CN112779517B - 一种自支撑纳米锥金刚石的制备方法 - Google Patents

一种自支撑纳米锥金刚石的制备方法 Download PDF

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CN112779517B
CN112779517B CN202011578907.8A CN202011578907A CN112779517B CN 112779517 B CN112779517 B CN 112779517B CN 202011578907 A CN202011578907 A CN 202011578907A CN 112779517 B CN112779517 B CN 112779517B
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袁晓溪
杨峰
曾旭
李楠
张文颖
李宏
郭明
冯悦姝
李美萱
杨璐赫
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Jilin Teachers Institute of Engineering and Technology
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/274—Diamond only using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

Abstract

本发明的一种自支撑纳米锥金刚石的制备方法，属于金刚石纳米结构及其制备的技术领域。首先以高CH4与H2流量比例并通入氮气掺杂，生长金刚石及非金刚石混合相，形成金刚石倒锥；再调低CH4与H2流量比例生长金刚石相；去除衬底，空气中高温退火刻蚀掉非金刚石相，制备出自支撑纳米锥金刚石。本发明通过不同CH4与H2流量比例沉积生长和通入氮气有助于生长100面晶向形成倒锥，制备了高密度纳米锥金刚石，大大增大了金刚石膜的表面积；并且相比于自上而下的掩膜法或等离子体刻蚀法，制备方法工艺简单，便于大规模制备。

Description

一种自支撑纳米锥金刚石的制备方法
技术领域
本发明属于金刚石纳米结构及其制备的技术领域，涉及一种新型自支撑纳米锥金刚石的制备方法。
背景技术
金刚石是一种具有超硬度、高导热系数、化学惰性、稳定性等优良性能的功能材料。制备金刚石的纳米结构(例如纳米织构、纳米线和多孔金刚石等)可应用于多领域研究。但是，由于极高的硬度和化学惰性，不便于能通过机械加工或湿化学腐蚀来改变金刚石的形貌。
本发明制备了一种利用自下而上法结合金刚石自身生长取向产生自支撑纳米锥的金刚石膜结构，大大增大了金刚石膜的表面积。
和本发明接近的现有技术是授权号为CN106835011B，名称为“一种具有类金刚石阵列的结构件及其制备方法”的专利申请，制备方法是通过对形成在基体上的一类金刚石涂层进行刻蚀得到。所述具有类金刚石阵列的结构件可以对细菌的细胞壁产生压力，穿刺细菌的细胞壁使其伸展并最终溶解,导致细菌死亡,有效破坏生物膜的形成，赋予该结构件显著的抗菌性能。
发明内容
本发明要解决的技术问题是通过自下而上法结合金刚石自身生长取向产生自支撑纳米锥的金刚石膜结构，大大增大了金刚石膜的表面积。
纳米锥金刚石膜制备的具体技术方案如下：
一种自支撑纳米锥金刚石的制备方法，以硅片或钼片为衬底，经过衬底预处理、微波等离子体化学气相沉积镀膜和高温退火的过程，其特征在于，
所述的微波等离子体化学气相沉积镀膜，是将预处理过的衬底置于化学气相沉积(CVD)装置的腔体中，在微波功率350W，腔体气压8KPa下，先以CH4、H2与N2流量比例5～8:100:0.5，生长金刚石及非金刚石混合相5小时，再关闭N2流量，调低CH4与H2流量比例为1:100，生长金刚石相；
所述的高温退火，是先去除衬底，再在空气中800℃高温退火，刻蚀掉非金刚石相，制得自支撑纳米锥金刚石。
所述的衬底预处理，可以按常规方法进行，也可以将衬底用纳米金刚石粉研磨，再置于纳米金刚石悬浊液中超声1～2小时，最后依次用丙酮、无水乙醇、去离子水超声清洗，取出后氮气吹干。
所述的去除衬底，对硅衬底是在生长金刚石相后，将其放入氢氟酸和硝酸混合溶液中浸泡24小时以上；对钼衬底是关闭化学气相沉积装置后，以80℃/min速率快速降温，使钼衬底与生长的金刚石及非金刚石混合相脱离。
本发明化学气相沉积(CVD)镀膜方法,是微波等离子体(MPCVD)法，也可以是热灯丝(HFCVD)，热阴极(DCCVD)等方法。可以是在硅、钛等衬底上异质外延生长多晶膜，薄膜可以是非掺杂的，或半导体掺杂的。
高温退火刻蚀非金刚石相后形成高密度纳米锥结构并表面氧终止，可以经过化学处理使表面为氢终止。
本发明解决的技术问题是自下而上结合金刚石生长取向制备了高密度纳米锥金刚石膜。以金刚石和非金刚石相共同生长，通入氮气有助于生长100面晶向，形成倒锥，然后刻蚀掉非金刚石相制备了自支撑高密度纳米锥金刚石，同时纳米锥表面具有很多坑式结构，这是本发明专利所涉及的主要内容和重要创新点。并且相比于自上而下的掩膜法或等离子体刻蚀法，制备方法工艺简单，便于大规模制备。本研究将对金刚石纳米锥结构及其制备领域具有重要意义。
附图说明
图1为纳米锥金刚石结构制备过程示意图。
图2为高甲烷氢气比例下纳米锥金刚石形貌图。其中(B)为(A)的放大图。
图3为测试实施例1纳米锥金刚石和金刚石膜比表面积的循环伏安(CV)曲线。
具体实施方式
以下结合附图与实施例对本申请作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本申请的理解，而对其不起任何限定作用。
实施例1：硅片衬底纳米锥金刚石膜的制备
选取1cm×1cm大小的硅片作为生长衬底，首先将硅片清洗，去除表面污染物。为了提高生长过程的成核密度，将其生长面放在含金刚石粉的砂纸上研磨15～30分钟，并放入含有金刚石粉的酒精中超声处理1小时，最后经过丙酮、酒精、去离子水依次超声清洗10min，用氮气吹干后放入CVD反应室沉积金刚石膜。主要生长参数为：氢气、甲烷、氮气的气体流量分别为200sccm、10sccm、1sccm，微波功率350W，腔体气压8KPa，生长时间5小时，得到金刚石与非金刚石混合相，薄膜沉积厚度约为20μm。关闭氮气流量、调低甲烷浓度，氢气、甲烷的气体流量分别为200sccm、2sccm，微波功率350W，腔体气压8KPa，生长时间5小时，生长金刚石相，薄膜沉积厚度约为4μm。将样品置于氢氟酸和硝酸混合溶液中24小时以上，去除硅衬底，用去离子水清洗，氮气吹干。将得到薄膜置于管式炉中，800℃高温退火20分钟，刻蚀掉非金刚石相，成功制备自支撑纳米锥金刚石。
制备过程示意图如图1所示。
扫描电镜图如图2所示。纳米锥高度4～6um,纳米锥密度1.3х107cm-2。纳米锥表面具有很多坑式晶界结构。
在高甲烷流量生长金刚石与非金刚石相中，氮气的主要作用是利于金刚石(100)面生长，形成倒四棱锥结构，如果不加氮气，就不能生长出本发明的锥结构。
为了验证纳米锥金刚石相比于生长面金刚石膜的实际面积增大，在0.1M Na2SO4溶液中测试了纳米锥金刚石和金刚石膜的循环伏安(CV)曲线，如图3所示，扫描电位区间介于-0.5～0.9V，扫速0.1mV/s，CV曲线的积分面积/扫速即是电量，通过库伦转移电量，可以计算出纳米锥金刚石的有效面积约为生长面金刚石膜的8.6倍，由此验证纳米锥金刚石具有更大的比表面积。
实施例2：钼衬底纳米锥金刚石膜的制备
选取1cm×1cm大小的钼片作为生长衬底，首先将钼片清洗，去除表面污染物。为了提高生长过程的成核密度，将其生长面放在含金刚石粉的砂纸上研磨15～30min，并放入含有金刚石粉的酒精中超声处理2h，最后经过丙酮、酒精、去离子水依次超声清洗，用氮气吹干后放入CVD反应室沉积金刚石膜。主要生长参数为：氢气、甲烷、氮气的气体流量分别为200sccm、16sccm、1sccm，微波功率350W，腔体气压8KPa，时间5小时，生长金刚石与非金刚石混合相，薄膜沉积厚度约为20μm。关闭氮气流量、调低甲烷浓度，氢气、甲烷的气体流量分别为200sccm、2sccm，微波功率350W，腔体气压8KPa，生长时间5小时，生长金刚石相，薄膜沉积厚度约为4μm。关闭CVD装置时采用快速降温模式去除钼衬底，由于钼片与金刚石热导率差异大，钼片易与金刚石薄膜分离。本实施例的钼衬底是关闭化学气相沉积装置后，以80℃/min速率快速降温，使钼衬底与生长的金刚石及非金刚石混合相脱离。将得到自支撑薄膜置于管式炉中，800℃高温退火20分钟，刻蚀掉非金刚石相，成功制备自支撑纳米锥金刚石。

Claims (3)

1.一种自支撑纳米锥金刚石的制备方法，以硅片或钼片为衬底，经过衬底预处理、微波等离子体化学气相沉积镀膜和高温退火的过程，其特征在于，
所述的微波等离子体化学气相沉积镀膜，是将预处理过的衬底置于化学气相沉积装置的腔体中，在微波功率350W，腔体气压8KPa下，先以CH4、H2与N2流量比例5～8:100:0.5，生长金刚石及非金刚石混合相5小时，再关闭N2流量，调低CH4与H2流量比例为1:100，生长金刚石相；
所述的高温退火，是先去除衬底，再在空气中800℃高温退火，刻蚀掉非金刚石相，制得自支撑纳米锥金刚石。
2.根据权利要求1所述的自支撑纳米锥金刚石的制备方法，其特征在于，所述的衬底预处理，是将衬底用纳米金刚石粉研磨，再置于纳米金刚石悬浊液中超声1～2小时，最后依次用丙酮、无水乙醇、去离子水超声清洗，取出后氮气吹干。
3.根据权利要求1或2所述的自支撑纳米锥金刚石的制备方法，其特征在于，所述的去除衬底，对硅衬底是在生长金刚石相后，将其放入氢氟酸和硝酸混合溶液中浸泡24小时以上；对钼衬底是关闭化学气相沉积装置后，以80℃/min速率快速降温，使钼衬底与生长的金刚石及非金刚石混合相脱离。
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