TiO_2及其掺杂膜的制备、结构及性能研究
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摘要
TiO2化学稳定性好、无污染、成本低廉、光催化活性高,是目前最具开发前途的催化剂。然而,由于TiO2光催化剂主要依赖于紫外光,对可见光的利用率低,因此限制了它的应用。为了提高TiO2在可见光区范围的吸收,必须对其改性。
本文采用电子束蒸发法分别制备了掺杂Fe、Cu、Al的TiO2薄膜,研究主要工艺参数：掺杂元素种类和含量、基底材料及退火温度对薄膜成分、结构和形貌的影响。借助原子力显微镜(AFM)、扫描电镜(SEM)、拉曼(Raman)光谱、X射线衍射(XRD)和X射线光电子能谱(XPS)等测试手段对薄膜的表面形貌、晶型结构和成分进行了表征,用紫外-可见分光光度计(UV-Vis)测试TiO2薄膜的吸光度,研究不同元素的掺杂对薄膜可见光吸收范围的影响。结果发现,金属离子的掺杂抑制了TiO2薄膜晶型的转变,并且掺杂后的TiO2薄膜吸收带边发生红移,扩展了其吸收波长的范围。
采用电子束蒸发法制备了掺杂B的TiO2薄膜,探讨了在普通玻璃片、石英玻璃和陶瓷三种不同基底及不同退火温度下对薄膜成分、结构和形貌的影响。研究表明,在石英基底上制备的B-TiO2薄膜效果最好,同时B的掺杂也扩展了薄膜的吸收波长范围。
将所制备的掺杂TiO2薄膜分别以一定比例添加到甲基橙溶液中,通过光催化实验研究其在不同光源、不同甲基橙初始浓度条件下的降解率,分析薄膜的制备工艺参数对其光催化作用的影响。
TiO2 is regarded as the most promising catalytic due to its nature stability, avirulent, low-cost and high photocatalyst activity. However, it high photocatalyst performance strongly depend on the irritation of the UV light while the utilization of the visible light is limited, which severely limit its application. In order to make full use of the solar rays, the titanium dioxide must be modified.
In this paper, Fe, Cu, Al-doped titanium dioxide (TiO2) thin films were prepared by electron beam evaporation method. The influence of substrate material, doping ions,dopping concentration and annealing temperature, etc. on the component, structure and the activities of the as-prepared TiO2 films were investigated. Atomic Force Microscope(AFM), Scanning Electron Microscopy(SEM),Raman Spectroscopy, X-ray Diffraction(XRD) and X-ray Photoelectrons Spectroscopy (XPS) were employed to characterize the surface morphology, the crystal structure and the component of the sample. In order to analysis the effect of doping different materials ions on the visible absorption range of TiO2 thin films, UV-Vis spectroscopy was used to test the absorption. Results showed that dopping of metal elements hindered phase transfer of TiO2, restrained growth of TiO2 particles and lead to red shift of the absorption limit of dopping TiO2 thin films, and expansion of absorbed wavelengths scope.
The B-doped TiO2 films were prepared by electron beam evaporation for further research. The impact of different substrates (such as quartz, glass, ceramic) and annealing temperature on the component, structure and the morphology of the as-prepared TiO2 films. The results showed that the film prepared on the quartz exhibits best performance and the absorbtion wavelength range can also be expanded by dopping B.
In the end, the photocatalyst property of the as-prepared TiO2 thin films are tested under different light source, different initial methyl orange concentration, and the preparation technical conditions on the photocatalyst property were analyzed.
本文采用电子束蒸发法分别制备了掺杂Fe、Cu、Al的TiO2薄膜,研究主要工艺参数：掺杂元素种类和含量、基底材料及退火温度对薄膜成分、结构和形貌的影响。借助原子力显微镜(AFM)、扫描电镜(SEM)、拉曼(Raman)光谱、X射线衍射(XRD)和X射线光电子能谱(XPS)等测试手段对薄膜的表面形貌、晶型结构和成分进行了表征,用紫外-可见分光光度计(UV-Vis)测试TiO2薄膜的吸光度,研究不同元素的掺杂对薄膜可见光吸收范围的影响。结果发现,金属离子的掺杂抑制了TiO2薄膜晶型的转变,并且掺杂后的TiO2薄膜吸收带边发生红移,扩展了其吸收波长的范围。
采用电子束蒸发法制备了掺杂B的TiO2薄膜,探讨了在普通玻璃片、石英玻璃和陶瓷三种不同基底及不同退火温度下对薄膜成分、结构和形貌的影响。研究表明,在石英基底上制备的B-TiO2薄膜效果最好,同时B的掺杂也扩展了薄膜的吸收波长范围。
将所制备的掺杂TiO2薄膜分别以一定比例添加到甲基橙溶液中,通过光催化实验研究其在不同光源、不同甲基橙初始浓度条件下的降解率,分析薄膜的制备工艺参数对其光催化作用的影响。
TiO2 is regarded as the most promising catalytic due to its nature stability, avirulent, low-cost and high photocatalyst activity. However, it high photocatalyst performance strongly depend on the irritation of the UV light while the utilization of the visible light is limited, which severely limit its application. In order to make full use of the solar rays, the titanium dioxide must be modified.
In this paper, Fe, Cu, Al-doped titanium dioxide (TiO2) thin films were prepared by electron beam evaporation method. The influence of substrate material, doping ions,dopping concentration and annealing temperature, etc. on the component, structure and the activities of the as-prepared TiO2 films were investigated. Atomic Force Microscope(AFM), Scanning Electron Microscopy(SEM),Raman Spectroscopy, X-ray Diffraction(XRD) and X-ray Photoelectrons Spectroscopy (XPS) were employed to characterize the surface morphology, the crystal structure and the component of the sample. In order to analysis the effect of doping different materials ions on the visible absorption range of TiO2 thin films, UV-Vis spectroscopy was used to test the absorption. Results showed that dopping of metal elements hindered phase transfer of TiO2, restrained growth of TiO2 particles and lead to red shift of the absorption limit of dopping TiO2 thin films, and expansion of absorbed wavelengths scope.
The B-doped TiO2 films were prepared by electron beam evaporation for further research. The impact of different substrates (such as quartz, glass, ceramic) and annealing temperature on the component, structure and the morphology of the as-prepared TiO2 films. The results showed that the film prepared on the quartz exhibits best performance and the absorbtion wavelength range can also be expanded by dopping B.
In the end, the photocatalyst property of the as-prepared TiO2 thin films are tested under different light source, different initial methyl orange concentration, and the preparation technical conditions on the photocatalyst property were analyzed.
引文
[1]Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode[J].Nature,1972,238:37～38.
[2]Andrew Mills, Ahmed Belghazi, Derek Rodman. Bromate removal from drinking water by semiconductor photocatalysis[J].Water Research,1996,30(9): 1973～1978
[3]Mills A, Davies R H, Worsley D. Water purification by semiconductor photocatalysis[J].Chem. Soc. Rev.,1993,22(6):417～425
[4]陈建华,龚竹青.二氧化钛半导体光催化材料离子掺杂[M].北京：科学出版社,2006
[5]Andrew Mills, Stephen Le Hunte. An overview of semiconductor photocatalysis[J].Journal of Photochemistry and Photobiology A:Chemistry, 1997,108(1):1-35
[6]Vainshtein B K, FridkinW M, Indenbom V L. Structure of crystal[M].Berlin: Macmillan India Ltd.,1994
[7]熊家林,贡长生,张克立.无机精细化学品的制备和应用[M].北京：化学工业出版社,1999
[8]贺蕴秋,王德平,林健.溶胶-凝胶Ti02的晶相转变温度[J].科学通报,2000,31(2)：149～151
[9]范崇政,肖建平,丁延伟.纳米Ti02的制备与光催化反映研究进展[J].科学通报,2001,46(4)：265～272
[10]Zhao lei, Lian jianshe. Effect of substrate temperature on structural properties and photocatalytic activity of TiO2 thin films[J].Trans.Nonferrous Met. SOC,2007, (17):772～776
[11]Nicholas T, Michael K, Seery, et al. Spectroscopic Investigation of the Anatase-to-Rutile Transformation of Sol-Gel Synthesized TiO2 Photocatalysts [J]. Phys. Chem.,2009,113:16151～16157
[12]Orendorz A, Brodyanski A, Losch J, et al. Phase transformation and particle growth in nanocrystalline anatase TiO2 films analyzed by X-ray diffraction and raman spectroscopy [J].Surface Science,2007,601:4390～4394
[13]Shimizu K I, Murayama H S,Nagai A, et al.Degradation of Hydrophobic Organic Pollutants by Titania Pillared Fluorine Mica as a Substrate Specific Photocatalyst[J].Applied Catalysis B:Environmental,2005,55(2):141～148
[14]黄锦勇,刘国光,张万辉,等.TiO2光催化还原重金属离子的研究进展[J].环境科学与技术,2008,31(12)：104～107
[15]O'Regan B, Gratzel M. A low-cost high-efficiency solar cell based on dye-sensitised colloidal TiO2 films[J].Nature,1991,353:737～738.
[16]刘彭义,叶勤,唐振方,等.退火温度对纳米Ti02薄膜结构对亲水性的影响[J].真空科学与技术学报,2004,24(2)：133～36.
[17]Sopyan I, Watanabe M, Murasawa S,et al. Efficient TiO2 powder and film photocatalysts with rutile crystal structure[J].Chemistry Letters,1996,1:69～70.
[18]刘香玲,潘家荣,李瑞萍,等.紫外光照射下纳米Ti02降解水中有机氯酚化合物[J].三峡大学学报,2006,28(2)：176～80
[19]王侃,陈英旭,叶芬霞.不同光源对Ti02光催化降解染料污染物的影响[J].太阳能学报,2005,26(1)：39～43
[20]Tanaka K, Reddy K S N. Photodegradation of phenoxyacetic acid and carbamate pesticides on TiO2[J].Applied catalysis B:Environmental,2002,1216:41～60
[21]肖劲松,訾学红,尹雪云.纳米Ti02涂料光催化清除空气中主要污染物的研究[J].暖通空调,2005,32(5)：23～25
[22]万悦,方晓东.Ti02薄膜光催化用于空气灭菌净化[J].功能材料,2004,35(4)：489～494
[23]Lin H, Kozuka H, Yoko T. Preparation of TiO2 films on self-assembled monolayers by sol-gel method[J].Thin Solid Films,1998,315(1-2):111～117
[24]薛霞,唐超群,周文斌,等.镧铁掺杂纳米Ti02薄膜的光吸收性能的研究[J].材料导报,2006,20：87～88
[25]任学昌,史载锋,等.Fe3+改性纳米Ti02薄膜的制备及其光催化性能[J].中国给水排水,2008,13(24)：70～73
[26]展红全,孙彦平,徐海萍,等.RF-PCVD法制备条件对纳米Ti02微晶的影响[J].钛工业进展,2004,21(5)：29～33
[27]王薇薇,郭玉,张溪文,等.Ti02薄膜发展现状及APCVD制备掺氮Ti02性能研究[J].材料导报,2006,(20)：57～61
[28]Zhang Xingwang, Lei Lecheng. Development of supported boron-doping TiO2 catalysts by chemical vapor deposition[J].Science Letters,2008,9(1):109～112
[29]曹逊,李效民,于伟东.PLD法制备Ti02薄膜及电阻转变特性研究[J].无机材料学报,2009,24(1)：48～52
[30]Kim J H, Lee S, Im H S.The effect of target density and its morphology on TiO2 thin films grown on Si(100)by PLD[J].Surface Science,1999,151:6-16
[31]Li Z G, Wu Y X, Miyake S.Metallic sputtering growth of high quality anatase phase TiO2 films by inductively coupled plasma assisted DC reactive magnetron sputtering[J].Surface and Coatings Technology,2009, (23):3661～3668
[32]Meng Fanming, Song Xueping, Sun Zhaoqi. Photocatalytic activity of TiO2 thin films deposited by RF magnetron sputtering[J].Vacuum,2009,83:1147～1151
[33]Cheol Ho Heo, Soon-Bo Lee, Jin-Hyo Boo.Deposition of TiO2 thin films using RF magnetron sputtering method and study of their surface characteristics[J]. Thin Solid Films,2005,(475):183～188
[34]Wen jie, Li Ying, Wang Fuhui, et al.Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering[J].Vacuum,2007,82(3):328～335
[35]唐伟忠.薄膜材料制备原理、技术及应用[M].北京：冶金工业出版社,2003
[36]何永华,于国萍,魏正和,等.射频建设法制备掺铂的Ti02薄膜的基本性质[J].武汉大学学报,2004,50(1)：51～54
[37]李海玲,王文静,亢国虎,等.磁控溅射法制备Ti02薄膜的光催化特性[J].太阳能学报,2006,11(27)：1103～1107
[38]Yoo D S, Kim I, Kim S S.Effects of annealing temperature and method on structural and optical properties of TiO2 films prepared by RF magnetron sputtering at room temperature[J].Applied Surface Science,2007, (253): 3888～3892
[39]李云,王六定.铈掺杂对氧化钛薄膜光吸收性能的影响[J].科学技术与工程,2008,8(8)：46～49
[40]杨陈,樊慧庆,李创,等.离子束辅助反应电子束蒸发Ti02薄膜的结构和光学性能[J].材料科学与工程学报,2007,25(1)：14～17.
[41]于华,李新军,郑少健,等.Ni控制掺杂Ti02薄膜的光电化学行为及光催化活性[J].无机化学学报,2006,22(6)：978～982
[42]李粉玲.金属沉积对Ti02薄膜光催化性能的影响[J].天津化工,2006,20(4)：24～26
[43]Naoomi Yamada, Taro Hitosugi, Ngoc Lam Huong Hoang. et al.Structural, electrical and optical properties of sputter-deposited Nb-doped TiO2 (TNO) polycrystalline films[J].Thin Solid Films,2008,516:5754～5757
[44]姜洪波,高濂,张青红.铜离子掺杂对Ti02纳米颗粒膜机构和性能的影响[J].无机材料学报,2002,4(17)：787～791
[45]Wang J,Sun W,Zhao H, et al.Preparation of Fe-doped mixed crystal TiO2 catalyst and investigation of its sonocatalytic activity during degradation of azo fuchsine under ultrasonic irradiation[J].Colloid and Interface Science,2008, (320):202～209
[46]金丽娜,史志铭,闫龙.Zn2+掺杂对Ti02相变温度和晶粒尺寸的影响[J].人工晶体学报,2007,36(3)：630～633
[47]Carneiro J O, Teixeira V, Portinha A. Study of the deposition parameters and Fe-doped effect in the photocatalytic activity of TiO2 films prepared by DC reactive magnetron sputtering[J].Vacuum,2005,(78):37～46
[48]张晓伟,周文芳,刘强,等.N掺杂Ti02光催化剂的制备及性能研究[J].材料导报,2008,22：86～88
[49]Wu G S,Chen A C. Direct growth of F-doped TiO2 particulate thin films with high photocatalytic activity for environmental applications[J].Photochemistry and Photobiology A:Chemistry,2008,195(1):47～53
[50]Maria Crisan, Ana Braileanu, Malina Raileanu. Sol-gel S-doped TiO2 materials for environmental protection[J].Non-Crystalline Solids,2008, (354):705～711
[51]石建稳,郑经堂,胡燕,等.纳米TiO2光催化剂共掺杂的研究进展[J].化工进展,2006,25(60)：604～607
[52]石宗利,徐松梅,高朋召.Fe,Gd共掺杂改性Ti02的可见光光催化活性[J].湖南大学学报,2009,36(3)：51～54
[53]高堃,傅敏.铁氮共掺杂纳米Ti02的制备及其光催化性能的研究[J].重庆工商大学学报,2009,26(2)：109～112
[54]周学东,倪佳苗,赵修建,等.磁控溅射法制备Ce-Ti02紫外吸收薄膜[J].武汉理工大学学报,2006,28(1)：13～15.
[55]王君安,王浩,薛双喜,等.反应磁控溅射制备超亲水性Si02/Ti02多层膜的研究[J].真空科学与技术学报,2006,26(2)：110～113.
[56]Nam H J,Amemiya T, Murabayashi M, et al. Photocatalytic activity of sol-gel TiO2 thin films on various kinds of glass substrates:The effects of Na+ and primary particle size[J].J Phys Chem B,2004,108:8254～8259
[57]陈光华,邓金祥,等.新型电子薄膜材料[M].北京：化学工业出版社,2002
[58]张光寅,蓝国祥.晶格振动光谱学(第一版)[M].北京：高等教育出版社,1991
[59]叶志镇,吕建国,吕斌,等.半导体薄膜技术与物理[M].浙江：浙江大学出版社,2008
[60]蔡殉,石玉龙,周建.现代薄膜材料与技术[M].上海：华东理工大学出版社.2007
[61]Zhou Q F, Wu S H, Zhang J X, et al. Structure and Raman spectroscopy of
nanocrystalline TiO2 powder derived by sol-gel process[J].Chin. Phys. Lett.,. 1997,14(4):306～309
[62]Zhang Y, Shen Y, Gu F, et al.Influence of Fe ions in characteristics and optical properties of mesoporous titanium oxide thin films[J].Applied Surface Science, 2009,256:85～89
[63]Faria D L A de, Venancio S S, Oliveira M T de. Raman mircro spectroscopy of some Iron Oxides and Oxyhydroxides[J].Raman Spectroscopy,1997,28: 873～876
[64]Zhao Z W, Tay B K. Study of nanocrystal TiO2 thin films by thermal annealing [J]. Electroceram,2006,16:489～493
[65]赵丽特,叶勤,丁瑞钦.射频磁控溅射法制备Ti02薄膜的拉曼光谱[J].材料导报,2006,20：89～90
[66]J. David Casey, John S.Haggerty. Laser-induced vapour-phase synthesis of titanium dioxide[J].Journal of materials science,1982,22:4307～4312
[67]刘千钧,余煜棉,张音波,等.Ti02光催化降解甲基橙若干反应条件的研究[J].环境科学与技术,2003,26(6)：13～17
[68]赵晓兰、张鹏,徐瑞芬,等.纳米Ti02对甲基橙的吸附及光催化降解[J].北京化工大学学报,2003,30(6)：10～13
[69]史载锋,范益群,徐南平,等.不同光源对光催化降解亚甲基蓝的影响[J].南京化工大学学报,2000,22(1)：59～63
[70]Chan C C, Chang C C, Hsu WC,et al. Photocatalytic activities of Pd-loaded mesoporous TiO2 thin films[J].Chemical Engineering Journal,2009,(152): 492～497
[71]任成军,钟本和,陈国强,等.铜离子掺杂对二氧化钛薄膜光催化性能的影响[J].硅酸盐学报,2006,34(1)：39-43
[72]Zaman P, Takabayashi S.Nano-scaled photocatalytic TiO2 thin films prepared by magnetron sputtering[J].Thin Solid Films,2003,433:57～62.
[73]Wang M C,Lin H J,Yang T S.Characteristics and optical properties of iron ion (Fe3+)-doped titanium oxide thin films prepared by a sol-gel spin coating[J]. Jouranl of Alloys and Compounds,2009,473:394～400
[2]Andrew Mills, Ahmed Belghazi, Derek Rodman. Bromate removal from drinking water by semiconductor photocatalysis[J].Water Research,1996,30(9): 1973～1978
[3]Mills A, Davies R H, Worsley D. Water purification by semiconductor photocatalysis[J].Chem. Soc. Rev.,1993,22(6):417～425
[4]陈建华,龚竹青.二氧化钛半导体光催化材料离子掺杂[M].北京：科学出版社,2006
[5]Andrew Mills, Stephen Le Hunte. An overview of semiconductor photocatalysis[J].Journal of Photochemistry and Photobiology A:Chemistry, 1997,108(1):1-35
[6]Vainshtein B K, FridkinW M, Indenbom V L. Structure of crystal[M].Berlin: Macmillan India Ltd.,1994
[7]熊家林,贡长生,张克立.无机精细化学品的制备和应用[M].北京：化学工业出版社,1999
[8]贺蕴秋,王德平,林健.溶胶-凝胶Ti02的晶相转变温度[J].科学通报,2000,31(2)：149～151
[9]范崇政,肖建平,丁延伟.纳米Ti02的制备与光催化反映研究进展[J].科学通报,2001,46(4)：265～272
[10]Zhao lei, Lian jianshe. Effect of substrate temperature on structural properties and photocatalytic activity of TiO2 thin films[J].Trans.Nonferrous Met. SOC,2007, (17):772～776
[11]Nicholas T, Michael K, Seery, et al. Spectroscopic Investigation of the Anatase-to-Rutile Transformation of Sol-Gel Synthesized TiO2 Photocatalysts [J]. Phys. Chem.,2009,113:16151～16157
[12]Orendorz A, Brodyanski A, Losch J, et al. Phase transformation and particle growth in nanocrystalline anatase TiO2 films analyzed by X-ray diffraction and raman spectroscopy [J].Surface Science,2007,601:4390～4394
[13]Shimizu K I, Murayama H S,Nagai A, et al.Degradation of Hydrophobic Organic Pollutants by Titania Pillared Fluorine Mica as a Substrate Specific Photocatalyst[J].Applied Catalysis B:Environmental,2005,55(2):141～148
[14]黄锦勇,刘国光,张万辉,等.TiO2光催化还原重金属离子的研究进展[J].环境科学与技术,2008,31(12)：104～107
[15]O'Regan B, Gratzel M. A low-cost high-efficiency solar cell based on dye-sensitised colloidal TiO2 films[J].Nature,1991,353:737～738.
[16]刘彭义,叶勤,唐振方,等.退火温度对纳米Ti02薄膜结构对亲水性的影响[J].真空科学与技术学报,2004,24(2)：133～36.
[17]Sopyan I, Watanabe M, Murasawa S,et al. Efficient TiO2 powder and film photocatalysts with rutile crystal structure[J].Chemistry Letters,1996,1:69～70.
[18]刘香玲,潘家荣,李瑞萍,等.紫外光照射下纳米Ti02降解水中有机氯酚化合物[J].三峡大学学报,2006,28(2)：176～80
[19]王侃,陈英旭,叶芬霞.不同光源对Ti02光催化降解染料污染物的影响[J].太阳能学报,2005,26(1)：39～43
[20]Tanaka K, Reddy K S N. Photodegradation of phenoxyacetic acid and carbamate pesticides on TiO2[J].Applied catalysis B:Environmental,2002,1216:41～60
[21]肖劲松,訾学红,尹雪云.纳米Ti02涂料光催化清除空气中主要污染物的研究[J].暖通空调,2005,32(5)：23～25
[22]万悦,方晓东.Ti02薄膜光催化用于空气灭菌净化[J].功能材料,2004,35(4)：489～494
[23]Lin H, Kozuka H, Yoko T. Preparation of TiO2 films on self-assembled monolayers by sol-gel method[J].Thin Solid Films,1998,315(1-2):111～117
[24]薛霞,唐超群,周文斌,等.镧铁掺杂纳米Ti02薄膜的光吸收性能的研究[J].材料导报,2006,20：87～88
[25]任学昌,史载锋,等.Fe3+改性纳米Ti02薄膜的制备及其光催化性能[J].中国给水排水,2008,13(24)：70～73
[26]展红全,孙彦平,徐海萍,等.RF-PCVD法制备条件对纳米Ti02微晶的影响[J].钛工业进展,2004,21(5)：29～33
[27]王薇薇,郭玉,张溪文,等.Ti02薄膜发展现状及APCVD制备掺氮Ti02性能研究[J].材料导报,2006,(20)：57～61
[28]Zhang Xingwang, Lei Lecheng. Development of supported boron-doping TiO2 catalysts by chemical vapor deposition[J].Science Letters,2008,9(1):109～112
[29]曹逊,李效民,于伟东.PLD法制备Ti02薄膜及电阻转变特性研究[J].无机材料学报,2009,24(1)：48～52
[30]Kim J H, Lee S, Im H S.The effect of target density and its morphology on TiO2 thin films grown on Si(100)by PLD[J].Surface Science,1999,151:6-16
[31]Li Z G, Wu Y X, Miyake S.Metallic sputtering growth of high quality anatase phase TiO2 films by inductively coupled plasma assisted DC reactive magnetron sputtering[J].Surface and Coatings Technology,2009, (23):3661～3668
[32]Meng Fanming, Song Xueping, Sun Zhaoqi. Photocatalytic activity of TiO2 thin films deposited by RF magnetron sputtering[J].Vacuum,2009,83:1147～1151
[33]Cheol Ho Heo, Soon-Bo Lee, Jin-Hyo Boo.Deposition of TiO2 thin films using RF magnetron sputtering method and study of their surface characteristics[J]. Thin Solid Films,2005,(475):183～188
[34]Wen jie, Li Ying, Wang Fuhui, et al.Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering[J].Vacuum,2007,82(3):328～335
[35]唐伟忠.薄膜材料制备原理、技术及应用[M].北京：冶金工业出版社,2003
[36]何永华,于国萍,魏正和,等.射频建设法制备掺铂的Ti02薄膜的基本性质[J].武汉大学学报,2004,50(1)：51～54
[37]李海玲,王文静,亢国虎,等.磁控溅射法制备Ti02薄膜的光催化特性[J].太阳能学报,2006,11(27)：1103～1107
[38]Yoo D S, Kim I, Kim S S.Effects of annealing temperature and method on structural and optical properties of TiO2 films prepared by RF magnetron sputtering at room temperature[J].Applied Surface Science,2007, (253): 3888～3892
[39]李云,王六定.铈掺杂对氧化钛薄膜光吸收性能的影响[J].科学技术与工程,2008,8(8)：46～49
[40]杨陈,樊慧庆,李创,等.离子束辅助反应电子束蒸发Ti02薄膜的结构和光学性能[J].材料科学与工程学报,2007,25(1)：14～17.
[41]于华,李新军,郑少健,等.Ni控制掺杂Ti02薄膜的光电化学行为及光催化活性[J].无机化学学报,2006,22(6)：978～982
[42]李粉玲.金属沉积对Ti02薄膜光催化性能的影响[J].天津化工,2006,20(4)：24～26
[43]Naoomi Yamada, Taro Hitosugi, Ngoc Lam Huong Hoang. et al.Structural, electrical and optical properties of sputter-deposited Nb-doped TiO2 (TNO) polycrystalline films[J].Thin Solid Films,2008,516:5754～5757
[44]姜洪波,高濂,张青红.铜离子掺杂对Ti02纳米颗粒膜机构和性能的影响[J].无机材料学报,2002,4(17)：787～791
[45]Wang J,Sun W,Zhao H, et al.Preparation of Fe-doped mixed crystal TiO2 catalyst and investigation of its sonocatalytic activity during degradation of azo fuchsine under ultrasonic irradiation[J].Colloid and Interface Science,2008, (320):202～209
[46]金丽娜,史志铭,闫龙.Zn2+掺杂对Ti02相变温度和晶粒尺寸的影响[J].人工晶体学报,2007,36(3)：630～633
[47]Carneiro J O, Teixeira V, Portinha A. Study of the deposition parameters and Fe-doped effect in the photocatalytic activity of TiO2 films prepared by DC reactive magnetron sputtering[J].Vacuum,2005,(78):37～46
[48]张晓伟,周文芳,刘强,等.N掺杂Ti02光催化剂的制备及性能研究[J].材料导报,2008,22：86～88
[49]Wu G S,Chen A C. Direct growth of F-doped TiO2 particulate thin films with high photocatalytic activity for environmental applications[J].Photochemistry and Photobiology A:Chemistry,2008,195(1):47～53
[50]Maria Crisan, Ana Braileanu, Malina Raileanu. Sol-gel S-doped TiO2 materials for environmental protection[J].Non-Crystalline Solids,2008, (354):705～711
[51]石建稳,郑经堂,胡燕,等.纳米TiO2光催化剂共掺杂的研究进展[J].化工进展,2006,25(60)：604～607
[52]石宗利,徐松梅,高朋召.Fe,Gd共掺杂改性Ti02的可见光光催化活性[J].湖南大学学报,2009,36(3)：51～54
[53]高堃,傅敏.铁氮共掺杂纳米Ti02的制备及其光催化性能的研究[J].重庆工商大学学报,2009,26(2)：109～112
[54]周学东,倪佳苗,赵修建,等.磁控溅射法制备Ce-Ti02紫外吸收薄膜[J].武汉理工大学学报,2006,28(1)：13～15.
[55]王君安,王浩,薛双喜,等.反应磁控溅射制备超亲水性Si02/Ti02多层膜的研究[J].真空科学与技术学报,2006,26(2)：110～113.
[56]Nam H J,Amemiya T, Murabayashi M, et al. Photocatalytic activity of sol-gel TiO2 thin films on various kinds of glass substrates:The effects of Na+ and primary particle size[J].J Phys Chem B,2004,108:8254～8259
[57]陈光华,邓金祥,等.新型电子薄膜材料[M].北京：化学工业出版社,2002
[58]张光寅,蓝国祥.晶格振动光谱学(第一版)[M].北京：高等教育出版社,1991
[59]叶志镇,吕建国,吕斌,等.半导体薄膜技术与物理[M].浙江：浙江大学出版社,2008
[60]蔡殉,石玉龙,周建.现代薄膜材料与技术[M].上海：华东理工大学出版社.2007
[61]Zhou Q F, Wu S H, Zhang J X, et al. Structure and Raman spectroscopy of
nanocrystalline TiO2 powder derived by sol-gel process[J].Chin. Phys. Lett.,. 1997,14(4):306～309
[62]Zhang Y, Shen Y, Gu F, et al.Influence of Fe ions in characteristics and optical properties of mesoporous titanium oxide thin films[J].Applied Surface Science, 2009,256:85～89
[63]Faria D L A de, Venancio S S, Oliveira M T de. Raman mircro spectroscopy of some Iron Oxides and Oxyhydroxides[J].Raman Spectroscopy,1997,28: 873～876
[64]Zhao Z W, Tay B K. Study of nanocrystal TiO2 thin films by thermal annealing [J]. Electroceram,2006,16:489～493
[65]赵丽特,叶勤,丁瑞钦.射频磁控溅射法制备Ti02薄膜的拉曼光谱[J].材料导报,2006,20：89～90
[66]J. David Casey, John S.Haggerty. Laser-induced vapour-phase synthesis of titanium dioxide[J].Journal of materials science,1982,22:4307～4312
[67]刘千钧,余煜棉,张音波,等.Ti02光催化降解甲基橙若干反应条件的研究[J].环境科学与技术,2003,26(6)：13～17
[68]赵晓兰、张鹏,徐瑞芬,等.纳米Ti02对甲基橙的吸附及光催化降解[J].北京化工大学学报,2003,30(6)：10～13
[69]史载锋,范益群,徐南平,等.不同光源对光催化降解亚甲基蓝的影响[J].南京化工大学学报,2000,22(1)：59～63
[70]Chan C C, Chang C C, Hsu WC,et al. Photocatalytic activities of Pd-loaded mesoporous TiO2 thin films[J].Chemical Engineering Journal,2009,(152): 492～497
[71]任成军,钟本和,陈国强,等.铜离子掺杂对二氧化钛薄膜光催化性能的影响[J].硅酸盐学报,2006,34(1)：39-43
[72]Zaman P, Takabayashi S.Nano-scaled photocatalytic TiO2 thin films prepared by magnetron sputtering[J].Thin Solid Films,2003,433:57～62.
[73]Wang M C,Lin H J,Yang T S.Characteristics and optical properties of iron ion (Fe3+)-doped titanium oxide thin films prepared by a sol-gel spin coating[J]. Jouranl of Alloys and Compounds,2009,473:394～400