腔体材料对氧化铜箔衬底上制备石墨烯的影响

摘要/Abstract

摘要： 传统的化学气相沉积法制备的石墨烯普遍存在晶畴面积小、晶界缺陷多的问题,严重制约了大面积石墨烯的性能及应用。本文采用低压化学气相沉积技术在受限生长腔中的氧化铜箔衬底上制备石墨烯,对比研究了石英和刚玉两种材质的受限生长腔中,不同甲烷流量和生长时间条件下氧化铜箔衬底上石墨烯的形核生长状况。结果表明,相同生长条件下,相较于石英受限生长腔,虽然刚玉受限生长腔中石墨烯的晶畴尺寸较小,但是氧化铜箔衬底表面沉积的杂质颗粒较少,因而石墨烯的形核密度较低,晶体质量较高,更有利于大尺寸、高质量石墨烯的制备。

关键词: 石墨烯, 低压化学气相沉积, 受限生长腔, 氧化铜箔, 衬底, 形核

Abstract: Graphene prepared by the traditional chemical vapor deposition are generally subjected to small domain area and multiple grain boundary defects, which seriously restricts the performance and application of large-area graphene. In this study, the low-pressure chemical vapor deposition technology was used to prepare graphene on the oxidized copper foils substrate in the restricted growth chambers. The growth behavior of the graphene on two kinds of restricted growth chambers (quartz and corundum) were studied. The effects of the quartz restricted growth chamber and the corundum restricted growth chamber on the nucleation and growth of graphene on the oxidized copper foils under different methane flow rates and growth time were compared. The results indicates that, compared to the quartz restricted growth chamber, although the domain sizes of graphene on the oxidized copper foils substrate in the restricted growth chamber of corundum are smaller, there are fewer deposited impurity particles on the surface of the oxidized copper foils substrate, resulting in lower nucleation density and higher crystal quality of graphene, which is more conducive to the preparation large-sized and high-quality graphene.

Key words: graphene, low pressure chemical vapor deposition, restricted growth chamber, oxidized copper foil, substrate, nucleation

中图分类号:

TQ127.1⁺1

沈曦, 史永贵, 万玉慧, 付影, 马嘉恒, 杨浩东, 王艺佳. 腔体材料对氧化铜箔衬底上制备石墨烯的影响[J]. 人工晶体学报, 2024, 53(9): 1648-1654.

SHEN Xi, SHI Yonggui, WAN Yuhui, FU Ying, MA Jiaheng, YANG Haodong, WANG Yijia. Effects of Chamber Materials on the Preparation of Graphene on the Oxidized Copper Foils Substrate[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1648-1654.

参考文献

[1] 汪礼丽. 石墨烯单晶铜衬底上外延生长及透明电磁屏蔽性能研究[D]. 哈尔滨: 哈尔滨工业大学, 2021.
WANG L L. Epitaxial growth and transparent electromagnetic shielding properties on graphene single crystal copper substrate[D]. Harbin: Harbin Institute of Technology, 2021 (in Chinese).
[2] DREYER D R, PARK S, BIELAWSKI C W, et al. The chemistry of graphene oxide[J]. Chemical Society Reviews, 2010, 39(1): 228-240.
[3] STANKOVICH S, DIKIN D A, PINER R D, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon, 2007, 45(7): 1558-1565.
[4] NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696): 666-669.
[5] TROMP R M, HANNON J B. Thermodynamics and kinetics of graphene growth on SiC(0001)[J]. Physical Review Letters, 2009, 102(10): 106104.
[6] LI X S, CAI W W, AN J, et al. Large-area synthesis of high-quality and uniform graphene films on copper foils[J]. Science, 2009, 324(5932): 1312-1314.
[7] 陈克新, 苗鸿雁. 我国科学家把石墨烯单晶的生长速度提高了150倍[J]. 中国科学基金, 2017, 9: 30.
CHEN K X, MIAO H Y, Chinese scientists have increased the growth rate of graphene single crystals by 150 times[J]. China Science Foundation, 2017, 9: 30.
[8] HUANG M, BISWAL M, PARK H J, et al. Highly oriented monolayer graphene grown on a Cu/Ni(111) alloy foil[J]. ACS Nano, 2018, 12(6): 6117-6127.
[9] ZHANG X F, WU T R, JIANG Q, et al. Epitaxial growth of 6 in. single-crystalline graphene on a Cu/Ni (111) film at 750 ℃ via chemical vapor deposition[J]. Small, 2019, 15(22): 1805395.
[10] HAO Y F, BHARATHI M S, WANG L, et al. The role of surface oxygen in the growth of large single-crystal graphene on copper[J]. Science, 2013, 342(6159): 720-723.
[11] 史永贵, 桑昭君, 王允威, 等. 气相捕获腔对石墨烯低压化学气相沉积形核生长的影响[J]. 人工晶体学报, 2020, 49(3): 439-445.
SHI Y G, SANG Z J, WANG Y W, et al. Effect of the vapor trapping chamber on the nucleation and growth of graphene by low pressure chemical vapor deposition[J]. Journal of Synthetic Crystals, 2020, 49(3): 439-445 (in Chinese).
[12] CHEN C C, KUO C J, LIAO C D, et al. Growth of large-area graphene single crystals in confined reaction space with diffusion-driven chemical vapor deposition[J]. Chemistry of Materials, 2015, 27(18): 6249-6258.
[13] DAI C Y, WANG W C, TSENG C A, et al. Spatial confinement approach using Ni to modulate local carbon supply for the growth of uniform transfer-free graphene monolayers[J]. The Journal of Physical Chemistry C, 2020, 124(42): 23094-23105.
[14] ZHANG Y N, HUANG D P, DUAN Y W, et al. Batch production of uniform graphene films via controlling gas-phase dynamics in confined space[J]. Nanotechnology, 2021, 32(10): 105603.
[15] ZHANG Z H, XU X Z, QIU L, et al. The way towards ultrafast growth of single-crystal graphene on copper[J]. Advanced Science, 2017, 4(9): 1700087.
[16] 袁良川. 不同氧调控措施对石墨烯形核及生长的影响[D]. 广州: 华南理工大学, 2021.
YUAN L C. Effects of different oxygen control measures on nucleation and growth of graphene[D].Guangzhou: South China University of Technology, 2021 (in Chinese).
[17] CAO Q J, SHI B Y, DOU W D, et al. Background pressure does matter for the growth of graphene single crystal on copper foil: key roles of oxygen partial pressure[J]. Carbon, 2018, 138: 458-464.
[18] 王璐, 高峻峰, 丁峰. 经典晶体生长理论在石墨烯CVD成核和连续生长中的应用[J]. 化学学报, 2014, 72(3): 345-358.
WANG L, GAO J F, DING F. Application of crystal growth theory in graphene CVD nucleation and growth[J]. Acta Chimica Sinica, 2014, 72(3): 345-358 (in Chinese).
[19] RAO R, TISHLER D, KATOCH J, et al. Multiphonon Raman scattering in graphene[J]. Physical Review B, 2011, 84(11): 113406.
[20] KROES J M H, AKHUKOV M A, LOS J H, et al. Mechanism and free-energy barrier of the type-57 reconstruction of the zigzag edge of graphene[J]. Physical Review B, 2011, 83(16): 165411.
[21] BIRÓ L P, LAMBIN P. Nanopatterning of graphene with crystallographic orientation control[J]. Carbon, 2010, 48(10): 2677-2689.
[22] CHEN H, ZHANG J C, LIU X T, et al. Effect of gas-phase reaction on the CVD growth of graphene[J]. Acta Physico Chimica Sinica, 2022, 38(1): 2101053.