超声喷雾热解法制备SnO_2：F薄膜及性能分析
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摘要
SnO2是一种宽带隙氧化物半导体材料,禁带宽度Eg=3.6-4.0eV。SnO2薄膜由于具有对可见光透过性好、紫外吸收系数大、电阻率低、化学性能稳定以及室温下抗酸碱能力强等优点,已被广泛的应用在太阳能电池、电热材料、透明电极材料以及气敏材料等方面。
喷雾热解法以其设备简单、成本低、制备样品快等优点成为一种很有应用潜力的制备SnO2薄膜的方法,另外喷雾热解法在镀膜玻璃的工业化生产中有着广阔的应用领域。
以SnCl4·5H20和NH4F为原料,本文采用超声喷雾热解法在石英玻璃管内壁制备掺F的二氧化锡薄膜。运用正交方法设计实验,研究了制备SnO2：F薄膜过程中的五种影响因素,如：F浓度(F% mol)、Sn浓度(Sn% mol)、酒精浓度、喷涂时间以及基底温度,对薄膜方阻和在可见光范围内的平均透过率的影响,得出最佳工艺组合为基底温度为500℃,F的浓度为2%(mol)、Sn的浓度为15%(mo1)、酒精浓度为30%(m1)、喷涂时间为15s。最后利用回归分析,建立了光透过率、方阻与F%、Sn%、酒精浓度、基底温度以及喷涂时间这五个影响因素之间的线性关系。
通过实验分析了SnO2：F透明导电薄膜方阻随温度变化的实验规律,用SPSS软件拟合,得到的二次拟合曲线很好的反映了薄膜的温度随方阻变化的特性。拟合优度R2=0.883,二次拟合回归方程R=87.688+0.10t+4.25×10-5t2。
SnO2 is a kind of wide-band oxide semiconductor material with a bandwidth of Eg=3.6-4.0eV. Due to its excellent characterics, such as high light transmission in visible region, low resistivity, high chemical stability and so on, it has been widely used in many fields such as solar cells, electric heating devices, transparent electrodes, and gas sensors, etc.
The spray pyrolysis technique has a great potential to prepare the tin dioxide films because of its unsophisticated equipment, low-cost and high deposition rate. And the spray pyrolysis technique has been widely used in industrial production on coated glass.
The spray pyrolysis technique was used to prepare SnO2:F films on the quartz glass tube substrate by using SnCl4·5H2O and NH4F as raw material.The Fluorin-doped SnO2 thin film has very excellent photoelectrical character. The orthogonal experiment was used to design the experiment, and analyze the preparation influence-factors of the SnO2:F transparent conductivity films such as the substrate temperature, F%, Sn%, the percentage of alcohol and the time of ultrasonic spray which influences the films on visible light transmission and the sheet resistance. By this study, optimal proportionings were confirmed, namely, the substrate temperature is 500℃,2% of F%(mol),15% of Sn%(mol),30%(ml) of the percentage of alcohol,15 minutes of the time of ultrasonic spray. In the end, the regression analysis was used to found the linear relation between the light transmission and the sheet resistance and influence factors (the substrate temperature, F%(mol), Sn%(mol), the percentage of alcohol and the time of ultrasonic spray). The value of the light transmission and the sheet resistance will be estimated ahead of schedule in our following experiments by Regression equation.
The relationship between the resistance of SnO2:F transparent conductor films and various temperature was obtained by the experiment. A quadratic curve obtained by the SPSS Software reflects the rule of the sheet resistance with the vary temperature. The goodness of fit is R2=0.883 and the equation of quadratic curve is R=87.688+0.10t+4.25×10-5t2.
喷雾热解法以其设备简单、成本低、制备样品快等优点成为一种很有应用潜力的制备SnO2薄膜的方法,另外喷雾热解法在镀膜玻璃的工业化生产中有着广阔的应用领域。
以SnCl4·5H20和NH4F为原料,本文采用超声喷雾热解法在石英玻璃管内壁制备掺F的二氧化锡薄膜。运用正交方法设计实验,研究了制备SnO2：F薄膜过程中的五种影响因素,如：F浓度(F% mol)、Sn浓度(Sn% mol)、酒精浓度、喷涂时间以及基底温度,对薄膜方阻和在可见光范围内的平均透过率的影响,得出最佳工艺组合为基底温度为500℃,F的浓度为2%(mol)、Sn的浓度为15%(mo1)、酒精浓度为30%(m1)、喷涂时间为15s。最后利用回归分析,建立了光透过率、方阻与F%、Sn%、酒精浓度、基底温度以及喷涂时间这五个影响因素之间的线性关系。
通过实验分析了SnO2：F透明导电薄膜方阻随温度变化的实验规律,用SPSS软件拟合,得到的二次拟合曲线很好的反映了薄膜的温度随方阻变化的特性。拟合优度R2=0.883,二次拟合回归方程R=87.688+0.10t+4.25×10-5t2。
SnO2 is a kind of wide-band oxide semiconductor material with a bandwidth of Eg=3.6-4.0eV. Due to its excellent characterics, such as high light transmission in visible region, low resistivity, high chemical stability and so on, it has been widely used in many fields such as solar cells, electric heating devices, transparent electrodes, and gas sensors, etc.
The spray pyrolysis technique has a great potential to prepare the tin dioxide films because of its unsophisticated equipment, low-cost and high deposition rate. And the spray pyrolysis technique has been widely used in industrial production on coated glass.
The spray pyrolysis technique was used to prepare SnO2:F films on the quartz glass tube substrate by using SnCl4·5H2O and NH4F as raw material.The Fluorin-doped SnO2 thin film has very excellent photoelectrical character. The orthogonal experiment was used to design the experiment, and analyze the preparation influence-factors of the SnO2:F transparent conductivity films such as the substrate temperature, F%, Sn%, the percentage of alcohol and the time of ultrasonic spray which influences the films on visible light transmission and the sheet resistance. By this study, optimal proportionings were confirmed, namely, the substrate temperature is 500℃,2% of F%(mol),15% of Sn%(mol),30%(ml) of the percentage of alcohol,15 minutes of the time of ultrasonic spray. In the end, the regression analysis was used to found the linear relation between the light transmission and the sheet resistance and influence factors (the substrate temperature, F%(mol), Sn%(mol), the percentage of alcohol and the time of ultrasonic spray). The value of the light transmission and the sheet resistance will be estimated ahead of schedule in our following experiments by Regression equation.
The relationship between the resistance of SnO2:F transparent conductor films and various temperature was obtained by the experiment. A quadratic curve obtained by the SPSS Software reflects the rule of the sheet resistance with the vary temperature. The goodness of fit is R2=0.883 and the equation of quadratic curve is R=87.688+0.10t+4.25×10-5t2.
引文
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[2]赵谢群.透明导电氧化物薄膜研究现状与产业化进展[J].电子元件与材料,2000,19(1)：40.
[3]王敏,蒙继龙.透明导电氧化物薄膜的研究进展[J].表面技术,2003,32(1)：5.
[4]宋健全,刘正堂.红外增透膜系软件设计及应用[J].红外技术,2001,23(2)：1-7.
[5]Choong H Y, Itaru Y, Shigesato Y. Effects of tin concentrations on structural characteristics and electrooptical properties of tin-doped indium oxide films prepared by RF magnetron sputtering[J]. Japanese journal of applied physics,1995,34(1):600.
[6]孟扬,杨锡良,陈华仙,等.新型透明导电薄膜In2O3:Mo[J].真空科学与技术,2000,20(5)：331.
[7]Goebberta C, Nonningerb R, Aegerter M A, et al. Wet chemical deposition of ATO and ITO coatings using crystal-line nanoparticles redispersable in solutions[J]. Thin Solid Films,1999,351(1):79-84.
[8]Kelly P J, Zhou Y, Postill A. A novel technique for the deposition of aluminum-doped zinc oxide films[J]. Thin Solid Films 2003,426(1):111-116.
[9]Bernardi M L, Soledade L E, Santos I A, et al. Influence of the concentration of Sb2O3 and the viscosity of the precursor solution on the electrical and optical properties of SnO2 thin films produced by the Pechini method[J]. Thin Solid Films,2002,405(1-2):228-233.
[10]Shanthi S, Subramanian C, Ramasamy P. Growth and characterization of antimony doped tin oxide thin films[J]. J Crystal Growth,1999,197(4):858-864.
[11]Dutta J, Perrin J, Emeraud T, et al. Pyrosol deposition of fluorine-doped tin dioxide thin films[J]. J Mater Sci,1995,30(1):53.
[12]Gordon R G Criteria for choosing transparent conductors[J]. MRS Bull,2000,25(8):52.
[13]徐慢,夏冬林,赵修建.透明导电氧化物薄膜材料及其制备技术研究进展[J].材料导报,2006,20：312-314.
[14]赵丽娜.喷雾热解法制备P型透明导电的二氧化锡薄膜[D],浙江：浙江大学,2006,10-13.
[15]Z.B.Zhou, R.Q.Cui, Q.J.Pang, et al. Preparation of indium tin oxide films and doped tin oxide films by an ultrasonic spray CVD process[J]. Applied Surface Science,2001,172(3):245-252.
[16]D.Davazoglou, et al. Optical properties of SnO2 thin films grown by atmospheric pressure chemical vapor deposition oxidizing SnCl4[J],Thin Solid Films,1997,302(1):204-213.
[17]R.Dolbec, M.A.EI Khakani, A.M.Serventi, et al. Microstructure and physical properties of nanostrued tin oxide thin films grown by means for pulsed laser deposition[J], Thin Solid Films, 2002,419(1-2),230.
[18]F.R.Sensato, O.Treu Filho, E.Longo, et al. Theoretical analysis of the energy levels induced by
oxygen vacancies and the doping process(Co, Cu and Zn) on SnO2(110) surface models[J]. Molecular Structure,2001,541(1-3):69-79.
[19]H.M.PhilliPs, Y.Li, Z.Bi, B.Zhang. Reactive Pulsed laser deposition and laser induced crystallization of SnO2 transparent conducting thin films[J]. Applied Physics A:Material Science& Processing, 1996,63(4):347-351.
[20]徐国昌,凌一鸣编著.光电子物理基础[M].南京：东南大学出版社,2000,123-300.
[21]马黎君,魏京花.掺杂与SnO2薄膜性能影响研究[J].北京建筑工程学院学报,2001,17(2),70-73.
[22]秦友兰,王万录等.用Sol-Gel法制备气敏传感器SnO2薄膜的研究[J].广西师范大学学报(自然科学版),2000,18(3),16-19.
[23]J.Pichlmaier. Physical interpretation of the influence of humidity on an SnO2 sensor[M]. Sensors and Actuators B,1995,27(1-3):552-554.
[24]滕树新,王矜奉等.CeO2掺杂引起SnO2压敏电阻的晶粒尺寸效应,电子元件与材料[J].2003,22(11),31-34.
[25]齐甸农.ITO和SnO2透明导电膜的用途和制备[J].上海有色金属,1992,13(2)：45-52.
[26]郝喜红.喷雾热解法制备掺杂二氧化锡导电薄膜[D].西安：西安建筑科技大学,2005：10-16.
[27]王平.导电涂料[J].现代涂料与涂装,1997,3(2)：6-11.
[28]刘恩科,朱秉升,罗晋生.半导体物理学[M].北京：电子工业出版社,2003：98-156.
[29]黄昆,韩汝琦.半导体物理基础[M].北京：科学出版社,1979：65-90.
[30]加尔彼林著,周孔章译.半导体电子学[M].北京：科学出版社,1961：80-121.
[31]陈光华，邓金详.新型电子薄膜材料[M].北京：电子工业出版社,2002：120-200.
[32]邓志杰,郑安生编著.半导体材料[M].北京：科学出版社,2004：156-246.
[33]郭玉忠,王剑华,黄瑞安等.掺杂SnO2透明导电薄膜电学及光学性能研究[J].无机材料学报,2002,17(1)：131-138.
[34]Svane A, Antocik J E. The property and structure of tin oxide thin film[J]. Phys. chem. Solids,1987, 48(2):171-180.
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