CN111320478B - 一种碳硅陶瓷靶材的制备方法 - Google Patents

一种碳硅陶瓷靶材的制备方法 Download PDF

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CN111320478B
CN111320478B CN202010234099.7A CN202010234099A CN111320478B CN 111320478 B CN111320478 B CN 111320478B CN 202010234099 A CN202010234099 A CN 202010234099A CN 111320478 B CN111320478 B CN 111320478B
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silicon
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CN111320478A (zh
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白雪
刘宇阳
王星奇
杨磊
桂涛
王星明
储茂友
韩沧
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China Youyan Technology Group Co ltd
GRINM Resources and Environment Technology Co Ltd
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Abstract

本发明公开了一种碳硅陶瓷靶材的制备方法。该制备方法包括以下步骤：(1)根据要制备的靶材的碳硅比，称量石墨粉体、单质硅粉体、SiC粉体，其中单质硅粉体占三者总量的5at％‑15at％；(2)将石墨粉体与单质硅粉体采用卧轴球磨法破碎和混合，得到碳硅预球磨粉体；(3)在碳硅预球磨粉体中添加已称量好的SiC粉体，并置于卧轴球磨罐内球磨混合2小时，得到复合原料粉体；(4)将复合原料粉体筛分后，装入石墨模具中，将模具放在热压炉中，抽真空＜500pa时充入氩气，采用前段快速升温、中段液相烧结和高温氩气保护烧结；(5)冷却得到碳硅陶瓷靶材坯料，经加工、清洗、烘干得到碳硅陶瓷靶材。本发明制备的碳硅陶瓷靶材的相对密度大于90％，硅掺杂含量误差+/‑1at％，电阻率低于0.05Ω·cm，适用于溅射制备DLC薄膜。

Description

一种碳硅陶瓷靶材的制备方法
技术领域
本发明涉及一种碳硅陶瓷靶材的制备方法，属于陶瓷靶材技术领域。
背景技术
类金刚石薄膜(简称DLC)有三个特点：首先其具有较高的电阻率、高硬度、耐磨抗蚀、高热导率和红外区透明等类似于金刚石的优异性能；除此之外，类金刚石还具有很好的化学稳定性和生物相容性，并与硅、锗、石英等材料的折射率能较好地匹配，且与这些基底材料的附着性很好，可以作为一些光学和电子产品的保护层；最后其制备工艺简单、沉积温度低、大面积成膜时膜面光滑平整等优点吸引了科研和产业界的广泛关注。
在DLC薄膜中掺入N、Si金属等杂质可以显著降低内应力，提高热稳定性。已有研究发现掺杂Si之后薄膜性能得到优化，例如降低内应力，提高热稳定性；Si氧化成SiO2覆盖在薄膜表面，阻止薄膜进一步氧化；形成Si-C键，提高薄膜的硬度。
DLC薄膜的制备工艺主要有两种：化学气相沉积法和物理气相沉积法(PVD-Physical Vapor Deposition)。离子束沉积是采用电弧蒸发石墨靶材或以甲烷等为气体源，产生碳离子或碳氢离子并沉积在基体表面形成DLC薄膜，此方法制备温度高，工艺复杂；兰州大学陈丽在CN105887051A专利中以离子液体溶液为原料制备得到离子液体薄膜，将所述离子液体薄膜在惰性气氛下进行热处理得到类金刚石碳薄膜，工艺复杂，不利于工业化生产；溅射沉积属于物理气相沉积，是用高能粒子轰击石墨靶材将原子溅射出来并沉积在基体上形成薄膜。磁控溅射制备DLC薄膜的优势在于制备温度低、工艺简单、大面积成膜均匀性好，一般采用高纯石墨靶材或者共掺杂的方法。
目前，常见的靶材制备方法是采用高温无压烧结或将石墨浸入已预先熔化的硅溶液中产生自发反应等方法制备化学计量比1∶1at％的SiC靶材，此类方法烧结温度高或工艺复杂，对于非化学计量比的硅碳靶材的比例无法精准控制。
发明内容
针对现有技术的不足和缺陷，本发明的目的是提供一种碳硅陶瓷靶材的制备方法，本发明所制备的硅掺杂碳靶材能满足精准的硅掺杂含量，是磁控溅射制备DLC薄膜的优质原材料。
为实现上述目的，本发明采用以下技术方案：
一种碳硅陶瓷靶材的制备方法，包括以下步骤：
(1)称量石墨粉体、单质硅粉体、SiC粉体，其中单质硅粉体占三者总量的5at％-15at％；
(2)将石墨粉体、单质硅粉体采用卧轴球磨法破碎和混合，得到碳硅预球磨粉体；
(3)根据要制备的靶材的碳硅比，向碳硅预球磨粉体中添加SiC粉体，并放置于卧轴球磨罐内球磨混合2小时，得到复合原料粉体；
(4)将复合原料粉体筛分后，装入石墨模具中，将模具放在热压炉中，抽真空＜500pa时充入氩气，开始加热，1小时升温至600-900℃，再经过20-60min(升温时间)升温至1380-1450℃并保温1-2小时后升温至1700-1800℃，保温30-60min；继续升温，在该升温过程中缓慢施加压力，当温度升至1900-2000℃，压力达到50-70MPa时，开始保温保压1-2小时后，关闭加热电源，开始降温；等温度降至1300-1500℃，逐渐缓慢泄压，至常压；
(5)等热压炉完全冷却后，得到碳硅陶瓷靶材坯料，将该靶材坯料进行机械加工、超声清洗、真空烘干，得到碳硅陶瓷靶材。
在所述步骤(1)中，所述石墨粉体的纯度≥99.99％，所述单质硅粉体的纯度≥99.9％。
在所述步骤(2)中，所得碳硅预球磨粉体粒度≤15μm。
在所述步骤(3)中，所用SiC粉体粒径为纳米级，结构为β型，纯度≥99.5％。
在所述步骤(4)中，所述的机械加工为磨削；所述的清洗为将靶材放入纯净水中进行超声清洗10min-20min。
本发明所制备的碳硅陶瓷靶材中硅的掺杂含量范围为10at％-20at％。
本发明与现有技术相比，具有以下有益效果：
本发明制备的碳硅陶瓷靶材的相对密度大于90％，硅掺杂含量误差+/-lat％，电阻率低于0.05Ω.cm。所制备的碳硅陶瓷靶材外观均匀黑色，适用于溅射制备DLC薄膜。具体来讲，本发明的制备方法具有以下优点：
1、采用石墨粉和硅单质粉体为原料，采用卧轴球磨混合预处理工艺制备出晶粒细小混合均匀的碳硅预球磨粉体，有利于提高硅粉在碳粉中的均匀性分散并降低混合粉体的粒度，提高烧结活性；
2、采用纳米β-SiC粉体为掺杂物相，提高靶材致密度；
3、添加Si单质，并在1380-1450℃保温，促使Si元素熔化成液相，利用液相烧结扩散技术，提高靶材的致密度和均匀性。
4、采用前段快速升温、中段液相烧结和高温氩气保护烧结，在致密化速率较快的时间段(1750℃，β型SiC收缩率大)插入保温点均匀了坯料的温度场，从而得到晶粒细小且高致密的靶材。
附图说明
图1为本发明实施例中碳硅混合粉体球磨前的物相结构分析图(XRD)。
图2为本发明实施例中碳硅混合粉体球磨后的物相结构分析图(XRD)。
图3为本发明实施例中碳硅混合粉体球磨前后的组织形貌分析图(SEM)，(a)为球磨前；(b)为球磨后。
图4为本发明实施例中碳硅混合粉体球磨24h的粒径分布图(D50＝14.64μm)。
图5为本发明实施例中碳硅混合粉体球磨48h的粒径分布图(D50＝11.39μm)。
图6为本发明实施例1中所得碳硅靶材的XRD晶体结构分析图。
图7为本发明实施例1中所得碳硅靶材的显微组织图，(a)表示碳硅靶材表面；(b)表示碳硅靶材断面。
图8为实施例2中所得碳硅靶材的组织形貌分析图(SEM)。
图9为实施例3中所得碳硅靶材的组织形貌分析图(SEM)。
具体实施方式
下面通过具体实施方式对本发明做进一步说明，但并不意味着对本发明保护范围的限制。
本发明采用石墨粉体、单质硅粉体、SiC粉体为原料，先将石墨粉体、单质硅粉体混合而成碳硅混合粉体并采用卧轴球磨混合预处理工艺制备出晶粒细小混合均匀的碳硅预球磨粉体，再加入一定量的SiC粉体混合均匀。
首先，根据要制备的碳硅陶瓷靶材的硅碳比，称量一定量的纯度≥99.99％的石墨粉体，按照限定的比例添加硅单质粉体，过筛混合均匀后放置在卧轴球磨中，球料比5∶1，球磨罐大小2.5L，装料量不超过体积的2/3，球磨时间48h，磨球材质为玛瑙。图1-图5是碳硅比为70/10at％的预球磨粉体分析结果，如图1、2所示，通过碳硅混合粉体球磨前后的XRD图谱观察半高宽明显宽化；如图3所示，对比碳硅混合粉体球磨前后的组织形貌分析图(SEM)，观察到颗粒细化和相互包覆，达到了均匀细化效果。图4、5分别为碳硅混合粉体球磨24h、48h的粒径分布图，D50分别为14.64μm、11.39μm。
然后，在碳硅预球磨粉体中加入计算并称量好的纳米β-SiC粉体继续球磨混合2h后过筛得到复合原料粉体。然后称取一定量上述步骤所得到的原料粉体，装入石墨模具中，将石墨模具放置于热压炉内，抽真空到＜500pa时充入氩气并开始升温，1小时温度达到600-900℃，20-60min升温至1380-1450℃，保温1-2小时后升温至1700-1800℃，保温30-60min；继续升温，在该升温过程中缓慢施加压力，当温度升至1900-2000℃，压力达到50-70MPa时，开始保温保压1-2小时，关闭加热电源，开始降温；等温度降至1300-1500℃，逐渐缓慢泄压，至常压；待炉内温度冷却到室温，取出碳硅坯料进行机械加工、清洗、烘干，得到碳硅陶瓷靶材。
实施例1
一种碳硅靶材的制备方法，包括如下步骤：
采用135×213mm的石墨模具，称取1710g预处理复合碳硅粉体(粒度D50＝11.39μm，碳硅预球磨粉体添加β-纳米SiC混合均匀，最终复合粉体组成C/Si/SiC＝70/10/10at％)，平均分为3份(即570g每片，设计厚度8mm)，依次装入石墨模具中，每片粉体采用石墨纸加石墨垫片的方式隔开；将装备好的石墨模具放入热压炉中，调整上下压头的位置，记录当前行程，将压头自然下降后，再次记录初始行程，抽真空至210pa时充入高纯氩气，开始升温，1小时快速升温至880℃，随后40min升温至1380℃保温30min，30min升温至1450℃保温30min，再升温至1700℃，开始缓慢施加压力并保温40min，随后将温度升至1980℃时，压力达到68Mpa，保温2-3小时，关闭电源，随后保压至1526℃，停压停炉。
设计靶材出炉厚度为8mm，靶材实际密度为2.34-2.35g/cm3，相对密度为90％左右，强度好，外观完整，呈黑色靶材。
测试预球磨硅碳混合粉体的粒径分布、靶材电阻率、氮氧含量、金属杂质含量、物相结构、微观形貌结果如下：
四探针测试靶材电阻率：0.0047ohm·cm；
惰气脉冲红外法测试O含量：0.034wt％；
惰气脉冲热导法测试N含量：0.022wt％；
重量法测试Si含量：36.22wt％(Si含量+/-lat％范围为36.1～37.87wt％)；
如图6所示，所得靶材的物相结构为C和SiC。该靶材的SEM微观形貌图如图7所示。
实施例2(对比例)
一种碳硅靶材的制备方法，包括如下步骤：
采用119×134mm的石墨模具，称取81g纳米β-SiC粉体、18.9g Si粉以及105.1g C粉过筛混合均匀(无球磨处理)，单质Si含量5at％原子比，总碳硅比80∶20at％，C粉粒度D50＝23μm。将上述过筛混合粉体205g(设计厚度5mm)，装入石墨模具中，采用石墨纸加石墨垫片的方式隔开；将装备好的石墨模具放入热压炉中，调整上下压头的位置，记录当前行程，将压头自然下降后，再次记录初始行程，抽真空至500pa时充入高纯氩气，开始升温，1小时快速升温至600℃，随后55min升温至1380℃-1450℃保温1h15min，再升温至1700℃，开始缓慢施加压力并保温30min，随后将温度升至1980℃时，压力达到30Mpa，保温2-3小时，关闭电源，随后保压至1573℃，停压停炉。
设计靶材出炉厚度为5mm，实际靶材出炉为5.58mm，靶材实际密度为2.11g/cm3，相对密度为82％左右，外观完整，呈黑色靶材，检测其微观组织形貌图如图8所示，存在SiC富集区域，组织成分不均匀。
实施例3(对比例)
一种碳硅靶材的制备方法，包括如下步骤：
采用119×134mm的石墨模具，称取81g纳米β-SiC粉体、18.9g Si粉以及105.1g C粉过筛混合均匀后，放置在卧轴球磨罐中球磨混合8小时，单质Si含量5at％原子比，总碳硅比80∶20at％。称取上述粉体194g(设计厚度5mm)，装入石墨模具中，采用石墨纸加石墨垫片的方式隔开；将装备好的石墨模具放入热压炉中，调整上下压头的位置，记录当前行程，将压头自然下降后，再次记录初始行程，抽真空至330pa时充入高纯氩气，开始升温，1小时快速升温至900℃，随后60min升温至1380℃-1450℃保温1h，再升温至1700℃-1750℃，开始缓慢施加压力并保温40min，随后将温度升至1980℃时，压力达到34Mpa，保温2-3小时，关闭电源，随后保压至1538℃，停压停炉。
设计靶材出炉厚度为5mm，实际靶材出炉为5.12mm，靶材实际密度为2.28g/cm3，相对密度为87％左右，外观完整，呈黑色靶材，检测其微观组织形貌图如图9所示，存在SiC富集区域，组织成分不均匀。

Claims (6)

1.一种碳硅陶瓷靶材的制备方法，其特征在于，包括以下步骤：
（1）根据要制备的靶材的碳硅比，称量石墨粉体、单质硅粉体、SiC粉体，其中单质硅粉体占三者总量的5at%-15at%；
（2）将石墨粉体、单质硅粉体采用卧轴球磨法破碎和混合，得到碳硅预球磨粉体；
（3）向碳硅预球磨粉体中添加SiC粉体，并放置于卧轴球磨罐内球磨混合2小时，得到复合原料粉体；
（4）将复合原料粉体筛分后，装入石墨模具中，将模具放在热压炉中，抽真空<500pa时充入氩气，开始加热，1小时升温至600-900℃，再经过20-60min升温至1380-1450℃并保温1-2小时后升温至1700-1800℃，保温30-60min；继续升温，在该升温过程中缓慢施加压力，当温度升至1900-2000℃，压力达到50-70MPa时，开始保温保压 1-2小时后，关闭加热电源，开始降温；等温度降至1300-1500℃，逐渐缓慢泄压，至常压；
（5）等热压炉完全冷却后，得到碳硅陶瓷靶材坯料，将该靶材坯料进行机械加工、超声清洗、真空烘干，得到碳硅陶瓷靶材。
2.根据权利要求1所述的碳硅陶瓷靶材的制备方法，其特征在于，在所述步骤（1）中，所述石墨粉体的纯度≥99.99%，所述单质硅粉体的纯度≥99.9%。
3.根据权利要求1所述的碳硅陶瓷靶材的制备方法，其特征在于，在所述步骤（2）中，所得碳硅预球磨粉体粒度≤15μm。
4.根据权利要求1所述的碳硅陶瓷靶材的制备方法，其特征在于，在所述步骤（3）中，所用SiC粉体粒径为纳米级，结构为β型，纯度≥99.5%。
5.根据权利要求1所述的碳硅陶瓷靶材的制备方法，其特征在于，在所述步骤（5）中，所述的机械加工为磨削；所述的清洗为将靶材放入纯净水中进行超声清洗10min-20min。
6.根据权利要求1-5中任一项所述的碳硅陶瓷靶材的制备方法，其特征在于，所述碳硅陶瓷靶材中硅的掺杂含量范围为10at%-20at%。
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