石墨烯掺杂的研究进展

doi:10.6023/A14020093

摘要/Abstract

石墨烯的p型和n型掺杂调控对于石墨烯基功能器件的构筑至关重要. 近年来，随着化学气相沉积（CVD）石墨烯技术的发展和广泛应用，CVD石墨烯掺杂技术及相应性能调控的研究也取得了极大进展. 本文主要介绍了近几年来石墨烯，特别是CVD生长石墨烯掺杂研究的发展，讨论了金属电极接触、气体小分子吸附、氧化性及还原性极性分子吸附及晶格掺杂等多种石墨烯掺杂的方法，同时介绍了近期出现的对双层石墨烯能带调控以及制造石墨烯p-n结的研究，展望了石墨烯掺杂对于其功能器件研究的作用和发展前景.

关键词: 石墨烯, 掺杂, 半导体, 带隙

Doping is the most feasible and convenient method to modulate the band structure of graphene from semimetal to p-type or n-type material. In recent years, the chemical vapor deposition methods have been well developed to grow graphene layer with high quality and large area. This paper briefly reviews the recent research progress on doping methods of CVD graphene, including the doping effects by metals, small molecules, chemical reactions and replacement of lattice atoms. The methods of bilayer graphene band regulation as well as the fabrication of graphene p-n junction are also introduced, and the future tendency and potential applications of doped graphene are proposed. For graphene, it is relatively easy to produce p-type doping via surface absorption, exposing pristine graphene in those molecules with electron withdrawing groups (H₂O, O₂, N₂, NO₂, PMMA et al.) will lead to evident p-type doping, and graphene of this kind of p-type doping can rapidly recover to its original state when doping molecules are removed. If boron source was introduced into the CVD growth process of graphene, substitutional p-doping that some carbon atoms in graphene hexagonal lattice are replaced by boron atoms can be formed. Compared to the p-type doping, stable n-type doping is not facile for graphene. It has been proved that some electron-donating molecules such as ammonia, potassium, phosphorus, hydrogen and poly(ethyleneimine) (PEI) can produce n-type doping in graphene through surface electron transfer, but these doping effects are unstable. By introducing nitrogen-containing precursors in growth approach, small part of lattice carbon atoms will be replaced by nitrogen atoms which can result in effectively n-doping effect. Combine the p-type and n-type doping method together, the p-n junction can be produced in mono- or bi-layer graphene, a series of novel functional devices like photothermoelectric devices have been constructed using these hetero-doped graphene p-n junctions.

Key words: graphene, doping, semiconductor, bandgap

引用此文

张芸秋, 梁勇明, 周建新. 石墨烯掺杂的研究进展[J]. 化学学报, 2014, 72(3): 367-377.

Zhang Yunqiu, Liang Yongming, Zhou Jianxin. Recent Progress of Graphene Doping[J]. Acta Chimica Sinica, 2014, 72(3): 367-377.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Allen, M. J.; Tung, V. C.; Kaner, R. B. Chem. Rev. 2010, 110, 132.

[2] Zhou, L.; Zhang, L.-M. Acta Chim. Sinica 2014, 72, 289. (周琳, 张黎明, 廖磊, 杨明媚, 谢芹, 彭海琳, 刘志荣, 刘忠范, 化学学报, 2014, 72, 289.)

[3] Lin, Y.-W.; Guo, X.-F. Acta Chim. Sinica 2014, 72, 277. (林源为, 郭雪峰, 化学学报, 2014, 72, 277.)

[4] Mayorov, A. S.; Gorbachev, R. V.; Morozov, S. V.; Britnell, L.; Jalil, R.; Ponomarenko, L. A.; Blake, P.; Novoselov, K.; Watanabe, K.; Taniguchi, T.; Geim, A. K. Nano Lett. 2011, 11, 2396.

[5] Novoselov, K.; Fal, V.; Colombo, L.; Gellert, P.; Schwab, M.; Kim, K. Nature 2012, 490, 192.

[6] Moser, J.; Verdaguer, A.; Jimenez, D.; Barreiro, A.; Bachtold, A. Appl. Phys. Lett. 2008, 92, 123507.

[7] Geim, A. K. Science 2009, 324, 1530.

[8] Guo, B.; Fang, L.; Zhang, B.; Gong, J. R. Insciences J. 2011, 1, 80.

[9] Liu, H.; Liu, Y.; Zhu, D. J. Mater. Chem. 2011, 21, 3335.

[10] Neto, A. C.; Guinea, F.; Peres, N. M. R.; Novoselov, K. S.; Geim, A. K. Rev. Mod. Phys. 2009, 81, 109.

[11] Geim, A. K.; Novoselov, K. S. Nat. Mater. 2007, 6, 183.

[12] Gierz, I.; Riedl, C.; Starke, U.; Ast, C. R.; Kern, K. Nano Lett. 2008, 8, 4603.

[13] Wu, J.-X.; Xu, H.; Zhang, J. Acta Chim. Sinica 2014, 72, 301. (吴娟霞, 徐华, 张锦, 化学学报, 2014, 72, 301.)

[14] Hu, Y.-J.; Jin, J.; Zhang, H. Acta Phys.-Chim. Sin. 2010, 26, 2073. (胡耀娟, 金娟, 张卉, 物理化学学报, 2010, 26, 2073.)

[15] Ristein, J. Science 2006, 313, 1057.

[16] Yavari, F.; Kritzinger, C.; Gaire, C.; Song, L.; Gulapalli, H.; Borca‐Tasciuc, T.; Ajayan, P. M.; Koratkar, N. Small 2010, 6, 2535.

[17] Leenaerts, O.; Partoens, B.; Peeters, F. Phys. Rev. B 2009, 79, 235440.

[18] Docherty, C. J.; Lin, C.-T.; Joyce, H. J.; Nicholas, R. J.; Herz, L. M.; Li, L.-J.; Johnston, M. B. Nat. Commun. 2012, 3, 1228.

[19] Giovannetti, G.; Khomyakov, P.; Brocks, G.; Karpan, V.; Van den Brink, J.; Kelly, P. Phy. Rev. Lett. 2008, 101, 026803.　

[20] Lee, W. H.; Suk, J. W.; Lee, J.; Hao, Y.; Park, J.; Yang, J. W.; Ha, H.-W.; Murali, S.; Chou, H.; Akinwande, D.; Kim, K. S.; Ruoff, R. S. ACS Nano 2012, 6, 1284.

[21] Kalbac, M.; Reina-Cecco, A.; Farhat, H.; Kong, J.; Kavan, L.; Dresselhaus, M. S. ACS Nano 2010, 4, 6055.

[22] Crowther, A. C.; Ghassaei, A.; Jung, N.; Brus, L. E. ACS Nano 2012, 6, 1865.

[23] Wang, X.; Li, X.; Zhang, L.; Yoon, Y.; Weber, P. K.; Wang, H.; Guo, J.; Dai, H. Science 2009, 324, 768.

[24] Bae, S.; Kim, H.; Lee, Y.; Xu, X.; Park, J.-S.; Zheng, Y.; Balakrishnan, J.; Lei, T.; Kim, H. R.; Song, Y. I. Nat. Nanotechnol. 2010, 5, 574.

[25] Li, X.; Fan, L.-L.; Li, Z.; Wang, K.-L.; Zhong, M.-L.; Wei, J.-Q.; Wu, D.-H.; Zhu, H.-W. Adv. Eng. Mater. 2012, 2, 425.

[26] Wang, H.; Zhou, Y.; Wu, D.; Liao, L.; Zhao, S.-L.; Peng, H.-L.; Liu, Z.-F. Small 2013, 9, 1316.

[27] Wu, J.; Xie, L.; Li, Y.; Wang, H.; Ouyang, Y.; Guo, J.; Dai, H. J. Am. Chem. Soc 2011, 133, 19668.

[28] Zhou, L.; Zhou, L.-S.; Yang, M.-M.; Wu, D.; Liao, L.; Yan, K.;X, Q.; L, Z.-R.;P, H.-L.;Liu, Z.-F. Small 2013, 9, 1388.

[29] Li, B.; Zhou, L.; Wu, D.; Peng, H.-L.; Yan, K.; Zhou, Y.; Liu, Z.-F. ACS Nano 2011, 5, 5957.

[30] Some, S.; Kim, J.; Lee, K.; Kulkarni, A.; Yoon, Y.; Lee, S.; Kim, T.; Lee, H. Adv. Mater. 2012, 24, 5481.

[31] Gierz, I.; Riedl, C.; Starke, U.; Ast, C. R.; Kern, K. Nano Lett. 2008, 8, 4603.

[32] Wei, P.; Liu, N.; Lee, H. R.; Adijanto, E.; Ci, L.; Naab, B. D.; Zhong, J. Q.; Park, J.; Chen, W.; Cui, Y.; Bao, Z. N. Nano Lett. 2013, 13, 1890.

[33] Farmer, D. B.; Golizadeh-Mojarad, R.; Perebeinos, V.; Lin, Y. M.; Tulevski, G. S.; Tsang, J. C.; Avouris, P. Nano Lett. 2008, 9, 388.

[34] Bult, J. B.; Crisp, R.; Perkins, C. L.; Blackburn, J. L. ACS Nano 2013, 7, 7251.

[35] Gao, M.; Pan, Y.; Zhang, C.; Hu, H.; Yang, R.; Lu, H.; Cai, J.; Du, S.; Liu, F.; Gao, H.-J. Appl. Phys. Lett. 2010, 96, 053109.

[36] Wei, D.-C.; Liu, Y.-Q.; Wang, Y.; Zhang, H.-L.; Huang, L.-P.; Yu, G. Nano Lett. 2009, 9, 1752.

[37] Qu, L.; Liu, Y., Baek, J. B.; Dai, L.-M. ACS Nano 2010, 4, 1321.

[38] Reddy, A. L. M.; Srivastava, A.; Gowda, S. R.; Gullapalli, H.; Dubey, M.; Ajayan, P. M. ACS Nano 2010, 4, 6337.

[39] Jin, Z.; Yao, J.; Kittrell, C.; Tour, J. M. ACS Nano 2011, 5, 4112.

[40] Luo, Z.; Lim, S.-H.; Tian, Z.-Q.; Shang, J.-Z.; Lai, L.-F.; MacDonald, B.; Fu, C.; Shen, Z.-X.; Yu, T.; Lin, J.-Y. J. Mater. Chem. 2011, 21, 8038.

[41] Zhang, C.-H.; Fu, L.; Liu, N.; Liu, M.-H.; Wang, Y.-Y.; Liu, Z.-F. Adv. Mater. 2011, 23, 1020.

[42] Ci, L.; Song, L.; Jin, C.; Jariwala, D.; Wu, D.; Li, Y.; Srivastava, A.; Wang, Z.; Storr, K.; Balicas, L. Nat. Mater.. 2010, 9, 430.

[43] Liu, L.; Feng, Y.; Shen, Z. X. Phys. Rev. B 2003, 68, 104102.

[44] Bokdam, M.; Khomyakov, P. A.; Brocks, G.; Zhong, Z.; Kelly, P. J. Nano Lett. 2011, 11, 4631.

[45] Kim, B. H.; Hong, S. J.; Baek, S. J.; Jeong, H. Y.; Park, N.; Lee, M.; Lee, S. W.; Park, M.; Chu, S. W.; Shin, H. S.; Lim, J.; Lee, J. C.; Jun, Y.; Park, Y. W. Sci. Rep. 2012, 2, 690.

[46] Castro, E. V.; Novoselov, K.; Morozov, S.; Peres, N.; Dos Santos, J. L.; Nilsson, J.; Guinea, F.; Geim, A.; Neto, A. C. Phys. Rev. Lett. 2007, 99, 216802.

[47] Zhang, Y.; Tang, T.-T.; Girit, C.; Hao, Z.; Martin, M. C.; Zettl, A.; Crommie, M. F.; Shen, Y. R.; Wang, F. Nature 2009, 459, 820.

[48] Ohta, T.; Bostwick, A.; Seyller, T.; Horn, K.; Rotenberg, E. Science 2006, 313, 951.

[49] Pinto, H.; Jones, R.; Goss, J.; Briddon, P. J. Phys.-Condens. Matter 2009, 21, 402001.

[50] Park, J.; Jo, S. B.; Yu, Y. J.; Kim, Y.; Yang, J. W.; Lee, W. H.; Kim, H. H.; Hong, B. H.; Kim, P.; Cho, K. Adv. Mater. 2012, 24, 407.

[51] Samuels, A. J.; Carey, J. D. ACS Nano 2013, 7, 2790.

[52] Yu, W. J.; Liao, L.; Chae, S. H.; Lee, Y. H.; Duan, X. Nano Lett. 2011, 11, 4759.

[53] Kim, S.; Shin, D. H.; Kim, C. O.; Kang, S. S.; Kim, J. M.; Jang, C. W.; Joo, S. S.; Lee, J. S.; Kim, J. H.; Choi, S.-H. ACS Nano 2013, 7, 5168.

[54] Huard,B.; Sulpizio, J.; Stander, N.; Todd, K.; Yang, B.; Goldhaber-Gordon, D. Phys. Rev. Lett. 2007, 98, 236803.

[55] Özyilmaz, B.; Jarillo-Herrero, P.; Efetov, D.; Abanin, D. A.; Levitov, L. S.; Kim, P. Phys. Rev. Lett. 2007, 99, 166804.

[56] Farmer, D. B.; Lin, Y.-M.; Afzali-Ardakani, A.; Avouris, P. Appl. Phys. Lett. 2009, 94, 213106.

[57] Peters, E. C.; Lee, E. J.; Burghard, M.; Kern, K. Appl. Phys. Lett. 2010, 97, 193102.

[58] Yan, K.; Wu, D.; Peng, H.; Jin, L.; Fu, Q.; Bao, X.; Liu, Z. Nat. Commun. 2012, 3, 1280.

[59] Wu, D.; Yan, K.; Zhou, Y.; Wang, H.; Lin, L.; Peng, H.; Liu, Z. J. Am. Chem. Soc. 2013, 135, 10926.