CN106367717B - 一维碳纳米管和三维石墨烯复合材料图形化生长方法 - Google Patents

一维碳纳米管和三维石墨烯复合材料图形化生长方法 Download PDF

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CN106367717B
CN106367717B CN201610695734.5A CN201610695734A CN106367717B CN 106367717 B CN106367717 B CN 106367717B CN 201610695734 A CN201610695734 A CN 201610695734A CN 106367717 B CN106367717 B CN 106367717B
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于乐泳
胡云
孙泰
杨俊�
魏大鹏
史浩飞
杜春雷
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Chongqing Institute of Green and Intelligent Technology of CAS
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Abstract

本发明提供了一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，隶属微纳制造领域。该方法先对生长基底进行图形化处理，再对图形化后的生长基底进行制绒处理，然后采用磁控溅射方法在生长基底上沉积催化剂，再复合生长一维碳纳米管和三维石墨烯，最后将一维碳纳米管和三维石墨烯复合材料从生长基底上剥离。该方法解决了传统工艺中程序复杂，且不能直接从生长基底剥离的问题，此方法可以直接把图形化后的石墨烯复合材料应用于柔性器件等领域。

Description

一维碳纳米管和三维石墨烯复合材料图形化生长方法
技术领域
本发明涉及一种纳米复合材料的图形化生长方法，具体为一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，隶属微纳制造领域。
背景技术
石墨烯，一个杂化的SP2六角型薄膜，它是目前发现最薄的二维材料。石墨烯具有很多优异的特性，它具有很好的柔韧性和透光性，石墨烯中的载流子迁移率远高于传统的硅材料，室温下本征载流子迁移率高达2.0×105cm2/(V.S)。另外，它具有高的热导率(约5000W/m.k)、极高的杨氏模量(1.06TPa)和巨大的比表面积2630m2/g。这些性质使石墨烯受到人们广泛的关注，它在高性能复合材料、柔性显示、光通信、光电探测和传感器件等诸多领域都具有广阔的应用前景。
碳纳米管是由单层或多层石墨烯片围绕同一中心轴按一定的螺旋角卷曲而成的无缝纳米级管结构，两端通常被由五元环和七元环参与形成的半球形大富勒烯分子封住，由于碳纳米管管壁中的碳原子采用的是SP2杂化，因此碳纳米管沿轴向具有高模量和高强度，另外其特殊的结构也赋予碳纳米管特异的光、电、磁、热、化学和力学特性，具有极其广泛的应用。
石墨烯和碳纳米管都是纳米尺寸的碳材料，具有极大的比表面积、良好的导电性以及优秀的机械性能等特性，它们之间可以产生一种协同效应，使其各种物理化学性能得到增强，因而这种复合材料在很多领域有着极大的应用前景，这也使得石墨烯/碳纳米管复合材料的制备得到了广泛的关注。
目前单层石墨烯薄膜跟碳纳米管的复合材料制备方法已经得到了广泛研究，但是对三维石墨烯跟碳纳米管复合的研究还非常少。目前常用的石墨烯/碳纳米管复合材料的制备方法有：化学气相沉积法(CVD)，一般步骤为首先在铜箔上沉积石墨烯薄膜，然后在石墨烯薄膜涂上一层催化剂，然后再次利用CVD法在催化剂表面沉积碳纳米管，最后出去铜箔。此方法，工艺流程繁多，不利用产业化生产。
发明内容
针对传统石墨烯复合材料生长流程复杂且不能直接图形化应用到器件上，本发明提出了一种图形化生长一维碳纳米管和三维石墨烯复合材料的方法，该方法包括如下步骤：
(1)对生长基底进行图形化：先采用微纳米加工技术在掩模板上制作掩模板图形，再利用掩模板对生长基底进行图形化处理，掩模板图形可为任意形状；
(2)对图形化后的生长基底进行制绒处理：将图形化后的生长基底浸泡于浓度为2-10％氢氟酸溶液中，然后取出生长基底，用无水乙醇、去离子水分别超声5-10分钟，最后将生长基底吹干；
(3)采用磁控溅射方法在生长基底上沉积催化剂：将掩模板对齐图形化并制绒的生长基底上，采用磁控溅射方法，在生长基底上沉积不连续的2-6nm的金属粒子，作为生长一维碳纳米管的催化剂；
(4)复合生长一维碳纳米管和三维石墨烯：保持掩模板与生长基底对齐，将沉积完催化剂的生长基底放置于微波CVD反应炉中，通入碳源和辅助气体，温度为200-600℃，生长时间10-60分钟，最后冷却；
(5)剥离一维碳纳米管和三维石墨烯复合材料：将复合生长完一维碳纳米管和三维石墨烯的生长基底从反应炉中取出，从生长基底表面取掉掩模板，再在生长基底表面涂覆一层柔性材料，厚度为50-100um，并将其烘干，最后将一维碳纳米管和三维石墨烯复合材料从生长基底上剥离。
所述生长基底可以为硅基底、石英基底或泡沫镍。
所述图形化处理的方法为反应等离子体刻蚀。
所述催化剂可以为铁、钴或镍金属粒子。
所述碳源为同时含有SP3和SP2碳原子的有机化合物。
进一步，所述碳源为甲烷或乙烯。
所述辅助气体可以为氢气或氩气。
所述柔性材料为聚氨酯弹性体。
本发明提供了一种图形化生长一维碳纳米管和三维石墨烯复合材料的方法，解决了传统工艺中程序复杂，且不能直接从生长基底剥离的问题，此方法可以直接把图形化后的石墨烯复合材料应用于柔性器件等领域。
附图说明
图1为本发明所提供的一维碳纳米管和三维石墨烯复合材料图形化生长方法的流程图。
图2为实施例1中图形化后硅基底的俯视图。
图3为实施例1中图形化后硅基底的截面图。
图4为实施例1中一维碳纳米管和三维石墨烯复合材料图形化生长完成并从生长基底上剥离后的示意图。
具体实施方式
下面结合附图和实施例详细介绍本发明，但以下实施例仅限于解释本发明，本发明的保护范围应包括权利要求的全部内容。
实施例一
本实施例提供一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，该方法的流程图如附图1所示，具体步骤如下：
(1)对生长基底进行图形化：选用6cm×6cm尺寸大小铜板作为掩模板基材，，利用微纳米加工技术在铜板板上制作出掩模板图形，掩模板图形为5mm×5mm尺寸大小的正方形，掩模板图形以阵列方式排列；同时选取一块尺寸大小同样为6cm×6cm的硅衬底，厚度为2mm，在硅衬底表面涂覆一层az1500光刻胶，胶厚2um，然后将掩模板覆盖于涂有光刻胶的硅衬底之上，掩模板的边缘与硅衬底对齐，在365nm紫外曝光机下，采用接触式曝光方法，曝光剂量100mJ/cm2，显影30s，将光刻胶复制成掩模板图形，曝光完毕后，用酒精将未固化的光刻胶显影掉；然后将带有光刻胶的硅衬底放置于等离子体刻蚀机中，采用六氟化硫进行干法刻蚀，气体流量为6sccm，刻蚀功率100w，刻蚀时间5h，刻蚀深度为10um，刻蚀完毕后得到的图形化硅衬底即为一维碳纳米管和三维石墨烯复合材料的生长基底，图形化后的生长基底俯视图和截面示意图如附图2和附图3所示；
(2)对图形化后的生长基底进行制绒处理：将图形化后的硅基底放置于浓度为2％的氢氟酸溶液中浸泡8分钟，对硅基底进行制绒处理，然后取出硅基底，用无水乙醇、去离子水分别超声10分钟，最后将硅基底吹干；
(3)采用磁控溅射方法在生长基底上沉积催化剂：将掩模板放置于图形化后并经过制绒处理的硅基底上，并保持掩模板图形和硅基底上的图形对齐，将其一同放置于磁控溅射设备中，采用直流溅射，功率为100W，溅射气体为氩气，流量为10sccm，溅射压强为2Pa，溅射时间2秒，在硅基底的孔洞内沉积不连续的2-6nm的Fe粒子，作为生长一维碳纳米管的催化剂；
(4)复合生长一维碳纳米管和三维石墨烯：将沉积完催化剂的硅基底放置于微波CVD反应炉中，碳源为甲烷，甲烷流量为2sccm，辅助气体为氢气，氢气流量为10sccm，温度为600℃，微波功率600W，压强10毫巴，生长时间90分钟，最后冷却；
(5)剥离一维碳纳米管和三维石墨烯复合材料：将复合生长完一维碳纳米管和三维石墨烯的硅基底从反应炉中取出，从硅基底表面取掉掩模板，再在硅基底表面涂覆一层聚氨酯弹性体，厚度为100um，并将其烘干，最后将一维碳纳米管和三维石墨烯复合材料从硅基底上剥离，得到的复合材料如附图4所示。
实施例二
本实施例提供一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，该方法的流程图如附图1所示，具体步骤如下：
(1)对生长基底进行图形化：选用5cm×5cm尺寸大小铜板作为掩模板基材，，利用微纳米加工技术在铜板板上制作出掩模板图形，掩模板图形为4mm×3mm尺寸大小的长方形，掩模板图形以阵列方式排列；同时选取一块尺寸大小同样为5cm×5cm的石英衬底，厚度为2mm，在石英衬底表面涂覆一层az1500光刻胶，胶厚2um，然后将掩模板覆盖于涂有光刻胶的石英衬底之上，掩模板的边缘与石英衬底对齐，在365nm紫外曝光机下，采用接触式曝光方法，曝光剂量100mJ/cm2，显影30s，将光刻胶复制成掩模板图形，曝光完毕后，用酒精将未固化的光刻胶显影掉；然后将带有光刻胶的石英衬底放置于等离子体刻蚀机中，采用六氟化硫进行干法刻蚀，气体流量为6sccm，刻蚀功率100w，刻蚀时间5h，刻蚀深度为10um，刻蚀完毕后得到的图形化石英衬底即为一维碳纳米管和三维石墨烯复合材料的生长基底；
(2)对图形化后的生长基底进行制绒处理：将图形化后的石英基底放置于浓度为6％的氢氟酸溶液中浸泡2分钟，对石英基底进行制绒处理，然后取出石英基底，用无水乙醇、去离子水分别超声5分钟，最后将石英基底吹干；
(3)采用磁控溅射方法在生长基底上沉积催化剂：将掩模板放置于图形化后并经过制绒处理的石英基底上，并保持掩模板图形和石英基底上的图形对齐，将其一同放置于磁控溅射设备中，采用直流溅射，功率为100W，溅射气体为氩气，流量为10sccm，溅射压强为2Pa，溅射时间5秒，在石英基底的孔洞内沉积不连续的2-6nm的钴粒子，作为生长一维碳纳米管的催化剂；
(4)复合生长一维碳纳米管和三维石墨烯：将沉积完催化剂的石英基底放置于PECVD反应炉中，原料气体为乙烯，乙烯流量为7sccm，辅助气体为氩气，流量为40sccm，温度为400℃，射频功率100-W，气压为50Pa，生长时间60分钟，最后冷却；
(5)剥离一维碳纳米管和三维石墨烯复合材料：将复合生长完一维碳纳米管和三维石墨烯的石英基底从反应炉中取出，从石英基底表面取掉掩模板，再在石英基底表面涂覆一层聚氨酯弹性体，厚度为80um，并将其烘干，最后将一维碳纳米管和三维石墨烯复合材料从石英基底上剥离。
实施例三
本实施例提供一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，该方法的流程图如附图1所示，具体步骤如下：
(1)对生长基底进行图形化：选用4cm×4cm尺寸大小铜板作为掩模板基材，，利用微纳米加工技术在铜板板上制作出掩模板图形，掩模板图形为直径为2mm尺寸大小的圆形，掩模板图形以阵列方式排列；同时选取一块尺寸大小同样为4cm×4cm的泡沫镍衬底，厚度为2mm，在泡沫镍衬底表面涂覆一层az1500光刻胶，胶厚2um，然后将掩模板覆盖于涂有光刻胶的泡沫镍衬底之上，掩模板的边缘与泡沫镍衬底对齐，在365nm紫外曝光机下，采用接触式曝光方法，曝光剂量100mJ/cm2，显影30s，将光刻胶复制成掩模板图形，曝光完毕后，用酒精将未固化的光刻胶显影掉；然后将带有光刻胶的泡沫镍衬底放置于等离子体刻蚀机中，采用六氟化硫进行干法刻蚀，气体流量为6sccm，刻蚀功率100w，刻蚀时间5h，刻蚀深度为10um，刻蚀完毕后得到的图形化泡沫镍衬底即为一维碳纳米管和三维石墨烯复合材料的生长基底；
(2)对图形化后的生长基底进行制绒处理：将图形化后的泡沫镍基底放置于浓度为10％的氢氟酸溶液中浸泡30秒，对泡沫镍基底进行制绒处理，然后取出泡沫镍基底，用无水乙醇、去离子水分别超声8分钟，最后将泡沫镍基底吹干；
(3)采用磁控溅射方法在生长基底上沉积催化剂：将掩模板放置于图形化后并经过制绒处理的泡沫镍基底上，并保持掩模板图形和泡沫镍基底上的图形对齐，将其一同放置于磁控溅射设备中，采用直流溅射，功率为100W，溅射气体为氩气，流量为100sccm，溅射压强为2Pa，溅射时间10秒，在泡沫镍基底的孔洞内沉积不连续的2-6nm的镍粒子，作为生长一维碳纳米管的催化剂；
(4)复合生长一维碳纳米管和三维石墨烯：将沉积完催化剂的泡沫镍基底放置于PECVD反应炉中，原料气体为乙烯，乙烯流量为10sccm，辅助气体为氩气，流量为60sccm，温度为600℃，射频功率100W，气压为100Pa，生长时间30分钟，最后冷却；
(5)剥离一维碳纳米管和三维石墨烯复合材料：将复合生长完一维碳纳米管和三维石墨烯的泡沫镍基底从反应炉中取出，从泡沫镍基底表面取掉掩模板，再在泡沫镍基底表面涂覆一层聚氨酯弹性体，厚度为50um，并将其烘干，最后将一维碳纳米管和三维石墨烯复合材料从泡沫镍基底上剥离。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (4)

1.一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，其特征在于，该方法包括如下步骤：
(1)对生长基底进行图形化：先采用微纳米加工技术在掩模板上制作掩模板图形，再利用掩模板对生长基底进行图形化处理，掩模板图形可为任意形状；
(2)对图形化后的生长基底进行制绒处理：将图形化后的生长基底浸泡于浓度为2-10％氢氟酸溶液中，然后取出生长基底，用无水乙醇、去离子水分别超声5-10分钟，最后将生长基底吹干；
(3)采用磁控溅射方法在生长基底上沉积催化剂：将掩模板对齐图形化并制绒的生长基底上，采用磁控溅射方法，在生长基底上沉积不连续的2-6nm的铁、钴或镍金属粒子，作为生长一维碳纳米管的催化剂；
(4)复合生长一维碳纳米管和三维石墨烯：保持掩模板与生长基底对齐，将沉积完催化剂的生长基底放置于微波CVD反应炉中，通入甲烷或乙烯作为碳源，同时通入辅助气体氢气或氩气，温度为200-600℃，生长时间10-60分钟，最后冷却；
(5)剥离一维碳纳米管和三维石墨烯复合材料：将复合生长完一维碳纳米管和三维石墨烯的生长基底从反应炉中取出，从生长基底表面取掉掩模板，再在生长基底表面涂覆一层柔性材料，厚度为50-100um，并将其烘干，最后将一维碳纳米管和三维石墨烯复合材料从生长基底上剥离。
2.根据权利要求1所述的一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，其特征在于，所述生长基底为硅基底、石英基底或泡沫镍。
3.根据权利要求1所述的一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，其特征在于，所述图形化处理的方法为反应等离子体刻蚀。
4.根据权利要求1所述的一种一维碳纳米管和三维石墨烯复合材料图形化生长方法，其特征在于，所述柔性材料为聚氨酯弹性体。
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