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利用直流脉冲磁控溅射方法在室温下通过改变O2流量制备具有不同晶体结构的N掺杂TiO2薄膜,利用台阶仪、X射线光电子能谱仪、X射线衍射仪、紫外-可见分光光度计等设备对薄膜沉积速率、化学成分、晶体结构、禁带宽度等进行分析.结果表明:所制备的薄膜元素配比约为TiO1.68±0.06N0.11±0.01,N为替位掺杂,所有样品退火前后均未形成Ti—N相结构,N掺杂TiO2薄膜的沉积速率、晶体结构等主要依赖于O2流量.在O2流量为2 sccm时,N掺杂TiO2薄膜沉积速率相对较高,薄膜为非晶态结构,但薄膜内含有锐钛矿(anatase)和金红石(rutile)相晶核,退火后薄膜呈anatase和rutile相混合结构,禁带宽度仅为2.86 eV.随着O2流量的增加,薄膜沉积速率单调下降,退火后样品禁带宽度逐渐增加.当O2流量为12 sccm时,薄膜为anatase相择优生长,退火后呈anatase相结构,禁带宽度为3.2 eV.综合本实验的分析结果,要在室温条件下制备晶态N掺杂TiO2薄膜,需在高O2流量(>10 sccn)条件下制备.N doped TiO2 films were deposited in direct current pulsed magnetron sputtering system at room temperature. We have studied the influence of O2 flow rate on the crystal structure of deposited films by using stylus profilometer, X-ray photoelectron spectroscope, X-ray diffractometer, and ultraviolet-visible spectrophotometer. The results indicate that the growth behavior and crystal structure of N doped TiO2 film is dominated by the O2 flow rate. It was found that the chemical stiochiometry is close to TiO1.68±0.06N0.11±0.01 for all film samples, in which the N mainly exists in substitutional doped state. When O2 flow rate is 2 sccm (1 sccm=1 mL/min), N doped TiO2 film has amorphous structure with high growth rate, which contains both anatase phase and rutile phase crystal nucleuses. In this case, the film displays the mix-phase of anatase and rutile and the band gap is 2.86eV after annealing treatment. The film growth rate decreases with increasing O2 flow rate. After annealing treatment, the band gap of N doped TiO2 films decreases with increasing O2 flow rate. While N doped TiO2 film is anatase phase when O2 flow rate is 12sccm. In this case, the band gap is 3.2eV after annealing treatment. It should be noticed that no TiN phase appears for all samples before and after annealing treatment.
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Keywords:
- N doped TiO2 film /
- magnetron sputtering /
- chemical stiochiometry /
- crystal structure
[1] Fujishima A, Honda K 1972 Nature 37 238
[2] Wasielewski R, Domaradzki J, Wojcieszak D, Kaczmarek D, Borkowska A, Prociow E L, Ciszewski A 2008 Appl. Surf. Sci. 254 4396
[3] Press) p73 (in Chinese)[菅井秀郎 2002 等离子体电子工程学 (北京:科学出版社)]
[4] Solid Films 516 1434
[5] Borrás A, Yanguas-Gil A, Barranco A, Cotrino A, González-Elipe A R 2007 Phys. Rev. B 76 235303
[6] Tavares C J, Marques S M, Lanceros-Méndez S, Sencadas V, Teixeira V, Carneiro J O, Martins A J, Fernandes A J 2008 Thin
[7] Hu L H, Dai J, Liu W Q, Wang K J, Dai S Y 2009 Acta Phys. Sin. 58 1115 (in Chinese)[胡林华、戴 俊、刘伟庆、王孔嘉、戴松元2009 物理学报 58 1115]
[8] Shah I, Li W, Huang CP, Jung O, Ni C 2002 Proc. Natl. Acad. Sci. U. S. A. 99 6482
[9] Li W, Frenkel A I, Woicik J C, Ni C, Shah S I 2005 Phys. Rev. B 72 155315
[10] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y 2001 Science 293 269
[11] Tavares C J, Marques S M, Viseu T, Teixeira V, Carneiro J O, Alves E, Barradas N P, Munnik F, Girardeau T, Rivière J P 2009 J. Appl. Phys. 106 113535
[12] Sui R H, Young J L, Berlinguette C P 2010 J. Mater. Chem. 20 498
[13] Yasunori T 2009 Thin Solid Films 517 3167
[14] Tomás S A, Luna-Resendis A, Cortés-Cuautli L C, Jacinto D 2009 Thin Solid Films 518 1337
[15] Ding W Y, Wang H L, Miao Z, Zhang J J, Chai W P 2009 Acta Phys. Sin. 58 432 (in Chinese)[丁万昱、王华林、苗 壮、张俊计、柴卫平2009 物理学报 58 432]
[16] Zhang C, Ding W Y, Wang H L, Chai W P, Ju D Y 2008 J. Environ. Sci. 21 741
[17] Tang W Z 2003 The Theory and Technology of the Thin Film Production (Beijing: Melallurgical Industry Press)(in Chinese) [唐伟忠 2003 薄膜材料制备原理、技术及应用 (北京: 冶金工业出版社)]
[18] Sugai H 2002 Plasma Electronic Engineering (Beijing: Science
[19] Wang J Y 1993 The Theory of Film Growth (Wuhan: Huazhong University of Science and Technology Press) (in Chinese)[王敬义 1993 薄膜生长理论 (武汉:华中理工大学出版社)]
[20] Moulder J F, Stickle W F, Sobol P E, Bomben K D 1995 Handbook of X-ray Photoelectron Spectroscopy (Minnesota: Physical Electronics Inc. )
[21] Ding W Y 2007 Ph. D. Dissertation (Dalian: Dalian University of Technology) (in Chinese) [丁万昱 2007 博士学位论文 (大连:大连理工大学)]
[22] Ding W Y, Xu J, Lu W Q, Deng X L, Dong C 2009 Phys. Plasmas 16 053502
[23] Ding W Y, Xu J, Lu W Q, Deng X L, Dong C 2010 Thin Solid Films 518 2077
[24] PCPDFWIN card number: 00-021-1272 (Version 2.1, Copyright 2000)
[25] PCPDFWIN card number: 00-021-1276 (Version 2.1, Copyright 2000)
[26] Meng L J, Andritschky M, Santos dos M P 1993 Thin Solid Films 223 242
[27] Hagfeldtt A, Gratzel M 1995 Chem. Rev. 95 49
[28] Tauc J 1966 Physica Status Solidi B 15 627
[29] Xu L, Tang C Q, Dai L, Tang D H, Ma X G 2007 Acta Phys. Sin. 56 1048 (in Chinese)[徐 凌、唐超群、戴 磊、唐代海、马新国2007 物理学报 56 1048]
[30] PengL P, Xu L, Yin J W 2007 Acta Phys. Sin. 56 1585 (in Chinese)[彭丽萍、徐 凌、尹建武2007 物理学报 56 1585]
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[1] Fujishima A, Honda K 1972 Nature 37 238
[2] Wasielewski R, Domaradzki J, Wojcieszak D, Kaczmarek D, Borkowska A, Prociow E L, Ciszewski A 2008 Appl. Surf. Sci. 254 4396
[3] Press) p73 (in Chinese)[菅井秀郎 2002 等离子体电子工程学 (北京:科学出版社)]
[4] Solid Films 516 1434
[5] Borrás A, Yanguas-Gil A, Barranco A, Cotrino A, González-Elipe A R 2007 Phys. Rev. B 76 235303
[6] Tavares C J, Marques S M, Lanceros-Méndez S, Sencadas V, Teixeira V, Carneiro J O, Martins A J, Fernandes A J 2008 Thin
[7] Hu L H, Dai J, Liu W Q, Wang K J, Dai S Y 2009 Acta Phys. Sin. 58 1115 (in Chinese)[胡林华、戴 俊、刘伟庆、王孔嘉、戴松元2009 物理学报 58 1115]
[8] Shah I, Li W, Huang CP, Jung O, Ni C 2002 Proc. Natl. Acad. Sci. U. S. A. 99 6482
[9] Li W, Frenkel A I, Woicik J C, Ni C, Shah S I 2005 Phys. Rev. B 72 155315
[10] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y 2001 Science 293 269
[11] Tavares C J, Marques S M, Viseu T, Teixeira V, Carneiro J O, Alves E, Barradas N P, Munnik F, Girardeau T, Rivière J P 2009 J. Appl. Phys. 106 113535
[12] Sui R H, Young J L, Berlinguette C P 2010 J. Mater. Chem. 20 498
[13] Yasunori T 2009 Thin Solid Films 517 3167
[14] Tomás S A, Luna-Resendis A, Cortés-Cuautli L C, Jacinto D 2009 Thin Solid Films 518 1337
[15] Ding W Y, Wang H L, Miao Z, Zhang J J, Chai W P 2009 Acta Phys. Sin. 58 432 (in Chinese)[丁万昱、王华林、苗 壮、张俊计、柴卫平2009 物理学报 58 432]
[16] Zhang C, Ding W Y, Wang H L, Chai W P, Ju D Y 2008 J. Environ. Sci. 21 741
[17] Tang W Z 2003 The Theory and Technology of the Thin Film Production (Beijing: Melallurgical Industry Press)(in Chinese) [唐伟忠 2003 薄膜材料制备原理、技术及应用 (北京: 冶金工业出版社)]
[18] Sugai H 2002 Plasma Electronic Engineering (Beijing: Science
[19] Wang J Y 1993 The Theory of Film Growth (Wuhan: Huazhong University of Science and Technology Press) (in Chinese)[王敬义 1993 薄膜生长理论 (武汉:华中理工大学出版社)]
[20] Moulder J F, Stickle W F, Sobol P E, Bomben K D 1995 Handbook of X-ray Photoelectron Spectroscopy (Minnesota: Physical Electronics Inc. )
[21] Ding W Y 2007 Ph. D. Dissertation (Dalian: Dalian University of Technology) (in Chinese) [丁万昱 2007 博士学位论文 (大连:大连理工大学)]
[22] Ding W Y, Xu J, Lu W Q, Deng X L, Dong C 2009 Phys. Plasmas 16 053502
[23] Ding W Y, Xu J, Lu W Q, Deng X L, Dong C 2010 Thin Solid Films 518 2077
[24] PCPDFWIN card number: 00-021-1272 (Version 2.1, Copyright 2000)
[25] PCPDFWIN card number: 00-021-1276 (Version 2.1, Copyright 2000)
[26] Meng L J, Andritschky M, Santos dos M P 1993 Thin Solid Films 223 242
[27] Hagfeldtt A, Gratzel M 1995 Chem. Rev. 95 49
[28] Tauc J 1966 Physica Status Solidi B 15 627
[29] Xu L, Tang C Q, Dai L, Tang D H, Ma X G 2007 Acta Phys. Sin. 56 1048 (in Chinese)[徐 凌、唐超群、戴 磊、唐代海、马新国2007 物理学报 56 1048]
[30] PengL P, Xu L, Yin J W 2007 Acta Phys. Sin. 56 1585 (in Chinese)[彭丽萍、徐 凌、尹建武2007 物理学报 56 1585]
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