溶剂对FTO薄膜的结构和光电性能的影响
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摘要
采用喷雾热解法(SPD),分别使用甲醇、乙醇、异丙醇、正丁醇和去离子水作为溶剂制备F掺杂的SnO_2(FTO)透明导电薄膜,使用X射线衍射仪、扫描电子显微镜、四点探针电阻仪、霍尔效应仪和紫外可见分光光度计等手段对薄膜进行测试和表征,研究了溶剂对FTO薄膜结构、形貌和光电性能的影响,研究了溶剂对FTO薄膜结构与光电性能的影响。结果表明:FTO薄膜具有四方相金红石结构;使用不同溶剂制备的薄膜,其表面形貌和颗粒尺寸明显不同;使用甲醇为溶剂制备的FTO薄膜呈现饱满的金字塔状,晶粒尺寸均匀,结构致密,具有最佳的综合光学和电学性能,其电阻率可达4.43×10~(-4)Ω·cm,载流子浓度为9.922×10~(20)cm~(-3),品质因数为1.646×10~(-2)Ω~(-1),可见光区透射比均大于75%。
Transparent conductive thin films of fluorine Transparent conductive thin films of fluorine doped tin oxide(FTO)were prepared via spray-pyrolysis(SPD)process using with methanol,ethanol,isopropanol,n-butanol and deionized water as solvents respectively.The films were tested and characterized by X-ray diffraction,scanning electron microscope,four-point probe resistance meter,Hall effect meter and UV-visible spectrophotometer.The effects of solvent on the structure,morphology and photoelectric properties of FTO films were investigated.The results show that when the solvents were with different solvents,the prepared FTO thin films showed the same crystallographic,i.e.a tetrahedral rutile structure,and however their surface morphology and particle size were significantly different.Among others,the FTO thin films prepared with methanol as the solvent showed a dense and full pyramid-like structure al shape,with uniform grain size,compact structure,and the best comprehensive optical and electrical properties,namely,the best resistivity of the film can reach 4.43×10~(-4)Ω·cm,the carrier concentration is9.922×10~(20)cm~(-3),the figure of merit of the film is 1.63×10~(-2)Ω~(-1),and the visible light transmittance is greater than 75%.
Transparent conductive thin films of fluorine Transparent conductive thin films of fluorine doped tin oxide(FTO)were prepared via spray-pyrolysis(SPD)process using with methanol,ethanol,isopropanol,n-butanol and deionized water as solvents respectively.The films were tested and characterized by X-ray diffraction,scanning electron microscope,four-point probe resistance meter,Hall effect meter and UV-visible spectrophotometer.The effects of solvent on the structure,morphology and photoelectric properties of FTO films were investigated.The results show that when the solvents were with different solvents,the prepared FTO thin films showed the same crystallographic,i.e.a tetrahedral rutile structure,and however their surface morphology and particle size were significantly different.Among others,the FTO thin films prepared with methanol as the solvent showed a dense and full pyramid-like structure al shape,with uniform grain size,compact structure,and the best comprehensive optical and electrical properties,namely,the best resistivity of the film can reach 4.43×10~(-4)Ω·cm,the carrier concentration is9.922×10~(20)cm~(-3),the figure of merit of the film is 1.63×10~(-2)Ω~(-1),and the visible light transmittance is greater than 75%.
引文
[1]Swallow J E N, Williamson B A D, Whittles T J, et al. Self-Com-pensation in transparent conducting F-doped SnO2[J]. Adv. Funct.Mater., 2018, 28(4):1701900
[2]Yu X, Yu X, Zhang J, et al. Efficient inverted polymer solar cells based on surface modified FTO transparent electrodes[J]. Sol. En-erg. Mat. Sol. C., 2015, 136:142
[3]Benhaoua A, Rahal A, Benhaoua B, et al. Effect of fluorine doping on the structural, optical and electrical properties of SnO2thin films prepared by spray ultrasonic[J]. Superlattice. Microst., 2014,70:61
[4]Zhao X. Preparation of Large-scale SnO2:F transparent conductive film by atmospheric spray pyrolysis deposition and the effect of fluorine-doping[J]. Int. J. Electrochem. Sc., 2016, 11(7):5395
[5]Korotcenkov G, Cho B K. Spray pyrolysis deposition of undoped SnO2and In2O3films and their structural properties[J]. Prog.Cryst. Growth Charact. Mater., 2017, 63:1
[6]Smith A, Laurent J M, Smith D S, et al. Experimental survey of different precursor/solvent pairs for the deposition of tin dioxide by pyrosol[J]. Thin Solid Films, 1998, 315:17
[7]Ishida T, Kouno H, Kobayashi H, et al. Dependence of photo-voltages of spray-deposited indium tin oxide/silicon oxide/silicon junction solar cells on spray solvents[J]. J. Electrochem. Soc.,1994, 141:1357
[8]Mohd Napi M L, Seng N K, Ahmad M K. Surface morphology and electrical properties of FTO(fluorine doped tin oxide)with different precursor solution for transparent conducting oxide[J].Appl. Mech. Mater., 2015, 773-774:682
[9]Napi M L M, Maarof M F, Soon C F, et al. Fabrication of fluorine doped tin oxide(FTO)thin filmsusing spray pyrolysis deposition method for transparent conducting oxide[J]. J. Eng. Appl. Sci.,2015, 11:8800
[10]Ching-Prado E, Watson A, MIRANDA H. Optical and electrical properties of fluorine doped tin oxide thin film[J]. J. Mater. SciMater. El., 2018, 5:1
[11]Wang L K, Yu J Y, Niu X Y, et al. Effect of F and Nb co-doping on structural, electrical and optical properties of spray deposited tin oxide thin films[J]. Thin Solid Films, 2018, 649:147
[12]Turgut G, SNmez E. Synthesis and characterization of Mo doped SnO2thin films with spray pyrolysis[J]. Superlattice. Microst.,2014, 69:175
[13]Korotkov R Y, Ricou P, Farran A J E. Preferred orientations in polycrystalline SnO2, films grown by atmospheric pressure chemi-cal vapor deposition[J]. Thin Solid Films, 2006, 502(1-2):79
[14]Belanger D, Dodelet J P, Lombos B A, et al. Thickness depen-dence of transport properties of doped polycrystalline tin oxide films[J]. J. Electrochem. Soc., 1985, 132:1398
[15]Zhao H L, Liu Q Y, Yang J K, et al. Effect of catalyst water on the properties and structure of fluorine-doped tin oxide films[J]. Rare Metal Mat. Eng., 2008, 37(6):952(赵洪力,刘起英,杨静凯等.催化剂水对掺杂氟的氧化锡膜性能与结构的影响[J].稀有金属材料与工程, 2008, 37(6):952)
[16]Thangaraju B. Structural and electrical studies on highly conduct-ing spray deposited fluorine and antimony doped SnO2thin films from SnCl2precursor[J]. Thin Solid Films, 2002, 402:71
[17]Benouis C E, Benhaliliba M, Mouffak Z, et al. The low resistive and transparent Al-doped SnO2 films:p-type conductivity, nano-structures and photoluminescence[J]. J. Alloys Compd., 2014,603:213
[18]Kumar K D A, Valanarasu S, Jeyadheepan K, et al. Evaluation of the physical, optical, and electrical properties of SnO2:F thin films prepared by nebulized spray pyrolysis for optoelectronics[J]. J.Mater. Sci. Mater. M., 2018, 29(5):3648
[19]Yu S, Zheng H, Li L, et al. Highly conducting and transparent anti-mony doped tin oxide thin films:the role of sputtering power den-sity[J]. Ceram. Int., 2017, 43:5654
[20]Haitjema H, Elich J. The physical properties of fluorine-doped tin dioxide films and the influence of ageing and impurity effects[J].Sol. Energ. Mat., 1987, 16:79
[21]Adnane M, Cachet H, Folcher G, et al. Beneficial effects of hydro-gen peroxide on growth, structural and electrical properties of sprayed fluorine-doped SnO2films[J]. Thin Solid Films, 2005,492:240
[22]Mohagheghi M M B, Yazdi S T, Mousavi M. Transport, structural and optical properties of SnO2transparent semiconductor thin films alloyed with chromium:carrier type conversion[J]. J. Mater.Sci., 2017, 28(6):1
[23]Oshima M, Yoshino K. Electron scattering mechanism of FTO films grown by spray pyrolysis method[J]. J. Electron. Mater.,2010, 39:819
[24]Fauzia V, Yusnidar M N, Lalasari L H, et al. High figure of merit transparent conducting Sb-doped SnO2thin films prepared via ul-trasonic spray pyrolysis[J]. J. Alloys Compd., 2017, 720:79
[2]Yu X, Yu X, Zhang J, et al. Efficient inverted polymer solar cells based on surface modified FTO transparent electrodes[J]. Sol. En-erg. Mat. Sol. C., 2015, 136:142
[3]Benhaoua A, Rahal A, Benhaoua B, et al. Effect of fluorine doping on the structural, optical and electrical properties of SnO2thin films prepared by spray ultrasonic[J]. Superlattice. Microst., 2014,70:61
[4]Zhao X. Preparation of Large-scale SnO2:F transparent conductive film by atmospheric spray pyrolysis deposition and the effect of fluorine-doping[J]. Int. J. Electrochem. Sc., 2016, 11(7):5395
[5]Korotcenkov G, Cho B K. Spray pyrolysis deposition of undoped SnO2and In2O3films and their structural properties[J]. Prog.Cryst. Growth Charact. Mater., 2017, 63:1
[6]Smith A, Laurent J M, Smith D S, et al. Experimental survey of different precursor/solvent pairs for the deposition of tin dioxide by pyrosol[J]. Thin Solid Films, 1998, 315:17
[7]Ishida T, Kouno H, Kobayashi H, et al. Dependence of photo-voltages of spray-deposited indium tin oxide/silicon oxide/silicon junction solar cells on spray solvents[J]. J. Electrochem. Soc.,1994, 141:1357
[8]Mohd Napi M L, Seng N K, Ahmad M K. Surface morphology and electrical properties of FTO(fluorine doped tin oxide)with different precursor solution for transparent conducting oxide[J].Appl. Mech. Mater., 2015, 773-774:682
[9]Napi M L M, Maarof M F, Soon C F, et al. Fabrication of fluorine doped tin oxide(FTO)thin filmsusing spray pyrolysis deposition method for transparent conducting oxide[J]. J. Eng. Appl. Sci.,2015, 11:8800
[10]Ching-Prado E, Watson A, MIRANDA H. Optical and electrical properties of fluorine doped tin oxide thin film[J]. J. Mater. SciMater. El., 2018, 5:1
[11]Wang L K, Yu J Y, Niu X Y, et al. Effect of F and Nb co-doping on structural, electrical and optical properties of spray deposited tin oxide thin films[J]. Thin Solid Films, 2018, 649:147
[12]Turgut G, SNmez E. Synthesis and characterization of Mo doped SnO2thin films with spray pyrolysis[J]. Superlattice. Microst.,2014, 69:175
[13]Korotkov R Y, Ricou P, Farran A J E. Preferred orientations in polycrystalline SnO2, films grown by atmospheric pressure chemi-cal vapor deposition[J]. Thin Solid Films, 2006, 502(1-2):79
[14]Belanger D, Dodelet J P, Lombos B A, et al. Thickness depen-dence of transport properties of doped polycrystalline tin oxide films[J]. J. Electrochem. Soc., 1985, 132:1398
[15]Zhao H L, Liu Q Y, Yang J K, et al. Effect of catalyst water on the properties and structure of fluorine-doped tin oxide films[J]. Rare Metal Mat. Eng., 2008, 37(6):952(赵洪力,刘起英,杨静凯等.催化剂水对掺杂氟的氧化锡膜性能与结构的影响[J].稀有金属材料与工程, 2008, 37(6):952)
[16]Thangaraju B. Structural and electrical studies on highly conduct-ing spray deposited fluorine and antimony doped SnO2thin films from SnCl2precursor[J]. Thin Solid Films, 2002, 402:71
[17]Benouis C E, Benhaliliba M, Mouffak Z, et al. The low resistive and transparent Al-doped SnO2 films:p-type conductivity, nano-structures and photoluminescence[J]. J. Alloys Compd., 2014,603:213
[18]Kumar K D A, Valanarasu S, Jeyadheepan K, et al. Evaluation of the physical, optical, and electrical properties of SnO2:F thin films prepared by nebulized spray pyrolysis for optoelectronics[J]. J.Mater. Sci. Mater. M., 2018, 29(5):3648
[19]Yu S, Zheng H, Li L, et al. Highly conducting and transparent anti-mony doped tin oxide thin films:the role of sputtering power den-sity[J]. Ceram. Int., 2017, 43:5654
[20]Haitjema H, Elich J. The physical properties of fluorine-doped tin dioxide films and the influence of ageing and impurity effects[J].Sol. Energ. Mat., 1987, 16:79
[21]Adnane M, Cachet H, Folcher G, et al. Beneficial effects of hydro-gen peroxide on growth, structural and electrical properties of sprayed fluorine-doped SnO2films[J]. Thin Solid Films, 2005,492:240
[22]Mohagheghi M M B, Yazdi S T, Mousavi M. Transport, structural and optical properties of SnO2transparent semiconductor thin films alloyed with chromium:carrier type conversion[J]. J. Mater.Sci., 2017, 28(6):1
[23]Oshima M, Yoshino K. Electron scattering mechanism of FTO films grown by spray pyrolysis method[J]. J. Electron. Mater.,2010, 39:819
[24]Fauzia V, Yusnidar M N, Lalasari L H, et al. High figure of merit transparent conducting Sb-doped SnO2thin films prepared via ul-trasonic spray pyrolysis[J]. J. Alloys Compd., 2017, 720:79