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采用溶胶凝胶法在玻璃衬底上制备了Fe, Co共掺Zn0.9FexCo0.1-xO (x=0, 0.03, 0.05, 0.07)系列薄膜. 通过扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子谱(XPS)和光 致发光(PL)谱对薄膜样品的表面形貌、晶体结构、成分和光学性能进行了研究. XRD结果表明所有ZnO薄膜样品都呈六方纤锌矿结构, 在样品中没有观察到与Fe和Co相关的团簇, 氧化物及其他杂相的衍射峰, 表明共掺杂改善了Fe或Co在ZnO的分散性. XPS测试结果揭示样品中Co离子的价态为+2价; Fe离子的价态为+2价和+3价共存, 但Fe相对浓度的增大导致Fe3+含量增加. 所有样品的室温光致发光谱(PL)均观察到紫外发光峰和蓝光双峰, 其中Fe, Co共掺ZnO薄膜的紫外发光峰较本征ZnO 出现蓝移, 蓝光双峰峰位没有变化, 但发光强度有所减弱; 而掺杂ZnO薄膜的绿光发光峰几乎消失. 最后, 结合微结构和成分分析对薄膜样品的发光机理进行了讨论.The Fe, Co-codoped Zn0.9FexCo0.1-xO (x=0, 0.03, 0.05, 0.07) thin films are fabricated on the glass substrates by sol-gel method. The surface morphologies, crystal structures, elements and optical properties of the films are investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectrum. The XRD results reveal that all the ZnO films are of wurtzite structure. The diffraction peaks of the clusters, oxide or other impurity phase related to Fe and Co are not observed in the samples. This indicates that codoped is beneficial to the improvement on the dispersion of Fe or Co in ZnO. XPS results reveal that Co elements exist as Co2+, Fe elements exist as Fe2+ and Fe3+, but the increase of relative concentration of Fe leads to the increase of Fe3+ content. The ultraviolet emission peak and blue double emission are observed in the PL spectra of all the samples. Compared with the undoped ZnO film, the Co-codoped ZnO film has a blue shift of ultraviolet emission peak of Fe, the unchanged position of the blue double emission peak, and the weakened luminous intensity. Moreover, the green luminescence peak of the doped ZnO film almost disappears. Finally, the luminescence mechanisms of Fe, Co-codoped ZnO films are discussed by combining the microstructures and compositions of the samples.
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Keywords:
- ZnO thin films /
- sol-gel method /
- doping /
- photoluminescence
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[1] Wolf S A, Awschalom D D, Buhrman R, Daughton J M, Molnar S, Roukes M L, Chtchelkanova A Y, Treger D M 2001 Science 294 1488
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[5] [6] [7] Zhang J, Wang S, Wang Y, Xu M, Xia H J, Zhang S, Huang W, Guo X Z, Wu S 2009 Sens. Actuators B 139 411
[8] [9] Yang P D, Yan H Q, Mao S, Russo R, Johnson J, Saykally R, Morris N, Pham J, He R, Choi H J 2002 Adv. Funct. Mater. 12 323
[10] [11] Wang X D, Zhou J, Song J H, Liu J, Xu N S, Wang Z L 2006 Nano Lett. 6 2768
[12] Law M, Greene L E, Johnson J C, Saykally R, Yang P 2005 Nat. Mater. 4 455
[13] [14] Kumar R, Singh A P, Thakur P, Chae K H, Choi W K, Angadi B, Kaushik S D, Patnaik S 2008 J. Phys. D: Appl. Phys. 41 155002
[15] [16] Shan F K, Kim B I, Liu G X, Liu Z F, Sohn J Y, Lee W J, Shin B C, Yu Y S 2004 J. Appl. Phys. 95 4772
[17] [18] [19] Cui J B, Gibson U 2006 Phys. Rev. B 74 045416
[20] [21] Wu Y N, Xu M, Wu D C, Dong C J, Zhang P P, Ji H X, He L 2011 Acta Phys. Sin. 60 077505 (in Chinese) [吴艳南, 徐 明, 吴定才, 董成军, 张佩佩, 纪红萱, 何林 2001 物理学报 60 077505]
[22] [23] Wu Z H, Xu M, Duan W Q 2012 Acta Phys. Sin. 61 117502 (in Chinese) [吴忠浩, 徐明, 段文倩 2012 物理学报 61 117502]
[24] Li A X, Bi H, Liu Y M, Wu M Z 2008 Chin. J. Luminescence 29 289 (in Chinese) [李爱侠, 毕红, 刘艳美, 吴明在 2008 发光学报 29 289]
[25] [26] Han S J, Song J W, Yang C H, Park S H, Park J H, Jeong Y H 2002 Appl. Phys. Lett. 81 4212
[27] [28] Hu Z G, Duan Y M, Xu M, Zhou X, Chen Q Y, Dong C J, Linghu R F 2009 Acta Phys. Sin. 58 1166 (in Chinese) [胡志刚, 段满益, 徐明, 周勋, 陈青云, 董成军, 令狐荣峰 2009 物理学报 58 1166]
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[57]
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