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.

FullText HTML : translate this paragraph

References

[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

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

DownLoad: Full-Size Img PowerPoint

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

[1]	Shi Xiao-Hong, Hou Bin-Peng, Li Zhi-Shuo, Chen Jing-Jin, Shi Xiao-Wen, Zhu Zi-Zhong. Formation of oxygen vacancy clusters in Li-rich Mn-based cathode Materials of lithium-ion batteries: First-principles calculations. Acta Physica Sinica, 2023, 72(7): 078201. doi: 10.7498/aps.72.20222300
[2]	Lin Hong-Bin, Lin Chun, Chen Yue, Zhong Ke-Hua, Zhang Jian-Min, Xu Gui-Gui, Huang Zhi-Gao. First-principles study of effect of Mg doping on structural stability and electronic structure of LiCoO₂ cathode material. Acta Physica Sinica, 2021, 70(13): 138201. doi: 10.7498/aps.70.20210064
[3]	Mo Man, Zeng Ji-Shu, He Hao, Zhang Liang, Du Long, Fang Zhi-Jie. The first-principle study on the formation energies of Be, Mg and Mn doped CuInO₂. Acta Physica Sinica, 2019, 68(10): 106102. doi: 10.7498/aps.68.20182255
[4]	Chen Dong-Yun, Gao Ming, Li Yong-Hua, Xu Fei, Zhao Lei, Ma Zhong-Quan. First principle study of formation mechanism of molybdenum-doped amorphous silica in MoO₃/Si interface. Acta Physica Sinica, 2019, 68(10): 103101. doi: 10.7498/aps.68.20190067
[5]	Luo Ming-Hai, Li Ming-Kai, Zhu Jia-Kun, Huang Zhong-Bing, Yang Hui, He Yun-Bin. First-principles study on thermodynamic properties of CdxZn1-xO alloys. Acta Physica Sinica, 2016, 65(15): 157303. doi: 10.7498/aps.65.157303
[6]	Hou Qing-Yu, Xu Zhen-Chao, Wu Yun, Zhao Er-Jun. Effects of Cu doped ZnO diluted magnetic semiconductors on magnetic and electrical performance from simulation and calculation. Acta Physica Sinica, 2015, 64(16): 167201. doi: 10.7498/aps.64.167201
[7]	He Jing-Fang, Zheng Shu-Kai, Zhou Peng-Li, Shi Ru-Qian, Yan Xiao-Bing. First-principles calculations on the electronic and optical properties of ZnO codoped with Cu-Co. Acta Physica Sinica, 2014, 63(4): 046301. doi: 10.7498/aps.63.046301
[8]	Li Hong-Lin, Zhang Zhong, Lü Ying-Bo, Huang Jin-Zhao, Zhang Ying, Liu Ru-Xi. First principles study on the electronic and optical properties of ZnO doped with rare earth. Acta Physica Sinica, 2013, 62(4): 047101. doi: 10.7498/aps.62.047101
[9]	Hao Hong-Fei, Wang Jing, Sun Feng, Zhang Lan-Ting. First-principles calculation of preferential site occupation of Dy ions in Nd2Fe14B lattice and its effect on local magnetic moments of Fe ions. Acta Physica Sinica, 2013, 62(11): 117501. doi: 10.7498/aps.62.117501
[10]	Linghu Jia-Jun, Liang Gong-Ying. First-principles study on the luminescence property of In-doped ZnTe. Acta Physica Sinica, 2013, 62(10): 103102. doi: 10.7498/aps.62.103102
[11]	Zhang Wei, Xu Zhao-Peng, Wang Hai-Yan, Chen Fei-Hong, He Chang. First-principles study of the native defects in InI crystal. Acta Physica Sinica, 2013, 62(24): 243101. doi: 10.7498/aps.62.243101
[12]	Tang Dong-Hua, Xue Lin, Sun Li-Zhong, Zhong Jian-Xin. Doping effect of boron in Hg0.75Cd0.25Te: first-principles study. Acta Physica Sinica, 2012, 61(2): 027102. doi: 10.7498/aps.61.027102
[13]	Hou Qing-Yu, Zao Chun-Wang, Li Ji-Jun, Wang Gang. Frist principles study of effect of high Al doping concentrationof p-type ZnO on electric conductivity performance. Acta Physica Sinica, 2011, 60(4): 047104. doi: 10.7498/aps.60.047104
[14]	Shi Li-Bin, Xiao Zhen-Lin. Origin of ferromagnetic properties in Ni doped ZnO by the first principles study. Acta Physica Sinica, 2011, 60(2): 027502. doi: 10.7498/aps.60.027502
[15]	Liu Xian-Kun, Liu Ying, Qian Da-Zhi, Zheng Zhou. First-principles study of helium atom doped interstitial sites of Al. Acta Physica Sinica, 2010, 59(9): 6450-6456. doi: 10.7498/aps.59.6450
[16]	Huang Yun-Xia, Cao Quan-Xi, Li Zhi-Min, Li Gui-Fang, Wang Yu-Peng, Wei Yun-Ge. First-principles calculation of microwave dielectric properties of Al-doping ZnO powders. Acta Physica Sinica, 2009, 58(11): 8002-8007. doi: 10.7498/aps.58.8002
[17]	Li Hong, Wang Shao-Qing, Ye Heng-Qiang. Influence of Nb doping on oxidation resistance of γ-TiAl:A first principles study. Acta Physica Sinica, 2009, 58(13): 224-S229. doi: 10.7498/aps.58.224
[18]	Chen Kun, Fan Guang-Han, Zhang Yong, Ding Shao-Feng. First principles study of In-N codoped ZnO. Acta Physica Sinica, 2008, 57(5): 3138-3147. doi: 10.7498/aps.57.3138
[19]	Chen Kun, Fan Guang-Han, Zhang Yong. First principles study of optical properties of wurtzite ZnO with Mn-doping. Acta Physica Sinica, 2008, 57(2): 1054-1060. doi: 10.7498/aps.57.1054
[20]	Ye Hong-Gang, Chen Guang-De, Zhu You-Zhang, Zhang Jun-Wu. First principle study of the native defects in hexagonal aluminum nitride. Acta Physica Sinica, 2007, 56(9): 5376-5381. doi: 10.7498/aps.56.5376

Catalog

Vol. 68, Issue 8 - 2019-04-20

Metrics

Abstract views: 10784
PDF Downloads: 148
Cited By: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

Search

Article

留言板