承载石英坩埚以提供强度支撑。单晶硅拉制炉炉内温度高达1500℃，盛放硅料的石英坩埚会出现变形、软化等问题，使得石英坩埚与炭/炭复合材料坩埚之间结合很紧密，只能采用敲碎旧石英坩埚并换上新的石英坩埚后方可进行下一炉的拉制，因此，每炉次将消耗1件石英坩埚，而且敲击方式会对炭/炭复合材料坩埚造成机械损伤，降低了炭/炭复合材料坩埚的使用寿命。与此同时，生产石英坩埚的原材料石英砂相对紧缺，在未来高纯度石英砂的供给存在较大的缺口，将会加剧石英坩埚制造成本上升，进而提高单晶硅拉制成本。
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Si3N4涂层，使坩埚可利用次数显著上升，寿命明显提高，但Si3N4涂层表面较为粗糙，且对硅有一定的润湿性，在单晶硅的生产过程中有破坏Si3N4涂层的风险；专利CN 102731119 A公开了一种制备工艺简单、耐硅蒸汽侵蚀的碳/碳/碳化硅复合材料坩埚及制备方法，特征在于在预制体表面采用化学气相渗透法进行热解碳和碳化硅交替增密或者混合增密至1.30～2.50g/cm3，大幅度提高了炭/炭坩埚的使用寿命，但不能替换传统的石英坩埚加炭/炭坩埚的生产模式，制备成本较高。
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涂层的炭/炭-碳化硅复合材料坩埚，所述复合材料坩埚既具有支撑作用又可保证熔融硅纯度，避免了石英坩埚的使用，而且延长了复合材料坩埚的使用寿命，明显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。
本发明的目的是通过以下技术方案实现的。
一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，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、树脂浸渍炭化工艺以及化学气相渗透工艺依次对炭纤维预制体进行热解炭、树脂炭以及碳化硅增密处理获得的体积密度为1.6g/cm3～1.8g/cm3的C/C-SiC复合材料；其中，炭纤维预制体的体积密度为0.3g/cm3～0.6g/cm3，热解炭增密至1.0g/cm3～1.2g/cm3，树脂炭增密至1.4g/cm3～1.6g/cm3，碳化硅增密至1.6g/cm3～1.8g/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，采用树脂浸渍炭化工艺进行树脂炭增密过程中，先采用糠酮树脂或/和酚醛树脂进行压力浸渍，然后进行固化，再进行炭化，之后循环浸渍固化炭化操作处理直至增密至所需密度；其中，浸渍压力优选1.0MPa～3.0MPa，单次浸渍时间优选0.5h～5h，固化温度优选100℃～300℃，单次固化时间优选1h～10h，炭化温度优选900℃～1100℃，单次炭化时间优选2h～6h。
进一步地，先将热解炭和树脂炭增密处理后获得的炭/炭基体在1600℃～2200℃下高温纯化1h～5h，然后采用CVI工艺进行碳化硅增密，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500μm～700μm。
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30mm～50mm。
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，解决了石英坩埚原材料缺乏的现状，具有重要的行业价值；而且避免了对复合材料坩埚的机械损伤，提高了坩埚的使用寿命，进一步降低了生产成本，具有显著的经济效益。
(2)本发明所述坩埚本体中采用CVI工艺结合树脂浸渍炭化工艺进行热解炭和树脂炭增密，缩短了制备周期，有效降低了生产成本，而且热解炭的存在能够避免炭纤维的损伤，为坩埚本体提供强度支撑；同时，调控炭纤维、热解炭、树脂炭以及碳化硅的含量，能使其形成的炭陶基体致密性高，承载能力强，在1.6g/cm3～1.8g/cm3的体积密度下能够满足坩埚的使用要求。
(3)本发明采用CVI工艺进行碳化硅增密之前进行的高温纯化处理，一方面有利于树脂炭中杂质(例如N、H、O等元素)的逸出，从而保证了基体炭的纯度；另一方面使树脂炭发生晶格结构转变，从无序结构转化为稳定的石墨态结构，进一步提高了材料的热稳定性。
(4)本发明所述复合材料坩埚，在调控热解炭、树脂炭及碳化硅含量的基础上，通过优化的等离子喷涂工艺参数获得了厚度为500μm～700μm的α-Al2O3涂层，在基体和涂层的共同作用下，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涂层的炭/炭-碳化硅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涂层的炭/炭-碳化硅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涂层的炭/炭-碳化硅复合材料坩埚，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0.3g/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)先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，然后采用树脂浸渍炭化工艺进行树脂炭增密且增密至1.4g/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20L/min，沉积温度为900℃，总沉积时间为360h；
树脂浸渍炭化工艺的工艺条件如下：先采用糠酮树脂进行压力浸渍，然后进行固化，再进行炭化，之后循环浸渍固化炭化操作处理；其中，浸渍压力为1.0MPa，单次浸渍时间为5h，固化温度为100℃，单次固化时间为10h，炭化温度为900℃，单次炭化时间为6h，糠酮树脂浸渍固化炭化周期循环处理总共3次；
(3)先将炭/炭基体置于1600℃下高温纯化5h，然后采用化学气相渗透工艺对炭/炭基体进行碳化硅增密处理，得到体积密度为1.6g/cm3的炭/炭-碳化硅基体，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150h；
(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90MPa(根据GB/T 33501-2017标准测试)；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涂层的炭/炭-碳化硅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涂层的炭/炭-碳化硅复合材料坩埚，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0.45g/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)先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，然后采用树脂浸渍炭化工艺进行树脂炭增密且增密至1.5g/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60L/min，沉积温度为1000℃，总沉积时间为240h；
树脂浸渍炭化工艺的工艺条件如下：先采用酚醛树脂进行压力浸渍，然后进行固化，再进行炭化，之后循环浸渍固化炭化操作处理；其中，浸渍压力为2.0MPa，单次浸渍时间为3h，固化温度为200℃，单次固化时间为5h，炭化温度为1000℃，单次炭化时间为4h，酚醛树脂浸渍固化炭化周期循环处理总共2次；
(3)先将炭/炭基体置于1800℃下高温纯化3h，然后采用化学气相渗透工艺对炭/炭基体进行碳化硅增密处理，得到体积密度为1.7g/cm3的炭/炭-碳化硅基体，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100h；
(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40mm，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600μm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涂层的炭/炭-碳化硅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涂层的炭/炭-碳化硅复合材料坩埚，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)先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，然后采用树脂浸渍炭化工艺进行树脂炭增密且增密至1.6g/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120h；
树脂浸渍炭化工艺的工艺条件如下：先采用酚醛树脂进行压力浸渍，然后进行固化，再进行炭化，之后不需要循环浸渍固化炭化操作处理；其中，浸渍压力为3.0MPa，单次浸渍时间为0.5h，固化温度为300℃，单次固化时间为1h，炭化温度为1100℃，单次炭化时间为2h，酚醛树脂浸渍炭化周期循环处理总共1次；
(3)先将炭/炭基体置于2200℃下高温纯化1h，然后采用化学气相渗透工艺对炭/炭基体进行碳化硅增密处理，得到体积密度为1.8g/cm3的炭/炭-碳化硅基体，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50h；
(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30mm，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700μm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涂层的炭/炭-碳化硅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涂层的炭/炭-碳化硅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 BDA0003449161790000071
对本发明实施例1～3所制备的含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚中的炭/炭-碳化硅复合材料坩埚本体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
Figure BDA0003449161790000072
Figure BDA0003449161790000081
对本发明实施例1～3所制备的含有α-Al2O3涂层的炭/炭-碳化硅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>涂层的炭/炭-碳化硅复合材料坩埚]]> 10～11
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 (7)

1.一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，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、树脂浸渍炭化工艺以及化学气相渗透工艺依次对炭纤维预制体进行热解炭、树脂炭以及碳化硅增密处理获得的体积密度为1.6g/cm3～1.8g/cm3的C/C-SiC复合材料；其中，炭纤维预制体的体积密度为0.3g/cm3～0.6g/cm3，热解炭增密至1.0g/cm3～1.2g/cm3，树脂炭增密至1.4g/cm3～1.6g/cm3，碳化硅增密至1.6g/cm3～1.8g/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；
先将热解炭和树脂炭增密处理后获得的炭/炭基体在1600℃～2200℃下高温纯化1h～5h，然后采用化学气相渗透工艺进行碳化硅增密；
α-Al2O3涂层的厚度为500μm～700μm。
2.根据权利要求1所述的一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，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涂层的炭/炭-碳化硅复合材料坩埚，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涂层的炭/炭-碳化硅复合材料坩埚，其特征在于：采用树脂浸渍炭化工艺进行树脂炭增密过程中，先采用糠酮树脂或/和酚醛树脂进行压力浸渍，然后进行固化，再进行炭化，之后循环浸渍固化炭化操作处理直至增密至所需密度；
其中，浸渍压力1.0MPa～3.0MPa，单次浸渍时间0.5h～5h，固化温度100℃～300℃，单次固化时间1h～10h，炭化温度900℃～1100℃，单次炭化时间2h～6h。
5.根据权利要求1至4任一项所述的一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，其特征在于：硅源气体采用三氯甲基硅烷，硅源气体的流量10L/min～50L/min，化学气相沉积的温度1100℃～1300℃。
6.根据权利要求1所述的一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，其特征在于：采用等离子喷涂法制备α-Al2O3涂层，其中等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30mm～50mm。
7.根据权利要求6所述的一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚，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。
CN202111658795.1A 2021-12-30 2021-12-30 一种含有α-Al2O3涂层的炭/炭-碳化硅复合材料坩埚 Active CN114455963B (zh)

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