过渡金属与F共掺杂ZnO薄膜结构及磁、光特性

周攀钒; 袁欢; 徐小楠; 鹿轶红; 徐明

doi:10.7498/aps.64.247503

摘要

采用溶胶-凝胶法在玻璃衬底上制备了过渡金属元素与F共掺杂Zn0.98-xTMxF0.02O (TMx=Cu0.02, Ni0.01, Mn0.05, Fe0.02, Co0.05)薄膜, 进而利用X射线衍射仪、扫描电子显微镜、紫外-可见透过谱、光致发光及振动样品磁强计等研究了薄膜的表面形貌、微结构、禁带宽度及光致发光(PL)和室温磁学特性. 研究表明: 掺杂离子都以替位的方式进入了ZnO晶格, 掺杂不会破坏ZnO的纤锌矿结构. 其中Zn0.93Co0.05F0.02O薄膜样品的颗粒尺寸最大, 薄膜的结晶度最好且c轴择优取向明显; Zn0.93Mn0.05F0.02O薄膜样品的颗粒尺寸最小, 薄膜结晶度最差且无明显的c轴择优取; Cu, Ni, Fe与F共掺杂样品的颗粒尺寸大小几乎相同. TM掺杂样品均表现出很高的透过率, 同时掺杂后的薄膜样品的禁带宽度都有不同程度的红移. PL谱观察到Zn0.98-xTMxF0.02O薄膜的发射峰主要由较强的紫外发射峰和较弱的蓝光发射峰组成. Zn0.93Mn0.05F0.02O薄膜样品的紫外发光峰最弱, 蓝光发射最强, 饱和磁化强度最大; 与之相反的是Zn0.96Cu0.02F0.02O薄膜, 其紫外发光峰最强, 蓝光发射最弱, 饱和磁化强度最小. 结合微结构和光学性质对Zn0.98-xTMxF0.02O薄膜的磁学性质进行了讨论.

关键词:

Abstract

Transition metal (TM=Cu, Ni, Mn, Fe and Co)-doped ZnO:F thin films are deposited on glass substrates by a sol-gel method through using ethanol as solvent. All the samples are checked by using X-ray diffraction (XRD), atomic force microscope (AFM), X-ray photoelectron spectroscope (XPS), photoluminescence, UV spectrophotometer, and vibrating sample magnetometer. The XRD reveals that Cu, Ni, Mn, Fe and Co occupy the Zn sites successfully without changing the wurtzite structure of ZnO at moderate doping concentration, and no evidence of any secondary phases is found. The AFM measurements show that the average values of crystallite surface roughness of the samples are in a range from about 2 to 12.7 nm. The surface of ZnO:F thin film becomes less compact and uniform when ZnO:F thin film is doped with TM ions. The TM ions are indeed substituted at the Zn2+ site into the ZnO lattice as shown in the results obtained by XPS and XRD. Further studies show that most of the ZnO films exhibit preferred (002) orientations, while the best c-axis orientation occurs in Zn0.93Co0.05F0.02O film. However, the crystalline quality and preferential orientation of ZnO film become poor in Zn0.93Mn0.05F0.02O. The optical bandgaps of all the ZnO:F films decrease after doping TM. All the samples show high transmittance values in the visible region. Strong ultraviolet emission and weak blue emission are observed in the photoluminescence spectra measured at room temperature for all the samples. The Zn0.93Mn0.05F0.02O film shows the weakest ultraviolet emission peak and strongest blue emission peak, corresponding to the strongest ferromagnetism; while for the Zn0.96Cu0.02F0.02O film, the strongest ultraviolet emission peak and weakest blue emission peak are observed, accompanied by the weakest ferromagnetism. To determine the optical bandgap (Eg) of TM-doped ZnO:F thin film, we plot the curve of (α hv)2 versus photon energy (hv). It is found that the Eg decreases from 3.16 eV to 3.01 eV with the TM ions doping. We show the variations of saturation magnetization with the Vm O concentration for TM-doped ZnO:F thin films with the different transition metal ions. In the case of Cu-doped ZnO:F thin films, the ZnO sample shows that a weaker magnetism. ZnMnFO film exhibits well-defined hysteresis with a coercive field of 7.28×10-5 emu/g. Further studies reveal that these interesting magnetic properties are correlated with the defect-related model for ferromagnetism. Our results will expand the applications of ZnO:F thin films in visible light emitting diode, photovoltaic devices, photoelectrochromic devices, etc. Meanwhile, extreme cares should be taken to control the codoping of ZnO:F thin films for tuning the magnetization.

Keywords:

作者及机构信息

1.
西南民族大学电气信息工程学院, 信息材料四川省重点实验室, 成都 610041

通信作者: 徐明, hsuming_2001@aliyun.com

基金项目: 四川省学术和技术带头人培养基金(批准号: 25727502)和西南民族大学研究生学位点建设项目(批准号: 2015XWD-S0805)资助的课题.

Authors and contacts

1.
Key Laboratory of Information Materials of Sichuan Province, College of Electrical and Information Engineering Southwest University for Nationalities, Chengdu 610041, China

Corresponding author: Xu Ming, hsuming_2001@aliyun.com

Funds: Project supported by the Sichuan Provincial Foundation for Leaders of Disciplines in Science and Technique, China (Grant No. 25727502) and the Foundation for Graduate Degree of Southwest University for Nationalities, China (Grant No. 2015XWD-S0805).

参考文献

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[42]	Kittilstved K R, Liu W K, Gamelin D R 2006 Nat. Mater. 5 291
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施引文献

[1]	Wu F, Meng P W, Luo K, Liu Y F, Kan E J 2015 Chin. Phys. B 24 037504
[2]	Sato K, Katayams H 2000 Jpn. J. Appl. Phys. 39 L555
[3]	Dietl T, Ohno H, Matsukura F, Cibert J, Ferrand D 2000 Science 287 1019
[4]	Xu M, Yuan H, You B, Zhou P F, Dong C J, Duan M Y 2014 J. Appl. Phys. 115 093503
[5]	Renero-Lecuna C, Martín-Rodríguez R, Gonzaález J, Rodríguez F, Almonacid G, Segura A 2014 Chem. Mater. 26 1100
[6]	Yuan H, Xu M, Du X S 2015 Mater. Lett. 154 94
[7]	Zou C W, Wang H J, Liang F, Shao L X 2015 Appl. Phys. Lett. 106 142402
[8]	Ferhat M, Zaoui A, Ahuja R 2009 Appl. Phys. Lett. 94 142502
[9]	Beltrán J J, Osorio J A, Barrero C A, Hanna C B, Punnoose A 2013 J. Appl. Phys. 113 17C308
[10]	Shen Y B, Zhou X, Xu M, Ding Y C, Duan M Y, Linghu R F, Zhu W J 2007 Acta Phys. Sin. 56 3440 (in Chinese) [沈益斌, 周勋, 徐明, 丁迎春, 段满益, 令狐荣锋, 祝文军 2007 56 3440]
[11]	Xu M, Zhao H, Ostrikov K, Duan M Y, Xu L X 2009 J. Appl. Phys. 105 043708
[12]	Yan W S, Sun Z H, Liu Q H, Yao T, Jiang Q H, Hu F C, Li Y Y, He J F, Peng Y H, Wei S Q 2010 Appl. Phys. Lett. 97 042504
[13]	Gong J J, Chen J P, Zhang F, Wu H, Qin M H, Zeng M, Gao X S, Liu J M 2015 Chin. Phys. B 24 037505
[14]	Yamamoto T, Katayama Y H 1999 J. Appl. Phys. 38 166
[15]	Duan M Y, Xu M, Zhou H P, Shen Y B, Chen Q Y, Ding Y C, Zhu W J 2007 Acta Phys. Sin. 56 5359 (in Chinese) [段满益, 徐明, 周海平, 沈益斌, 陈青云, 丁迎春, 祝文军 2007 56 5359]
[16]	Lin X L, Yan S S, Zhao M W, Hu S J, Yao X X, Han C 2010 J. Appl. Phys. 107 033903
[17]	Shinde S S, Shine P S, Pawar S M, Moholkar A V, Bhosale C H, Rajpure K Y 2008 Solid Stat. Sci. 10 1209
[18]	Maldonado A, Guillen-Santiago A, de la Olvera L, Castanedo-Pérez R, Torres-Delgado G 2005 Mater. Lett. 59 1146
[19]	Altamirano-Juarez D C, Torres-Delgado G, Jimenez-Sandoval S, Jimenez-Sandoval O, Castanedo-Perez R 2004 Sol. Energ. Mat. Sol. C. 82 35
[20]	Coey J M D, Venkatesan M, Fitzgerald C B 2005 Nat. Mater. 4 173
[21]	Gilliland S J, Sans J A, Sánchez-Royo J F, Almonacid G, García-Domene B, Segura A, Tobias G, Canadell E 2012 Phy. Rev. B 86 155203
[22]	Yuan H, Xu M, Huang Q Z 2014 J. Alloys Compd. 616 401
[23]	Nesakumar N, Rayappan J B B, Jeyaprakash B G, Krishnan U M 2012 J. Appl. Sci. 12 1758
[24]	Alias S S, Ismail A B, Mohamad A A 2010 J. Alloys Compd. 499 231
[25]	Yuan H, Zhang L, Xu M, Du X S 2015 J. Alloys Compd. 651 571
[26]	Sudakar C, Thakur J S, Lawes G, Naik R, Naik V M 2007 Phys. Rev. B 75 054423
[27]	Hong R J, Huang J B, He H B, Fan Z X, Shao J D 2005 Appl. Surf. Sci. 242 346
[28]	Wu Z F 2010 Ph. D. Dissertation (Suzhou: Suzhou University) (in Chinese) [吴兆丰 2010 博士学位论文 (苏州: 苏州大学)]
[29]	Moulder J F, Sticlae W F, Sobol P E, et al. 1992 Handbook of X-ray Photoelectron Spectroscopy (Eden Prairie Minnesota: Perkin-Elmer Corporation) pp87-93
[30]	Javakumar O D, Sudakar C, Vinu A, Asthana A, Tyagi A K 2009 J. Phys. Chem. 113 4814
[31]	Pei Z X, Ding L Y, Hu J, Weng S X, Zheng Z Y, Huang M L, Liu P 2013 Appl. Catal. B: Environ. 142 736
[32]	Chen M, Wang X, Yu Y H, Pei Z L, Bai X D, Sun C, Huang R F, Wen L S 2000 Appl. Surf. Sci. 158 134
[33]	Hsieh P T, Chen Y C, Kao K S, Wang C M 2008 Appl. Phys. A 90 317
[34]	Jing L Q, Xu Z L, Sun X J, Shang J, Cai W M 2001 Appl. Surf. Sci. 108 308
[35]	Jing L Q, Yuan F L, Hou H G, Xin B F, Cai W M, Fu H G 2004 Chin. Sci. B: Chem. 34 310 (in Chinese) [井立强, 袁福龙, 侯海鸽, 辛柏福, 蔡伟民, 付宏刚 2004 中国科学B辑化学 34 310]
[36]	Venkataprasad S B, Deepak F L 2005 Solid State Commun. 135 345
[37]	Kurbanov S S, Panin G N, Kim T W, Kang T W 2008 Phys. Rev. B 78 045311
[38]	Li H D, Yu S F, Abiyasa A P, Yuen C, Lau S P, Yang H Y, Leong E S P 2005 Appl. Phys. Lett. 86 261111
[39]	Song C, Geng K W, Zeng F, Wang X B, Shen Y X, Pan F, Xie Y N, Liu T, Zhou H T, Fan Z 2006 Phys. Rev. B. 73 024405
[40]	Zhou P F, Yuan H, Zhang Q, Zhang Q P, Xu X N, Lu Y H, Zhang C L, Xu M 2014 J. Synth. Cryst. 43 3427 (in Chinese) [周攀钒, 袁欢, 张琴, 张秋平, 徐小楠, 鹿轶红, 章春来, 徐明 2014人工晶体学报 43 3427]
[41]	Janisch R, Gopal P, Spaldin N A 2005 J. Phys.: Condens. Matter 17 R657
[42]	Kittilstved K R, Liu W K, Gamelin D R 2006 Nat. Mater. 5 291
[43]	Quan Z, Li D, Sebo B, Liu W, Guo S S, Xu S, Huang H M, Fang G J, Li M Y, Zhao X Z 2010 Appl. Surf. Sci. 256 3669
[44]	Hu F C, Liu Q H, Sun Z H, Yao T, Pan Z Y, Li Y Y, He J F, He B, Xie Z, Yan W S, Wei S Q 2011 J. Appl. Phys. 109 103705
[45]	Naeem M, Hasanain S K, Afgan S S, Rumaiz A 2008 J. Phys.: Condens. Mater. 20 255223
[46]	Coey J M D, Douvalis A P, Fitzgerald C B, Venkatesan M 2004 Appl. Phys. Lett. 84 1332

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