CN111362258A - 一种蜂蜡作支撑层的石墨烯薄膜转移方法 - Google Patents
一种蜂蜡作支撑层的石墨烯薄膜转移方法 Download PDFInfo
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Abstract
本发明公开了一种金属基底石墨烯薄膜的转移方法，包括如下步骤：(1)将蜂蜡溶液旋涂至金属基底的石墨烯薄膜表面上，形成作为支撑层的蜂蜡层，得到蜂蜡层/石墨烯薄膜/金属基底；(2)用腐蚀液去除金属基底得到蜂蜡层/石墨烯薄膜，再将蜂蜡层/石墨烯薄膜转移至目标基底并干燥；(3)采用有机溶剂除去蜂蜡层，实现石墨烯薄膜的转移。该采用自然无毒无害的蜂蜡作为支撑层材料，可获得表面干净完整且面电阻低的单层石墨烯薄膜。
Description
技术领域
本发明涉及二维纳米材料技术领域，具体涉及一种蜂蜡作支撑层的石墨烯薄膜转移方法。
背景技术
近年来，芯片逐步向小型化、多功能化发展，这也对相关的光、电子器件及其材料提出了更高要求。以石墨烯为代表的二维(2D)材料，以纳米线(NWs)为代表的一维(1D)材料，以及以量子点(QDs)为代表的零维(0D)材料都因为在光电器件中具有极大的应用前景而受到学术界和工业界的广泛关注。
石墨烯是一种二维的单层碳材料，具有出色的电，光，机械和热学性能，同时还具有稳定的可调控性，已引起全球科学和工业界的极大关注。这些特性使石墨烯具备广泛的应用前景，尤其是在电子和光电设备中，例如光电探测器和光调制器。
现有的用于石墨烯薄膜大规模合成的方法有，化学气相沉积和在碳化硅衬底上外延生长等。其中，通常认为在催化金属基底(例如铜，镍)上进行化学气相沉积是制备高质量和高产量石墨烯薄膜的最可靠方法。为了将化学气相沉积合成的石墨烯薄膜集成到现代电子，光电子，传感器以及能量存储设备中去，有必要开发一种干净和完整地将石墨烯薄膜转移到目标基底上的方法。
由于石墨烯薄膜透明且易碎，因此必须引入聚合物支撑层以保护石墨烯薄膜，并使其在转移过程中可见。公开号为CN103449418A的专利说明书公开了一种采用聚甲基丙烯酸甲酯(PMMA)作为支撑层的石墨烯薄膜转移方法，PMMA固化后通过过硫酸铵溶液腐蚀除去金属基底，捞起干燥后选用乙酸溶剂溶解PMMA层，最后通过高温退火方式进一步除去石墨烯薄膜表面残留PMMA。该方法的不足在于，PMMA与石墨烯薄膜结合力较强，不能通过有机溶剂完全除去而需要后续退火，所需温度较高且耗时较长。
另根据最近文献报道，有学者使用樟脑作为支撑材料用于石墨烯薄膜转移(Bananakere Nanjegowda Chandrashekar等，《Journal of Colloid and InterfaceScience》，2019年546卷，11-19)。原因是樟脑与石墨烯薄膜之间的表面吸附能仅为0.09eV，远小于其他支撑层材料，如PMMA与石墨烯的表面吸附能为1.45eV，松香为1.04eV。樟脑作为石墨烯转移支撑层的优点是与石墨烯作用较小，易于除去。但是所得石墨烯完整性不佳，因而限制了这种方法的大规模实际应用。
根据用聚合物支撑层进行的石墨烯薄膜转移的基本原理，理想的支撑层必须满足以下要求。首先，聚合物必须在特定化学溶剂中具有足够的溶解度，以便旋涂到石墨烯表面上并从石墨烯表面完全去除。其次，支撑层必须与石墨烯形成足够牢固的相互作用，以避免在转移过程中发生结构破坏。
发明内容
针对本领域存在的不足之处，本发明提供了一种采用蜂蜡为支撑层材料的石墨烯薄膜转移方法。蜂蜡转移的石墨烯更加完整和干净，转移得到的石墨烯薄膜具有更好的质量。
一种蜂蜡作支撑层的石墨烯薄膜转移方法，所述方法包括：
(1)将蜂蜡溶液旋涂至金属基底的石墨烯薄膜表面上，形成作为支撑层的蜂蜡层，得到蜂蜡层/石墨烯薄膜/金属基底；
(2)用腐蚀液去除金属基底，再将蜂蜡层/石墨烯薄膜转移至目标基底并干燥；
(3)采用有机溶剂除去蜂蜡层，实现石墨烯薄膜的转移。
在本发明中，蜂蜡是一种从蜂窝中提取的天然物质，对环境友好且成本低廉。其主要成分是棕榈酸酯等，化学式近似为C15H31COOC30H61。
本发明所用的石墨烯薄膜是采用化学气相沉积法在金属铜基底上合成的单层石墨烯，但也可以是在其它金属衬底上制备的石墨烯薄膜。石墨烯是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢状晶格的平面薄膜，是只有一个碳原子厚度的二维材料，又可称为单层石墨烯。本发明所述的石墨烯薄膜为1-10层的石墨烯薄膜。
在步骤(1)中，所述旋涂的环境温度高于或等于60℃；旋涂后静置形成蜂蜡层。
所述旋涂时伴随温度高于或等于60℃的热风。
在步骤(1)中，所述蜂蜡溶液的浓度小于或等于1g·mL-1。最优浓度为0.2g·mL-1。
在步骤(1)中，所述蜂蜡层的厚度小于或等于10μm。最优厚度为约1μm。
在步骤(2)中，腐蚀金属的溶液包括但不限于过硫酸铵溶液和氯化铁溶液；优选的，所述腐蚀液选自过硫酸铵溶液或/和氯化铁溶液。
在步骤(3)中，所述有机溶剂包括但不限于氯仿，乙醚和苯；优选的，所述有机溶剂选自氯仿、乙醚或苯中的一种或多种。
本发明与现有技术相比，主要优点包括：本发明的石墨烯薄膜完整性好，表面残留杂质少，转移得到的石墨烯薄膜面电阻低，石墨烯薄膜质量高。所用支撑层材料蜂蜡成本低廉，根据国药试剂网信息，相同质量的蜂蜡价格仅为传统支撑层材料PMMA的6.35％，且对环境友好，操作简便。
附图说明
图1为本发明的石墨烯薄膜转移过程示意图；
图2为实施例1转移得到的石墨烯薄膜的光学显微镜照片；
图3为实施例1和比例1转移得到的石墨烯薄膜的X-射线光电子能谱(XPS)；
图4为实施例1和对比例1转移得到的石墨烯薄膜的面电阻平面分布图；
图5为实施例1转移得到的石墨烯薄膜的拉曼(Raman)图谱；
图6为对比例1转移得到的石墨烯薄膜的光学显微镜照片；
图7为对比例2转移得到的石墨烯薄膜的光学显微镜照片。
具体实施方式
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。
下述实施例1的石墨烯转移方法基本步骤如图1所示，石墨烯薄膜样品用胶带粘在玻璃片上，蜂蜡溶液在60摄氏度以上的热风下均匀旋涂于石墨烯样品上，在过硫酸铵腐蚀液中除去铜基底，去离子水清洗后用目标基底将其捞起并晾干，在有机溶剂氯仿中除去蜂蜡并用氮气吹干。其他实施例的基本操作步骤相同，只是所用的支撑层材料与有机溶剂有差异。
实施例1
1.将生长后的石墨烯薄膜样品(石墨烯/铜基底)用胶带粘贴于玻璃片上后，用0.2g mL-1的蜂蜡溶液以4000转每分钟的转速均匀旋涂于石墨烯样品上，并将样品在常温下静置10分钟，得到蜂蜡层/石墨烯/铜基底，蜂蜡层的厚度约1μm(厚度可以通过改变旋涂参数比如浓度、转速、时间、旋涂次数而调节)；
2.将原有胶带撕下，另一面朝上重新固定于玻璃片上，放入氧气等离子体清洗器中，无蜂蜡旋涂一面朝上，处理20分钟以去除背面的石墨烯；
3.将样品取下，有蜂蜡旋涂一面朝上放入腐蚀液过硫酸铵溶液中，静置1小时左右，待铜箔完全除去后，将样品用去离子水清洗数次，得到蜂蜡层/石墨烯；
4.将带有300nm氧化层的硅片切成1cm×1cm的若干正方形小块，清洗后作为目标衬底备用；
5.用经氧气等离子体处理过的硅片将蜂蜡层/石墨烯捞起晾干；
6.样品置于40摄氏度的有机溶剂氯仿中除去蜂蜡层。
图2为实施例1转移得到的石墨烯的光学显微镜图像。图3中的(a)为实施例转移得到的石墨烯的X-射线光电子能谱(XPS)。图4中的(a)为实施例1转移得到的石墨烯的面电阻平面分布图。图5为实施例1转移得到的石墨烯薄膜的拉曼(Raman)图谱。
对比例1
1.将生长后的石墨烯薄膜样品(石墨烯/铜基底)用胶带粘贴于玻璃片上后，用质量分数4％的PMMA(聚甲基丙烯酸甲酯溶于苯甲醚中)以3000转每分钟的转速均匀旋涂于石墨烯样品上，并将样品放在加热台上70摄氏度加热10分钟；
2.将原有胶带撕下，另一面朝上重新固定于玻璃片上，放入氧气等离子体清洗器中，无PMMA旋涂一面朝上，处理20分钟以去除背面的石墨烯；
3.将样品取下，有PMMA旋涂一面朝上放入腐蚀液过硫酸铵溶液中，静置1小时左右，待铜箔完全除去后，将样品用去离子水清洗数次；
4.将带有300nm氧化层的硅片切成1cm×1cm的若干正方形小块，清洗后备用；
5.用经氧气等离子体处理过的硅片将石墨烯捞起晾干，并将样品放在加热台上40摄氏度加热30分钟；
6.样品置于70摄氏度有机溶剂丙酮中30分钟除去PMMA层。
图3中的(b)为对比例1转移得到的石墨烯的X-射线光电子能谱(XPS)。图4中的(b)为对比例1转移得到的石墨烯的面电阻平面分布图。图6是对比例1转移得到的石墨烯薄膜的光学显微镜图，可以看到该方法虽然保证了石墨烯的完整性，但由于PMMA与石墨烯之间结合力较强，难以通过有机溶剂一步除去，表面残留PMMA颗粒较多。从图4中的(b)，X-射线光电子能谱图中检测到的PMMA特征信号也证明了该结论。
对比例2
1.将生长后的石墨烯样品用胶带粘贴于玻璃片上后，用质量分数50％的松香的乙酸乙酯溶液以1200转每分钟的转速均匀旋涂于石墨烯样品上，并将样品放在常温下固化30分钟；
2.将原有胶带撕下，另一面朝上重新固定于玻璃片上，放入氧气等离子体清洗器中，无松香旋涂一面朝上，处理20分钟以去除背面的石墨烯；
3.将样品取下，有松香旋涂一面朝上放入腐蚀液过硫酸铵溶液中，静置1小时左右，待铜箔完全除去后，将样品用去离子水清洗数次；
4.将带有300nm氧化层的硅片切成1cm×1cm的若干正方形小块，清洗后备用；
5.用经氧气等离子体处理过的硅片将石墨烯捞起晾干，并将样品放在加热台上40摄氏度加热30分钟；
6.样品置于有机溶剂乙酸异戊酯中20分钟除去松香层。
图7是对比例2转移得到的石墨烯薄膜的光学显微镜图，可以看出该方法转移得到的石墨烯表面颗粒比PMMA转移的更少。这是由于松香的分子量远小于PMMA，因此与石墨烯的结合力更小，易于除去。但是结合力太弱也导致松香支撑层无法对石墨烯薄膜提供足够的支撑，因此导致结构破坏，转移得到的石墨烯薄膜不完整。
与对比例1，2转移得到的石墨烯相比，实施例1转移的到的石墨烯表面上既没有高聚物残留，也不存在破损的现象，兼顾了石墨烯的干净和完整性。此外，还可以清晰地看到生长过程中由于石墨烯和铜基底热膨胀系数不同而产生的褶皱。由于石墨烯褶皱处与支撑层材料的结合力更强，残留的高聚物颗粒通常倾向于沿着石墨烯褶皱分布。在图2中，即使是在石墨烯褶皱处也无颗粒残留，进一步说明该转移方法可获得高质量石墨烯。
图3中的(a)和图3中的(b)分别为实施例1和对比例1转移得到的石墨烯薄膜在SiO2/Si基底上的X-射线光电子能谱图。对比可知，只有PMMA转移所得石墨烯表面检测到了对应支撑层材料的信号，这进一步表明在通过PMMA转移的石墨烯上残留了许多将损害石墨烯的电子性能的PMMA颗粒。为验证上述观点，使用完全相同的颜色标尺在图4中的(a)和(b)中绘制了实施例1和对比例1转移得到的石墨烯的面电阻分布。对于每个样品，使用四探针电阻率测量系统在20×20mm2的面积上以2mm为采样间距共测量了100组面电阻值。据统计，PMMA转移石墨烯的面电阻值分布在526到914Ω·□-1之间，平均值为753Ω·□-1。由图4(b)可知，PMMA转移石墨烯表面具有多处随机分布的、异常高的面电阻值，这可能是由于转移过程中的机械损伤和PMMA颗粒残留引起的。与之形成鲜明对比的是，蜂蜡转移的石墨烯薄膜面电阻值显示出非常窄的波动区间和较小的平均，其面电阻分布在在520至632Ω·□-1之间且在20×20mm2的区域内显示出均匀的分布，平均值为603Ω·□-1。尽管边缘电阻略有增加，但较低且均匀的面电阻仍然表明，蜂蜡转移的石墨烯在电子器件的应用中更具潜力。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (7)
1.一种蜂蜡作支撑层的石墨烯薄膜转移方法，其特征在于，所述方法包括：
(1)将蜂蜡溶液旋涂至金属基底的石墨烯薄膜表面上，形成作为支撑层的蜂蜡层，得到蜂蜡层/石墨烯薄膜/金属基底；
(2)用腐蚀液去除金属基底得到蜂蜡层/石墨烯，再将蜂蜡层/石墨烯薄膜转移至目标基底并干燥；
(3)采用有机溶剂除去蜂蜡层，实现石墨烯薄膜的转移。
2.根据权利要求1所述的石墨烯薄膜转移方法，其特征在于，在步骤(1)中，所述旋涂的环境温度高于或等于60℃；旋涂后静置形成蜂蜡层。
3.根据权利要求2所述的石墨烯薄膜转移方法，其特征在于，所述旋涂时伴随温度高于或等于60℃的热风。
4.根据权利要求1所述的石墨烯薄膜转移方法，其特征在于，在步骤(1)中，所述蜂蜡溶液的浓度小于或等于1g·mL-1。
5.根据权利要求1所述的石墨烯薄膜转移方法，其特征在于，在步骤(1)中，所述蜂蜡层的厚度小于或等于10μm。
6.根据权利要求1所述的石墨烯薄膜转移方法，其特征在于，在步骤(2)中，所述腐蚀液选自过硫酸铵溶液或/和氯化铁溶液。
7.根据权利要求1所述的石墨烯薄膜转移方法，其特征在于，在步骤(3)中，所述有机溶剂选自氯仿、乙醚或苯中的一种或多种。
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