Effect of intrinsic defects and copper impurities co-existing on electromagnetic optical properties of ZnO: First principles study

Zhang Mei-Ling; Chen Yu-Hong; Zhang Cai-Rong; Li Gong-Ping

doi:10.7498/aps.68.20182238

Abstract

For ZnO which is not magnetic itself, it is of great significance to study the source of ferromagnetism and its photoelectric properties when Cu doped ZnO coexists with internal defects. The effects of intrinsic defects on the electronic structures, magnetic and optical properties of Cu-doped ZnO (Cu_Zn) are studied by using first principle calculations based on the density functional theory combined with the Hubbard U (DFT + U_d + U_p). The results indicate that the doped Cu is a substitute acceptor, and the manufacturing environment plays an important role in forming the Cu_Zn with internal defects. Under the oxygen-rich condition, the doped Cu is favorable for forming internal defects, and the Cu_Zn—O_i bonds are easily formed. On the contrary, the Cu-doped ZnO is not conducive to forming internal defects under the O-poor condition. The 3d electrons of the substitute Cu form the unoccupied accepter energy level at the top of valence band, generating p-type conduction. Comparing with Cu_Zn system, the carrier concentration of positive hole decreases in Cu_Zn-V_O system and the conductivity is poor. In the Cu_Zn-V_Zn system, the number of carrier holes is almost constant, and the conductivity has no effect. In the Cu_Zn-O_i model, the carrier concentration of positive holes increases and the conductivity gets better. The pure ZnO system exhibits non-magnetic behavior. The study also reveals that the smaller the electro-negativity, the greater the contribution to magnetic moment is when O atom is connected with Cu atom. The magnetic moments in Cu_Zn and Cu_Zn-O_i system are mainly generated by the coupling between the Cu 3d and the O 2p orbital on the c axis. When V_O and V_Zn exist in Cu_Zn, the magnetic moment is mainly caused by the strong coupling of Cu 3d with O 2p in ab plane. In the presence of V_Zn in Cu_Zn, the magnetism also contains the contribution of the spin polarization of O(5, 6) atoms around V_Zn. In the defect states of Cu_Zn-V_Zn and Cu_Zn-O_i, the induced states in the deep energy levels are generated by the interaction between the O-O 2s orbital electrons. The reduced optical band gap of the Cu_Zn model results in the red shift of absorption spectrum. The enhanced absorption and reflection of the Cu_Zn-V_Zn model reduce the transmission.

Keywords:

Authors and contacts

1.
School of Science, Lanzhou University of Technology, Lanzhou 730050, China
2.
School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000, China

Corresponding author: Zhang Mei-Ling, Zhangml_2000@126.com

Funds: Project supported by National Natural Science Foundation of China (Grant Nos. 51562022, 11575074) and the HongLiu First-class Disciplines Development Program of Lanzhou University and Technology, China.

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References

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Cited By

图 1 2 × 2 × 2的ZnO的超胞 (红色代替O原子, 蓝紫色代替的是Zn原子)

Figure 1. 2 × 2 × 2 ZnO supercell (where the red components represent the O atoms, gray represents the Zn atoms)

DownLoad: Full-Size Img PowerPoint

图 2 (a) ZnO能带结构图; (b) ZnO分波态密度图

Figure 2. (a) Band Structures of ZnO; (b) PDOS of ZnO

DownLoad: Full-Size Img PowerPoint

图 3 优化后的晶体结构图　(a) Cu_Zn; (b) Cu_Zn-V_O; (c) Cu_Zn-V_Zn; (d) Cu_Zn-O_i

Figure 3. Structure of crystal cell after optimized: (a) Cu_Zn; (b) Cu_Zn-V_O; (c) Cu_Zn-V_Zn; (d) Cu_Zn-O_i

DownLoad: Full-Size Img PowerPoint

图 5 分波态密度(图中虚线为费米能级)　(a) Cu_Zn; (b) Cu_Zn-V_O; (c) Cu_Zn-V_Zn; (d) Cu_Zn-O_i

Figure 5. PDOS (the dotted line in the graph is the Fermi energy level ): (a) Cu_Zn; (b) Cu_Zn-V_O; (c) Cu_Zn-V_Zn; (d) Cu_Zn-O_i

DownLoad: Full-Size Img PowerPoint

图 4 能带结构图(图中虚线为费米能级)　(a) Cu_Zn; (b) Cu_Zn-V_O; (c) Cu_Zn-V_Zn; (d) Cu_Zn-O_i

Figure 4. Band structures (the dotted line in the graph is the Fermi energy level): (a) Cu_Zn; (b) Cu_Zn-V_O; (c) Cu_Zn-V_Zn; (d) Cu_Zn-O_i

DownLoad: Full-Size Img PowerPoint

图 6 ZnO, Cu_Zn及含不同内在缺陷时(Cu_Zn-V_O, Cu_Zn-V_Zn, Cu_Zn-O_i)介电函数的虚部

Figure 6. The imaginary part of the dielectric function of ZnO, Cu_Zn, Cu_Zn-V_O, Cu_Zn-V_Zn, Cu_Zn-O_i

DownLoad: Full-Size Img PowerPoint

图 7 有内在缺陷Cu_Zn的吸收光谱

Figure 7. Absorption of Cu_Zn with varying intrinsic defects

DownLoad: Full-Size Img PowerPoint

图 8 有内在缺陷Cu_Zn的反射光谱

Figure 8. Reflectivity of Cu_Zn with varying intrinsic defects

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表 1 ZnO和Cu_Zn缺陷的形成能(单位: eV)

Table 1. Formation energy of ZnO and Cu_Zn with intrinsic defects (in eV)

缺陷类型	V_O	V_Zn	O_i	Cu_i	Cu_Zn	Cu_Zn-V_O	Cu_Zn-V_Zn	Cu_Zn-O_i
O-rich	6.603	0.915	–0.548	5.795	–0.495	6.337	0.422	–0.965
O-poor	1.308	6.210	4.747	4.026	3.031	4.569	9.244	7.856

DownLoad: CSV

表 2 ZnO模型的带隙和空穴浓度P

Table 2. Band gap and hole concertration P of ZnO model

	ZnO	Cu_Zn	Cu_Zn-V_O	Cu_Zn-V_Zn	Cu_Zn-O_i
禁带宽度/eV	3.370	2.577	2.413	2.597	1.885
光学带隙/eV	3.370	0.980	0.228	1.108	0.195
P	0.068	1.344	1.107	1.321	1.574

DownLoad: CSV

[1]	Wang Z L 2008 ACS Nano 2 1987 Google Scholar
[2]	Ahn K S, Deutsch T, Yan Y, Jiang C S, Perkins C L, Turner J, Jassim M A 2007 J. Appl. Phys. 102 023517 Google Scholar
[3]	Wei M, Braddon N, Zhi D, Midgley P A, Chen S K, Blamire M G, Driscoll J L M 2005 Appl. Phys. Lett. 86 072514 Google Scholar
[4]	Drmosh Q A, Rao S G, Yamani Z H, Gondal M A 2013 Appl. Surf. Sci. 270 104 Google Scholar
[5]	Suja M, Bashar S B, Morshed M M, Liu J 2015 ACS Appl. Mater. Interfaces 7 8894 Google Scholar
[6]	Chakraborty M, Ghosh A, Thangavel R 2015 J. Sol-Gel Sci. Technol. 74 756 Google Scholar
[7]	Horzum S, Torun E, Serin T, Peeters F M 2016 Philos. Mag. 96 1743 Google Scholar
[8]	Vachhani P S, Bhatnagar A K 2013 Phys. Scr. 8715 045702
[9]	Xia C H, Wang F, Hu C L 2014 J. Alloys Compd. 589 604 Google Scholar
[10]	侯清玉, 许镇潮, 乌云, 赵二俊 2015 物理学报 64 167201 Google Scholar Hou Q Y, Xu Z C, Wu Y, Zhao E J 2015 Acta Phys. Sin. 64 167201 Google Scholar
[11]	Iqbal J, Jan T, Shafiq M, Arshad A, Ahmad N, Badshah S, Yu R H 2014 Ceram. Int. 40 2091 Google Scholar
[12]	Li T J, Li G P, Gao X X, Chen J S 2010 Chin. Phys. Lett. 27 211
[13]	Nia B A, Shahrokhi M, Moradian R, Manouchehri I 2014 Eur. Phys. J. Appl. Phys. 67 20403 Google Scholar
[14]	Keavney D J, Buchholz D B, Ma Q, Chang R P 2007 Appl. Phys. Lett. 91 012501 Google Scholar
[15]	Xu Q Y, Schmidt H, Zhou S Q, Potzger K, Helm M, Hochmuth H, Lorenz M, Setzer A, Esquinazi P, Meinecke C, Grundmann M 2008 Appl. Phys. Lett. 92 082508 Google Scholar
[16]	Zhu M Y, Zhang Z H, Zhong M, Tariq M, Li Y, Li W X, Jin H M, Skotnicova K, Li Y B 2017 Ceram. Int. 43 3166 Google Scholar
[17]	Luo J H, Liu Q, Yang L N, Sun Z Z, Li Z S 2014 Comput. Mater. Sci. 82 70 Google Scholar
[18]	Wang Q B, Zhou C, Wu J, Lü T 2013 Opt. Commun. 297 79 Google Scholar
[19]	Chen Y F, Song Q G, Yan H Y 2012 Comput. Theor. Chem. 983 65 Google Scholar
[20]	Lee M H, Peng Y C, Wu H C 2014 J. Alloys Compd. 616 122 Google Scholar
[21]	Wu H C, Peng Y C, Chen C C 2013 Opt. Mater. 35 509 Google Scholar
[22]	Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phys.: Condens. Matter 14 2717 Google Scholar
[23]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[24]	Ma X G, Lu B, Li D, Shi R, Pan C S, Zhu Y F 2011 J. Phys. Chem. C 115 4680
[25]	Anisimov V V, Zaanen J, Andersen K 1991 Phys. Rev. B: Condens. Matter 44 943 Google Scholar
[26]	Monkhost H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[27]	Vanderbilt D 1990 Phys. Rev. B: Condens. Matter 41 7892 Google Scholar
[28]	Janotti A, van de Walle C G 2007 Phys. Rev. B 76 165202 Google Scholar
[29]	Guo T T, Dong G B, Chen Q, Diao X G, Gao F Y 2014 J. Phys. Chem. Solids 75 42 Google Scholar
[30]	Sun H G, Fan W L, Li Y L, Cheng X F, Li P, Hao J C, Zhao X 2011 Phys. Chem. Chem. Phys. 13 1379 Google Scholar
[31]	Chen Y, Xu X L, Zhang G H, Xue H, Ma S Y 2009 Physica B 404 3645 Google Scholar
[32]	段壮芬, 王新强, 何阿玲, 程志梅 2011 原子与分子物理学报 28 343 Google Scholar Duan Z F, Wang X Q, He A L, Cheng Z M 2011 J. At. Mol. Phys. 28 343 Google Scholar
[33]	Ferhat M, Zaoui A, Ahuja R 2009 Appl. Phys. Lett. 94 142502 Google Scholar
[34]	Yan Y F, Aljassim M M, Wei S H 2006 Appl. Phys. Lett. 89 181912 Google Scholar
[35]	Narendra G L, Sreedhar B, Rao J L, Lakshman S V J 1991 J. Mater. Sci. 26 5342 Google Scholar
[36]	Lee H Y, Clark S J, Robertson J 2012 Phys. Rev. B 86 075209 Google Scholar
[37]	林俏露, 李公平, 许楠楠, 刘欢, 王苍龙 2017 物理学报 66 037101 Google Scholar Lin Q L, Li G P, Xu N N, Liu H, Wang C L 2017 Acta Phys. Sin. 66 037101 Google Scholar
[38]	Zhao L, Lu P F, Yu Z Y, Liu Y M, Wang D L, Ye H 2010 Chin. Phys. B 19 056104 Google Scholar
[39]	徐庆岩, 吴雪梅, 诸葛兰剑, 陈学梅, 吴兆丰 2008 微细加工技术 12 16 Xu Q Y, Wu X M, Zhuge L J, Chen X M, Wu Z F 2008 MicroFabric. Tech. 12 16

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