CN102583329A - 基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法 - Google Patents

基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法 Download PDF

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CN102583329A
CN102583329A CN2012100095036A CN201210009503A CN102583329A CN 102583329 A CN102583329 A CN 102583329A CN 2012100095036 A CN2012100095036 A CN 2012100095036A CN 201210009503 A CN201210009503 A CN 201210009503A CN 102583329 A CN102583329 A CN 102583329A
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郭辉
张克基
张玉明
邓鹏飞
雷天民
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Xidian University
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Abstract

本发明公开了一种基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，主要解决现有技术中制备的石墨烯面积小、层数不均匀的问题。(1)在4-12英寸的Si衬底基片上先生长一层碳化层作为过渡；(2)在温度为1150℃-1350℃下进行3C-SiC异质外延薄膜的生长，生长气源为C3H8和SiH4；(3)将3C-SiC在700-1100℃下与Cl2反应，生成碳膜，(4)将生成的碳膜样片的碳面置于Cu膜上，再将它们一同置于Ar气中，在温度为900-1100℃下退火10-30min生成石墨烯。用本发明方法生成的石墨烯面积大，表面光滑，连续性好，孔隙率低，可用于对气体和液体的密封。

Description

基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法
技术领域
本发明属于微电子技术领域，涉及一种半导体薄膜材料及其制备方法，具体地说是基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法。
技术背景
石墨烯出现在实验室中是在2004年，当时，英国曼彻斯特大学的两位科学家安德烈·杰姆和克斯特亚·诺沃消洛夫发现他们能用一种非常简单的方法得到越来越薄的石墨薄片。他们从石墨中剥离出石墨片，然后将薄片的两面粘在一种特殊的胶带上，撕开胶带，就能把石墨片一分为二。不断地这样操作，于是薄片越来越薄，最后，他们得到了仅由一层碳原子构成的薄片，这就是石墨烯。这以后，制备石墨烯的新方法层出不穷。目前的制备方法主要有两种：
1.化学气相沉积法提供了一种可控制备石墨烯的有效方法，它是将平面基底，如金属薄膜、金属单晶等置于高温可分解的前驱体，如甲烷、乙烯等气氛中，通过高温退火使碳原子沉积在基底表面形成石墨烯，最后用化学腐蚀法去除金属基底后即可得到独立的石墨烯片。通过选择基底的类型、生长的温度、前驱体的流量等参数可调控石墨烯的生长，如生长速率、厚度、面积等，此方法最大的缺点在于获得的石墨烯片层与衬底相互作用强，丧失了许多单层石墨烯的性质，而且石墨烯的连续性不是很好。
2.热分解SiC法：将单晶SiC加热以通过使表面上的SiC分解而除去Si，随后残留的碳形成石墨烯。然而，SiC热分解中使用的单晶SiC非常昂贵，并且生长出来的石墨烯呈岛状分布，层数不均匀，且尺寸较小，很难大面积制造石墨烯。
发明内容
本发明的目的在于针对上述已有技术的不足，提出一种基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，以提高表面光滑度和连续性、降低孔隙率、减少成本，实现在3C-SiC衬底上大面积的制造石墨烯。
为实现上述目的，本发明的制备方法包括以下步骤：
(1)对4-12英寸的Si衬底基片进行标准清洗；
(2)将清洗后的Si衬底基片放入CVD系统反应室中，对反应室抽真空达到10-7mbar级别；
(3)在H2保护的情况下逐步升温至碳化温度1000℃-1150℃，通入流量为40sccm的C3H8，对衬底进行碳化4-8min，生长一层碳化层；
(4)迅速升温至生长温度1150℃-1350℃，通入C3H8和SiH4，进行3C-SiC异质外延薄膜的生长，时间为36-60min，然后在H2保护下逐步降温至室温，完成3C-SiC外延薄膜的生长；
(5)将生长好的3C-SiC样片置于石英管中，加热至700-1100℃；
(6)向石英管中通入Ar气和Cl2气的混合气体，持续时间4-7min，使Cl2与3C-SiC反应生成碳膜；
(7)将生成的碳膜样片的碳面置于Cu膜上，再将它们一同置于Ar气中在温度为900-1100℃下退火10-30分钟，碳膜重构成石墨烯，再将Cu膜从石墨烯样片上取开。
本发明与现有技术相比具有如下优点：
1.本发明由于在生长3C-SiC时先在Si衬底上成长一层碳化层作为过渡，然后再生长3C-SiC，因而生长的3C-SiC质量高。
2.本发明由于3C-SiC可异质外延生长在Si圆片上，而Si圆片尺寸可达12英寸，因而用此方法可以生长大面积的石墨烯，且价格便宜。
3.本发明中3C-SiC与Cl2可在较低的温度和常压下反应，且反应速率快。
4.本发明由于利用3C-SiC与Cl2气反应，因而生成的石墨烯表面光滑，空隙率低，且厚度容易控制，可用于对气体和液体的密封。
5.本发明由于利用在Cu膜上退火，因而生成的碳膜更容易重构形成连续性较好的石墨烯。
附图说明
图1是本发明制备石墨烯的装置示意图；
图2是本发明制备石墨烯的流程图。
具体实施方式
参照图1，本发明的制备设备主要由石英管1和电阻炉2组成，其中石英管1设有进气口3和出气口4，电阻炉为2为环状空心结构，石英管1插装在电阻炉2内。
参照图2，本发明的制作方法给出如下三种实施例。
实施例1
步骤1：去除样品表面污染物。
对4英寸的Si衬底基片进行表面清洁处理，即先使用NH4OH+H2O2试剂浸泡样品10分钟，取出后烘干，以去除样品表面有机残余物；再使用HCl+H2O2试剂浸泡样品10分钟，取出后烘干，以去除离子污染物。
步骤2：将Si衬底基片放入CVD系统反应室中，对反应室抽真空达到10-7mbar级别。
步骤3：生长碳化层。
在H2保护的情况下将反应室温度升至碳化温度1000℃，然后向反应室通入流量为40sccm的C3H8，在Si衬底上生长一层碳化层，生长时间为8min。
步骤4：在碳化层上生长3C-SiC外延薄膜。
将反应室温度迅速升至生长温度1150℃，通入流量分别为15sccm和30sccm的SiH4和C3H8，进行3C-SiC异质外延薄膜的生长，生长时间为60min；然后在H2保护下逐步降温至室温，完成3C-SiC外延薄膜的生长。
步骤5：将3C-SiC样片装入石英管，并排气加热。
(5.1)将生长好的3C-SiC外延薄膜样片从CVD系统反应室取出后置于石英管5中，把石英管置于电阻炉2中；
(5.2)从进气口3向石英管中通入流速为80sccm的Ar气，对石英管进行排空10分钟，将空气从出气口4排出；
(5.3)打开电阻炉电源开关，升温至700℃，使在其中的石英管也加热至700℃。
步骤6：生成碳膜
向石英管通入流速分别为98sccm和2sccm的Ar气和Cl2气，时间为4分钟，使Cl2与3C-SiC反应生成碳膜。
步骤7：重构成石墨烯。
(7.1)将生成的碳膜样片从石英管中取出，将其碳面置于厚度为250nm的Cu膜上；
(7.2)将碳膜样片和Cu膜整体置于流速为100sccm的Ar气中，在温度为900℃下退火30分钟，通过金属Cu的催化作用使碳膜重构成连续的石墨烯；
(7.3)将Cu膜从石墨烯样片上取开。
实施例2
步骤一：去除样品表面污染物。
对8英寸的Si衬底基片进行表面清洁处理，即先使用NH4OH+H2O2试剂浸泡样品10分钟，取出后烘干，以去除样品表面有机残余物；再使用HCl+H2O2试剂浸泡样品10分钟，取出后烘干，以去除离子污染物。
步骤二：将Si衬底基片放入CVD系统反应室中，对反应室抽真空达到10-7mbar级别。
步骤三：生长碳化层。
在H2保护的情况下将反应室温度升至碳化温度1050℃，然后向反应室通入流量为40sccm的C3H8，在Si衬底上生长一层碳化层，生长时间为5min。
步骤四：在碳化层上生长3C-SiC外延薄膜。
将反应室温度迅速升至生长温度1200℃，通入流量分别为20sccm和40sccm的SiH4和C3H8，进行3C-SiC异质外延薄膜的生长，生长时间为45min；然后在H2保护下逐步降温至室温，完成3C-SiC外延薄膜的生长。
步骤五：将3C-SiC样片装入石英管，并排气加热。
将生长好的3C-SiC外延薄膜样片从CVD系统反应室取出后置于石英管5中，把石英管置于电阻炉2中；从进气口3向石英管中通入流速为80sccm的Ar气，对石英管进行排空10分钟，将空气从出气口4排出；再打开电阻炉电源开关，升温至1000℃，使在其中的石英管也加热至1000℃。
步骤六：生成碳膜
向石英管通入流速分别为97sccm和3sccm的Ar气和Cl2气，时间为5分钟，使Cl2与3C-SiC反应生成碳膜。
步骤七：重构成石墨烯。
将生成的碳膜样片从石英管中取出，将其碳面置于厚度为280nm的Cu膜上；将碳膜样片和Cu膜整体置于流速为75sccm的Ar气中，在温度为1050℃下退火15分钟，通过金属Cu的催化作用使碳膜重构成连续的石墨烯；再将Cu膜从石墨烯样片上取开。
实施例3
步骤A：对12英寸的Si衬底基片进行表面清洁处理，即先使用NH4OH+H2O2试剂浸泡样品10分钟，取出后烘干，以去除样品表面有机残余物；再使用HCl+H2O2试剂浸泡样品10分钟，取出后烘干，以去除离子污染物。
步骤B：将Si衬底基片放入CVD系统反应室中，对反应室抽真空达到10-7mbar级别。
步骤C：在H2保护的情况下将反应室温度升至碳化温度1150℃，然后向反应室通入流量为40sccm的C3H8，持续4min，以在Si衬底上生长一层碳化层。
步骤D：将反应室温度迅速升至生长温度1350℃，通入流量分别为25sccm和50sccm的SiH4和C3H8，进行3C-SiC异质外延薄膜的生长36min；然后在H2保护下逐步降温至室温。
步骤E：将生长好的3C-SiC外延薄膜样片从CVD系统反应室取出后置于石英管5中，把石英管置于电阻炉2中；从进气口3向石英管中通入流速为80sccm的Ar气，对石英管进行排空10分钟，将空气从出气口4排出；再打开电阻炉电源开关，升温至1100℃，使在其中的石英管也加热至1100℃。
步骤F：向石英管中通入流速分别为95sccm和5sccm的Ar气和Cl2气，时间为4分钟，使Cl2与3C-SiC反应生成碳膜。
步骤G：将生成的碳膜样片从石英管中取出，将其碳面置于厚度为300nm的Cu膜上；将碳膜样片和Cu膜整体置于流速为25sccm的Ar气中，在温度为1100℃下退火10分钟，通过金属Cu的催化作用使碳膜重构成连续的石墨烯；再将Cu膜从石墨烯样片上取开。

Claims (5)

1.一种基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，其特征在于，制备方法包括以下步骤：
(1)对4-12英寸的Si衬底基片进行标准清洗；
(2)将清洗后的Si衬底基片放入CVD系统反应室中，对反应室抽真空达到10-7mbar级别；
(3)在H2保护的情况下逐步升温至碳化温度1000℃-1150℃，通入流量为40sccm的C3H8，对衬底进行碳化4-8min，生长一层碳化层；
(4)迅速升温至生长温度1150℃-1350℃，通入C3H8和SiH4，进行3C-SiC异质外延薄膜的生长，时间为36-60min，然后在H2保护下逐步降温至室温，完成3C-SiC外延薄膜的生长；
(5)将生长好的3C-SiC样片置于石英管中，加热至700-1100℃；
(6)向石英管中通入Ar气和Cl2气的混合气体，持续时间4-7min，使Cl2与3C-SiC反应生成碳膜；
(7)将生成的碳膜样片的碳面置于Cu膜上，再将它们一同置于Ar气中在温度为900-1100℃下退火10-30分钟，碳膜重构成石墨烯，再将Cu膜从石墨烯样片上取开。
2.根据权利要求1所述的基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，其特征在于步骤(4)所述通入的SiH4和C3H8，其流量分别为15-25sccm和30-50sccm。
3.根据权利要求1所述的基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，其特征在于步骤(6)所述通入的Ar气和Cl2气，其流速分别为95-98sccm和5-2sccm。
4.根据权利要求1所述的基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，其特征在于所述步骤(7)退火时Ar气的流速为25-100sccm。
5.根据权利要求1所述的基于Cu膜辅助退火和Cl2反应的大面积石墨烯制备方法，其特征在于所述步骤(7)中的Cu膜厚度为250-300nm。
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