CN112624797A - 一种石墨表面梯度碳化硅涂层及其制备方法 - Google Patents
一种石墨表面梯度碳化硅涂层及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨表面梯度碳化硅涂层及其制备方法，方法包括以下步骤：S1：将纳米硅粉加入液态聚碳硅烷中，超声震荡混合均匀，得到含有硅粉的液态聚碳硅烷；将石墨试样加压浸渍于含有硅粉的液态聚碳硅烷中，取出后固化、裂解，从而在石墨表面形成初级碳化硅涂层。S2：采用化学气相沉积法在步骤S1的初级碳化硅涂层表面沉积次级碳化硅涂层，从而初级碳化硅涂层和次级碳化硅涂层形成石墨表面的梯度碳化硅涂层。本发明通过在聚碳硅烷中加入硅粉，硅粉随着聚碳硅烷固化分布在石墨表面，在1650℃‑1800℃与表面石墨反应生成碳化硅，既增强了涂层与石墨基体的结合强度，又避免影响后续CVD SiC的生长。
Description
技术领域
本发明涉及涂层制备技术领域，尤其涉及一种石墨表面梯度碳化硅涂层的制备方法。
背景技术
石墨具有优良的导电、导热性能，高温强度好，在特种工业炉中常用石墨作为发热体。随着半导体工业的全面发展，提炼单晶硅，单晶错，呻化嫁、磷化锢等材料的加热炉选择特种石墨作发热体，一些特殊的工业炉和实验炉用炭布或石墨布作发热体。除了石墨发热体以外，石墨甜桐，炭素保温材料等碳素材料在特种工业炉中大量使用，尤其是在半导体工业中的晶圆生长炉中。碳素材料核心部件损耗占用晶圆制造成本很高比例，碳石墨材料部件用量极大，且属于易耗件，这也是晶圆制造成本很难降低的原因之一。石墨材料的缺点是碳原子在高温下持续挥发，带来两个负面影响：一是碳原子扩散进晶圆，造成晶圆品质下降：二是石墨表面产生大量腐蚀坑，服役寿命减小。目前，随着晶圆产业规模急剧扩大，在太阳能光伏行业中，提高品质、降低成本己成为产业发展的关键，迫切要求延长石墨热场材料服役时间。作为一种航空航天涂层材料，纳米碳化硅涂层新材料导热系数高、热膨胀系数小、碳扩散系数小、化学性能稳定、耐磨损性能好，具有耐高温、抗热震、抗蠕变、抗氧化的优点。在航空航天领域，碳化硅涂层已经被用作碳材料和炭/炭复合材料的高温涂层，抵抗2500-3000的燃气流，表现出优良的抗氧化、抗烧蚀特征。将SiC涂层应用到半导体工业中晶圆生长炉内的石墨发热体等碳素材料，有望将晶圆品质提高3～5倍，石墨核心部件的寿命提高6～10倍，企业经济效益能显著提升。
申请号201510986408.5的中国专利公开了一种石墨热场表面制备SiC涂层的方法，该方法为：(1)以石墨发热体加热炉体作为沉积炉，将其抽真空，真空度达到100Pa以下；(2)将石墨发热体加热炉内温度升高至900～1200℃；(3)将甲院通入石墨发热体加热炉腔内，气体流量根据炉体尺寸调节，同时通入氢气，氩气，反应时间为1-10h；(4)通入四氧化硅气体，其流量与甲院气体流量比从1∶4逐渐升高到1∶1，依次形成25％碳化硅-75％碳复合涂层、50％碳化硅-50％碳复合涂层、75％碳化硅-25％碳复合涂层、100％碳化硅涂层，继续沉积10～30h，随后降温冷却，石墨热场材料表面出现SiC涂层。该方法制备SiC涂层质量好，涂层制备过程不需要专用化学气相沉积设备，成本低，涂层均匀且厚度灵活可控。
申请号为CN201910491081.2的中国专利公开了一种采用化学气相沉积工艺在硅基体上制备超厚碳化硅梯度涂层的方法，采用热激发式化学气相沉积系统，选择SiH4(硅烷)、CH3SiCl3(甲基三氯硅烷)、CH4(甲烷)和H2(氢气)气体体系并控制各组分气体流量线性变化，在工作压强100～1000Pa和温度为1050～1350℃条件下，沉积出结构致密、超厚的碳化硅梯度涂层。根据成分，由Si基材开始该涂层由Si/SiC梯度涂层、纯SiC涂层、SiC/C梯度涂层、纯C涂层、C/SiC梯度涂层以及纯SiC涂层组成。该方法沉积的SiC梯度涂层具有结构致密、无明显裂纹和与基材结合良好等优点。
虽然两种方式制备的梯度涂层虽然改善了涂层与基体的结合强度，但改善效果有限。
发明内容
本发明要解决的技术问题是克服现有技术的不足，提供一种提高涂层与基体结合强度、提高涂层综合性能的石墨表面梯度碳化硅涂层的制备方法。
为解决上述技术问题，本发明采用以下技术方案：
一种石墨表面梯度碳化硅涂层的制备方法，包括以下步骤：
S1：将纳米硅粉加入液态聚碳硅烷中，超声震荡混合均匀，得到含有硅粉的液态聚碳硅烷；将石墨试样加压浸渍于含有硅粉的液态聚碳硅烷中，取出后固化、裂解，从而在石墨表面形成初级碳化硅涂层。
S2：采用化学气相沉积法在步骤S1的初级碳化硅涂层表面沉积次级碳化硅涂层，从而初级碳化硅涂层和次级碳化硅涂层形成石墨表面的梯度碳化硅涂层。
聚碳硅烷浸渍裂解可以实现深入基体表面以下碳化硅涂层的制备，但制备出的碳化硅为分散的粉末状态，尤其是分布在表面的碳化硅，与石墨基体结合力差，还会影响后续CVD SiC涂层的生长，使其生长不均匀。本发明通过加入硅粉，硅粉随着聚碳硅烷固化分布在石墨表面，在1650℃-1800℃与表面石墨反应生成碳化硅，这样既增强了涂层与石墨基体的结合强度，又避免影响后续CVD SiC的生长。
上述的石墨表面梯度碳化硅涂层的制备方法，优选地，所述含有硅粉的液态聚碳硅烷中，所述纳米硅粉的质量分数为10％-20％。
上述的石墨表面梯度碳化硅涂层的制备方法，优选地，所述加压浸渍的压力为5-8MPa，浸渍时间为3-5h。
上述的石墨表面梯度碳化硅涂层的制备方法，优选地，所述固化的温度为150-200℃。
上述的石墨表面梯度碳化硅涂层的制备方法，优选地，所述裂解的具体过程为：在真空条件下，以0.5-2℃/min升温到1000-1200℃，保温2-4h，随后升温到1650-1800℃，保温3-5h。
上述的石墨表面梯度碳化硅涂层的制备方法，优选地，固化后裂解前，还包括：打磨石墨试样表面，以保留石墨试样表面0.5-1mm厚的固化的含硅聚碳硅烷。
上述的石墨表面梯度碳化硅涂层的制备方法，优选地，所述化学气相沉积法的具体过程为：以三氯甲基硅烷为碳化硅气源，氢气作为载气，氩气作为稀释气体，反应温度为1000-1300℃，三氯甲硅烷流量为60-100sccm，氢气流量为600-1000sccm，氩气流量为600-1000sccm，沉积时间为3-15h。
作为一个总的发明构思，本发明还提供一种由上述的石墨表面梯度碳化硅涂层的制备方法所制得的石墨表面梯度碳化硅涂层。
与现有技术相比，本发明的优点在于：
1、本发明的石墨表面梯度碳化硅涂层的制备方法，先通过PIP方法在石墨表面孔隙内形成碳化硅，再采用CVD方法制备一层致密碳化硅涂层，既增强了涂层与基体的结合强度，又缓解了碳化硅与石墨的热膨胀系数不匹配，大大增强了其使用寿命。
2、本发明的石墨表面梯度碳化硅涂层的制备方法，通过在PIP浸渍源——聚碳硅烷中加入硅粉，硅粉随着聚碳硅烷固化分布在石墨表面，在1650℃-1800℃与表面石墨反应生成碳化硅，这样既增强了涂层与石墨基体的结合强度，又避免影响后续CVD SiC的生长。
附图说明
图1为实施例1在石墨表面制备的梯度碳化硅涂层的截面SEM图。
具体实施方式
以下结合具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。
实施例1：
本实施例的石墨表面梯度碳化硅涂层的制备方法，包括以下步骤：
(1)将石墨试样放在去离子水中超声清洗，清洗完成后烘干；
(2)将纳米级硅粉加入液态聚碳硅烷中，纳米硅粉的质量分数为10％，超声震荡混合均匀；
(3)烘干后的试样放进含有硅粉的液态聚碳硅烷中，加压浸渍，浸渍压力在5MPa，随后150℃固化；
(4)打磨样品表面，保留1mm厚表面固化的聚碳硅烷；
(5)样品放入真空炉内，以0.5℃/min升温到1100℃，保温3h；随后升温到1700℃，保温5h；
(6)取出样品，将样品表面打磨平整，采用化学气相沉积法在表面制备碳化硅涂层，以三氯甲基硅烷为碳化硅气源，氢气作为载气，氩气作为稀释气体，反应温度为1100℃，三氯甲硅烷流量为100sccm，氢气流量为1000sccm，氩气流量为1000sccm，沉积时间为4h；
(7)最终在石墨表面得到梯度碳化硅涂层。
参见图1，在石墨表面制备的梯度碳化硅涂层的截面TEM图，可见，PIP方法制备的碳化硅形成于石墨表面孔隙内，CVD方法制备的碳化硅涂层致密，PIP方法制备的碳化硅和CVD方法制备的碳化硅涂层之间通过硅粉与石墨原位生成的碳化硅结合，所得梯度碳化硅涂层既增强了涂层与基体的结合强度，又缓解了碳化硅与石墨的热膨胀系数不匹配，大大增强了其使用寿命。
实施例2：
(1)将石墨试样放在去离子水中超声清洗，清洗完成后烘干；
(2)将纳米级硅粉加入液态聚碳硅烷中，纳米硅粉的质量分数为20％，超声震荡混合均匀；
(3)烘干后的试样放进含有硅粉的液态聚碳硅烷中，加压浸渍，浸渍压力在7MPa，随后200℃固化；
(4)打磨样品表面，保留0.5mm厚表面固化的聚碳硅烷；
(5)样品放入真空炉内，以1℃/min升温到1200℃，保温2h；随后升温到1800℃，保温3h；
(6)取出样品，将样品表面打磨平整，采用化学气相沉积法在表面制备碳化硅涂层，以三氯甲基硅烷为碳化硅气源，氢气作为载气，氩气作为稀释气体，反应温度为1200℃，三氯甲硅烷流量为60sccm，氢气流量为600sccm，氩气流量为600sccm，沉积时间为5h；
(7)最终在石墨表面得到梯度碳化硅涂层。
以上所述，仅是本申请的较佳实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。
Claims (8)
1.一种石墨表面梯度碳化硅涂层的制备方法，其特征在于，包括以下步骤：
S1：将纳米硅粉加入液态聚碳硅烷中，超声震荡混合均匀，得到含有硅粉的液态聚碳硅烷；将石墨试样加压浸渍于含有硅粉的液态聚碳硅烷中，取出后固化、裂解，从而在石墨表面形成初级碳化硅涂层。
S2：采用化学气相沉积法在步骤S1的初级碳化硅涂层表面沉积次级碳化硅涂层，从而初级碳化硅涂层和次级碳化硅涂层形成石墨表面的梯度碳化硅涂层。
2.根据权利要求1所述的石墨表面梯度碳化硅涂层的制备方法，其特征在于，所述含有硅粉的液态聚碳硅烷中，所述纳米硅粉的质量分数为10％-20％。
3.根据权利要求1所述的石墨表面梯度碳化硅涂层的制备方法，其特征在于，所述加压浸渍的压力为5-8MPa，浸渍时间为3-5h。
4.根据权利要求1所述的石墨表面梯度碳化硅涂层的制备方法，其特征在于，所述固化的温度为150-200℃。
5.根据权利要求1所述的石墨表面梯度碳化硅涂层的制备方法，其特征在于，所述裂解的具体过程为：在真空条件下，以0.5-2℃/min升温到1000-1200℃，保温2-4h，随后升温到1650-1800℃，保温3-5h。
6.根据权利要求1所述的石墨表面梯度碳化硅涂层的制备方法，其特征在于，固化后裂解前，还包括：打磨石墨试样表面，以保留石墨试样表面0.5-1mm厚的固化的含硅聚碳硅烷。
7.根据权利要求1-6任一项所述的石墨表面梯度碳化硅涂层的制备方法，其特征在于，所述化学气相沉积法的具体过程为：以三氯甲基硅烷为碳化硅气源，氢气作为载气，氩气作为稀释气体，反应温度为1000-1300℃，三氯甲硅烷流量为60-100sccm，氢气流量为600-1000sccm，氩气流量为600-1000sccm，沉积时间为3-15h。
8.一种由权利要求1-7任一项所述的石墨表面梯度碳化硅涂层的制备方法所制得的石墨表面梯度碳化硅涂层。
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