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本文采用5.4 keV不同剂量的He离子辐照单层石墨烯, 利用X射线光电子能谱(XPS)、拉曼光谱(Raman)和半导体参数分析仪表征辐照前后石墨烯微观结构和电学性能变化. 研究结果表明: 随着辐照剂量增大, 单层石墨烯的缺陷密度逐渐增加, 当辐照剂量增至1.6 × 1013 He+/cm2, 石墨烯开始由纳米晶结构向无定形碳结构转变, 不断增多的缺陷致使石墨烯电导率持续降低, 其电子输运机制也由玻尔兹曼扩散输运转变为跃迁输运; 狄拉克电压(Vdirac)向正电压方向的偏移量随辐照剂量增大而增大, 其主因是辐照缺陷和吸附杂质导致石墨烯P型掺杂效应增强.Graphene is a planar two-dimensional material composed of sp2-bonded carbon atoms with extraordinary electrical, optical and mechanical properties, and considered as one of the revolutionary electronic component materials in the future. Some studies have shown that the inert gas ion irradiation as a defect introducing technique can change the structure and properties of graphene without introducing additional effects. In this paper, the 5.4 keV He ion irradiation at the dose ranging from 0.7 × 1013 cm–2 to 2.5 × 1013 cm–2 has a strong effect on graphene deposited by CVD technology. The X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (Raman) and semi-conductor parameter analysis instrument are used to study the changes in the microstructure and electrical properties of graphene before and after irradiation. Detailed analysis shows that the defect density increases gradually with the irradiation dose increasing. Raman spectrum shows that when the irradiation dose increases to 1.6 × 1013 cm–2, the value of ID/IG begins to decrease, and XPS shows that the irradiation changes the structure of C chemical bond in graphene which causes the bonding state of C—C sp2 to be destroyed and partly converted into the C—C sp3 bonding state. Therefore, the structure of graphene begins to transform from nano-crystalline structure into sp3 amorphous structure. Simultaneously, increasing defects causes the graphene conductivity to continuously decrease, and also gives rise to the electrical transition from defect scattering mechanism based on Boltzmann transport to the hopping transport. The positive voltage direction offset of Vdirac increases nearly in direct proportion, which is due to the enhancement of graphene’s p-type doping effect caused by defects and adsorbed impurities. This work conduces to the understanding the mechanism of He ion interaction with graphene, and also provides an effective way of controlling the electronic properties.
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Keywords:
- graphene /
- He ion irradiation /
- microstructures /
- electrical properties
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[14] 曾健 2014 博士学位论文 (兰州: 兰州大学)
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表 1 辐照前后石墨烯样品C1 s峰面积比
Table 1. C1 s peak area ratio of graphene samples before and after irradiation.
辐照剂量 C-C sp2 C—C sp3 C—O—H C—O—C O—C=O 未辐照 0.52 0.19 0.10 0.09 0.10 0.7 × 1013 He+/cm2 0.50 0.30 0.13 0.05 0.02 1.6 × 1013 He+/cm2 0.37 0.32 0.15 0.10 0.06 2.5 × 1013 He+/cm2 0.28 0.35 0.20 0.12 0.05 -
[1] Karimi H, Yusof R, Rahmani R, Ahmadi M T 2013 J. Nanomater. 2013 789454Google Scholar
[2] Geim A K, Novoselov K S 2007 Nat. Mater. 6 183Google Scholar
[3] 张辉, 蔡晓明, 郝振亮, 阮子林, 卢建臣, 蔡金明 2017 物理学报 66 218103Google Scholar
Zhang H, Cai X M, Hao Z L, Ruan Z L, Lu J C, Cai J M 2017 Acta Phys. Sin. 66 218103Google Scholar
[4] Li M, Qu G F, Wang Y Z, Zhu Z S, Shi M G, Zhou M L, Liu D, Xu Z X, Song M J, Zhang J, Bai F, Liao X D, Han J F 2019 Chin. Phys. B 28 093401Google Scholar
[5] Zeng J, Liu J, Yao H J, Zhai P F, Zhang S X, Guo H, Hu P P, Duan J L, Mo D, Hou M D, Sun Y M 2016 Carbon 100 16Google Scholar
[6] Kumar S, Kumar A, Tripathi A, Tyagi C, AvasthiCitation D K 2018 J. Appl. Phys. 123 161533Google Scholar
[7] Hang S J, Moktadir Z, Mizuta H 2014 Carbon 72 233Google Scholar
[8] Tapasztó L, Dobrik G, Nemes-Incze P, Vertesy G, Lambin Ph, Biró L P 2008 Phys. Rev. B 78 233407Google Scholar
[9] Lucchese M M, Stavale F, Ferreira E M, Vilani C, Moutinho M, Capaz R B, Achete C, Jorio A 2010 Carbon 48 1592Google Scholar
[10] Al-Harthi S H, Kara’a A, Hysen T, Elzain M, Al-Hinai A T, Myint M T Z 2012 Appl. Phys. Lett. 101 213107Google Scholar
[11] Chen J H, Cullen W G, Jang C, Fuhrer M S, Williams E D 2009 Phys. Rev. Lett. 102 236805Google Scholar
[12] Amor S B, Baud G, Jacquet M, Nansé G, Fioux P, Nardin M 2000 Appl. Surf. Sci. 153 172Google Scholar
[13] 王淑芬 2018 博士学位论文 (合肥: 中国科学技术大学)
Wang S F 2018 Ph. D. Dissertation (Hefei: University of Science and Technology of China) (in Chinese)
[14] 曾健 2014 博士学位论文 (兰州: 兰州大学)
Zeng J 2014 Ph. D. Dissertation (Lanzhou: Lanzhou University) (in Chinese)
[15] Ferrari A C, Robertson J 2000 Phys. Rev. B 61 14095Google Scholar
[16] 吴娟霞, 徐华, 张锦 2014 化学学报 72 301Google Scholar
Wu J X, Xiu H, Zhang J 2014 Acta Chim. Sin. 72 301Google Scholar
[17] Kim J H, Hwang J H, Suh J, Tongay S, Kwon S, Hwang C C, Wu J Q, Park J Y 2013 Appl. Phys. Lett. 103 171604Google Scholar
[18] Wang H, Wu Y, Cong C, Shang J, Yu T 2010 ACS Nano 4 7221Google Scholar
[19] Pimenta M A, Dresselhaus G, Dresselhaus M S, Cancado L G, Jorio A, Saito R 2007 Phys. Chem. Chem. Phys. 9 1276Google Scholar
[20] Ferrari A C 2007 Solid State Commun. 143 47Google Scholar
[21] 白冰 2016 博士学位论文 (镇江: 江苏大学)
Bai B 2016 Ph. D. Dissertation (Zhenjiang: Jiangsu University) (in Chinese)
[22] 宋航, 刘杰, 陈超, 巴龙 2019 物理学报 68 097301Google Scholar
Song H, Liu J, Chen C, Ba L 2019 Acta Phys. Sin. 68 097301Google Scholar
[23] Guermoune A, Chari T, Popescu F, Sabri S S, Guillemette J, Skulason H S, Szkopek T, Siaj M 2011 Carbon 49 4204Google Scholar
[24] Yuan H Y, Chang S, Bargatin I 2015 Nano Lett. 15 6475
[25] Stauber T, Peres N M R, Guinea F 2007 Phys. Rev. B 76 205423Google Scholar
[26] Chen C F, Park C H, Boudouris B W, Horng J, Geng B, Girit C, Zettl A, Crommie M F, Segalman R A, Louie S G, Wang F 2011 Nature 471 617Google Scholar
[27] Wang Q, Liu S, Ren N F 2014 Appl. Phys. Lett. 105 133506Google Scholar
[28] Zhou Y B, Liao Z M, Wang Y F, Duesberg G S, Xu J, Fu Q, Wu X S, Yu D P 2010 J. Chem. Phys. 133 234703Google Scholar
[29] Cancado L G, Jorio A, Ferreira E H M, Stavale F, Achete C A, Capaz R B, Moutinho M V O, Lombardo A, Kulmala T S, Ferrari A C 2011 Nano Lett. 11 3190Google Scholar
[30] Zhou Y B, Han B H, Liao Z M, Wu H C, Yu D P 2011 Appl. Phys. Lett. 98 222502Google Scholar
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