铜基底预处理对CVD法生长石墨烯薄膜的影响

doi:10.15541/jim20190615

摘要/Abstract

摘要：

化学气相沉积法是制备大尺寸、高质量石墨烯的有效方法, 其中金属催化剂的性能直接关系到所制备的石墨烯材料的品质, 因此需对金属催化剂进行表面预处理。本文研究了不同的预处理工艺对常用的铜基底催化剂表面状态的影响, 提出了钝化膏酸洗和电化学抛光协同处理的有效方法, 并对电化学抛光工艺参数(抛光电压、时间)以及铜基底退火工艺(退火温度、时间)等进行了系统研究。研究表明: 电化学抛光电压过高、抛光时间过长容易导致过度抛光, 合适的抛光电压和抛光时间分别为8 V和8 min。退火温度和时间对铜催化剂表面晶粒形态影响较大, 经1000 ℃退火处理30 min后, 铜箔表面晶粒尺寸更大, 分布更均匀。此外, 对CVD法生长制备的石墨烯样品进行表征, 电镜图片和拉曼光谱显示, 获得的石墨烯薄膜的层数较少, 且结构缺陷较少。

关键词: 铜基底, 预处理, 化学气相沉积法, 石墨烯

Abstract:

Chemical vapor deposition (CVD) is an effective method for preparing large-size and high-quality graphene materials. The properties of the metal catalysts are direcly related to the quality of the prepared graphene films, so the surface pretreatment of the metal catalysts is required. In this study, the effects of different pretreatment methods on copper substrates are investigated, and the combination of passivation paste pickling and electrochemical polishing is proposed to be an effective method to modify the surface morphology of copper catalyst. The electrochemical polishing parameters (such as voltage, time) and the copper substrate annealing parameters (such as annealing temperature, time) are systematically studied. This study demonstrates that high electrochemical polishing voltage and long polishing time easily lead to the excessive polishing. It is appropriate to set the polishing voltage and polishing time to 8 V and 8 min, respectively. It is found that the annealing temperature and time have significant effects on the grain size of the copper catalyst. After annealing at 1000 ℃ for 30 min, the grain is larger and more uniform. In addition, the structure characterization of graphene prepared by CVD is also performed. According to the SEM image and Raman spectrum, the few-layer, high-quality graphene film is successfully prepared.

Key words: copper substrate, pretreatment, chemical vapor deposition, graphene

中图分类号:

TQ174

孙付通, 冯爱虎, 陈兵兵, 于云, 杨红. 铜基底预处理对CVD法生长石墨烯薄膜的影响[J]. 无机材料学报, 2020, 35(10): 1177-1182.

SUN Futong, FENG Aihu, CHEN Bingbing, YU Yun, YANG Hong. Effect of Copper Pretreatment on Growth of Graphene Films by Chemical Vapor Deposition[J]. Journal of Inorganic Materials, 2020, 35(10): 1177-1182.

图/表 7

Fig. 1 OM images of different copper substrates (a) Untreated copper substrate; (b) Hydrochloric acid etching treatment; (c) Hydrochloric acid etching and electrochemical polishing treatment; (d) Passivation paste etching; (e) Passivation paste etching and electrochemical polishing treatment

Fig. 2 OM images of copper substrates electrochemical polished with different voltages and time (a1) 1.2 V/10 min; (a2) 1.2 V/20 min; (a3) 1.2 V/30 min; (a4) 1.2 V/40 min; (b1) 4 V/10 min; (b2) 4 V/20 min; (b3) 4 V/30 min; (b4) 4 V/40 min; (c1) 8 V/6 min; (c2) 8 V/8 min; (c3) 8 V/10 min; (c4) 8 V/12 min

Fig. 3 OM images of copper substrates annealed at different temperatures for 30 min (a) 800 ℃; (b) 900 ℃; (c) 1000 ℃; (d) 1060 ℃

Fig. 4 OM images of copper substrates annealed at 1000 ℃ for different time (a) 0; (b) 30 min; (c) 90 min; (d) 120 min

Fig. 5 SEM image of graphene sample

Fig. 6 Raman spectra of quartz substrate (a), graphene sample in gray area (b), and graphene sample in dark gray area (c)

Table 1 Comparison of the Raman characteristic peak in different graphene areas

Area	D band/cm^-1	G band/cm^-1	2D band/cm^-1	I_D/I_G	I_2D/I_G
Gray area	1354	1581	2697	0.57	0.83
Dark gray area	1354	1592	2684	0.26	1.29

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