退火温度对旋涂法制备SnO_2薄膜性能的影响
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摘要
采用旋涂法在玻璃基底上制备SnO_2薄膜,通过原子力显微镜(AFM)、X射线反射(XRR)、傅氏转换红外线光谱仪(FT-IR)、X射线衍射(XRD)、紫外-可见分光光度计、四探针、开尔文探针系统对薄膜的表面形貌、结构及光学特性、电学特性进行分析,探讨了退火温度对薄膜质量的影响及作用机制。研究发现:随着退火温度升高,薄膜厚度和有机成分杂质减小,薄膜密度递增,但薄膜表面粗糙度有所上升;当退火温度升高至500℃时,薄膜结构由非晶转变为结晶,其主要晶面为氧化锡的(110)、(101)和(211)晶面。旋涂法制备的氧化锡薄膜在可见光区域的平均透光率在90%以上,随着退火温度上升,薄膜在400～800 nm波段的透光率先减小后增大,薄膜的带隙宽度分别为3. 840 eV(沉积态薄膜)、3. 792 eV(100℃)、3. 690 eV(300℃)和3. 768eV(500℃);薄膜的电导率也随着退火温度升高而增加,在500℃时电导率高达916 S/m;薄膜的功函数先增大后减小,分别为(4. 61±0. 005) eV(沉积态薄膜)、(4. 64±0. 005) eV(100℃)、(4. 82±0. 025) eV(300℃)、(4. 78±0. 065) eV(500℃)。
Tin oxide thin films were prepared on glass substrates by spin coating,then,films were annealed at different temperatures in the air. The morphology,structural characteristics,optical properties and electrical properties of the films were characterized by atomic force microscope (AFM),X-ray reflection system (XRR),FT-IR,X-ray diffraction (XRD),UV-visible spectrophotometer,four-probe tester and Kelvin Probe,and the effect of annealing temperature on the quality of film and its mechanism have been studied. The results show that,as the annealing temperatureincreases,the thickness of the films decreases,the content of organic in films reduces,and the density of the films increases,however,the surface roughness of the film increases. When the annealing temperature is 500 ℃,SnO_2 crystals appear on the film,the (101), (110), (211) crystal phases appear. Transmittance of samples in the visible light region is above 90%. As the annealing temperature increases,the transmittance of the film in 400-800 nm band decreases first and then increases,and bandgap widths of the films are 3. 840 eV (as-deposited),3. 792 eV (100 ℃),3. 690 eV (300 ℃),and 3. 768 eV (500 ℃); the conductivity of the film increases,and the conductivity reaches 916 S/m at 500 ℃; the work function of the film increases and then decreases,and work function of the films is (4. 61 ± 0. 005) eV (as-deposited), (4. 64 ± 0. 005) eV (100 ℃), (4. 82 ± 0. 025) eV (300 ℃), (4. 78 ± 0. 065) eV (500 ℃).
Tin oxide thin films were prepared on glass substrates by spin coating,then,films were annealed at different temperatures in the air. The morphology,structural characteristics,optical properties and electrical properties of the films were characterized by atomic force microscope (AFM),X-ray reflection system (XRR),FT-IR,X-ray diffraction (XRD),UV-visible spectrophotometer,four-probe tester and Kelvin Probe,and the effect of annealing temperature on the quality of film and its mechanism have been studied. The results show that,as the annealing temperatureincreases,the thickness of the films decreases,the content of organic in films reduces,and the density of the films increases,however,the surface roughness of the film increases. When the annealing temperature is 500 ℃,SnO_2 crystals appear on the film,the (101), (110), (211) crystal phases appear. Transmittance of samples in the visible light region is above 90%. As the annealing temperature increases,the transmittance of the film in 400-800 nm band decreases first and then increases,and bandgap widths of the films are 3. 840 eV (as-deposited),3. 792 eV (100 ℃),3. 690 eV (300 ℃),and 3. 768 eV (500 ℃); the conductivity of the film increases,and the conductivity reaches 916 S/m at 500 ℃; the work function of the film increases and then decreases,and work function of the films is (4. 61 ± 0. 005) eV (as-deposited), (4. 64 ± 0. 005) eV (100 ℃), (4. 82 ± 0. 025) eV (300 ℃), (4. 78 ± 0. 065) eV (500 ℃).
引文
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[17]秦苏梅,童梓洋,邓红梅,等.快速热退火对纳米晶粒Sn O2薄膜性质的影响[J].红外与毫米波学报,2008,27(2):101-104.QIN S M,TONG Z Y,DENG H M,et al..Effect of rapid thermal annealing on property of nano-Sn O2thin film[J].J.Infrared Millim.Waves,2008,27(2):101-104.(in Chinese)
[18]陈博,徐海燕,张欣,等.膜厚对Sn O2∶Sb薄膜红外光学性能的影响[J].材料导报,2016,30(S2):266-268.CHEN B,XU H Y,ZHANG X,et al..Influence of film thickness on infrared optical properties of Sn O2:Sb thin film[J].Mater.Rev.,2016,30(S2):266-268.(in Chinese)
[19]梁斐,赵修建,倪佳苗,等.热处理对Sb∶Sn O2透明导电薄膜光电性能的影响[J].硅酸盐通报,2017,36(9):2951-2957.LIANG F,ZHAO X J,NI J M,et al..Effect of heat treatment on the optical and electrical properties of Sb∶Sn O2transparent conduction films[J].Bull.Chin.Ceram.Soc.,2017,36(9):2951-2957.(in Chinese)
[20]刘绰,马蕾,彭英才.Sn O2薄膜的制备及其光电特性[J].河北大学学报(自然科学版),2017,37(2):123-127.LIU C,MA L,PENG Y C.Preparation of Sn O2thin film and photoelectric properties[J].J.Hebei Univ.(Nat.Sci.Ed.),2017,37(2):123-127.(in Chinese)
[21]林殷茵,汤庭鳌,姚熹.二氧化锡薄膜的MOD法制备和表征[J].功能材料,2001,32(3):277-279.LIN Y Y,TANG T A,YAO X.Preparation and characterization of Sn O2thin film by MOD method[J].J.Funct.Mater.,2001,32(3):277-279.(in Chinese)
[22]何瑞英,魏长平,王国栋,等.Ni/Sn O2复合薄膜的制备与光电性能[J].发光学报,2015,36(8):888-892.HE R Y,WEI C P,WANG G D,et al..Preparation and photoelectric properties of Ni/Sn O2composite thin films[J].Chin.J.Lumin.,2015,36(8):888-892.(in Chinese)
[23]李文英,钟建,张柯,等.退火对Zn O/Cu/Zn O透明导电薄膜性能的影响[J].材料工程,2015,43(1):44-48.LI W Y,ZHONG J,ZHANG K,et al..Effects of annealing on properties of Zn O/Cu/Zn O transparent conductive film[J].J.Mater.Eng.,2015,43(1):44-48.(in Chinese)
[24]ZHENG H R,LI L X,SUN Z,et al..Preferential orientation,microstructure and functional properties of Sn O2∶Sb thin film:the effects of post-growth annealing[J].Appl.Surf.Sci.,2016,362:230-236.
[25]EZEMA F I,EKWEALOR A B C,OSUJI R U.Effect of thermal annealing on the band GAP and optical properties of chemical bath deposited Zn Se thin films[J].Turk.J.Phys.,2006,30(3):157-163.
[26]UYSAL B?,ARIERü?A.Structural and optical properties of Sn O2nano films by spin-coating method[J].Appl.Surf.Sci.,2015,350:74-78.
[27]周向东,李子亨,李志有.化学沉积法制备Cd S纳米薄膜及成膜机理[J].吉林大学学报(理学版),2007,45(1):116-120.ZHOU X D,LI Z H,LI Z Y.Preparation and formation mechanism of Cd S Nano-films via chemical bath deposition technique[J].J.Jilin Univ.(Sci.Ed.),2007,45(1):116-120.(in Chinese)
[28]汤猛,李勇男,殷波,等.H2O2对溶液法制备a-IGZO薄膜光学特性的影响[J].液晶与显示,2016,31(12):1124-1130.TANG M,LI Y N,YIN B,et al..Influence of hydrogen peroxide on optical properties of a-IGZO thin films by solution process[J].Chin.J.Liq.Cryst.Disp.,2016,31(12):1124-1130.(in Chinese)
[2]闫艳花.超声雾化法制备Er3+掺杂Sn O2薄膜结构与性质研究[D].天津:南开大学,2012.YAN Y H.Research on The Structure and Properties of Er3+Doped Sn O2Film by Ultrasonic Atomization[D].Tianjin:Nankai University,2012.(in Chinese)
[3]宣鑫科.掺铟二氧化锡薄膜(ITO)的制备及其性质研究[D].上海:华东师范大学,2010.XUAN X K.Preparation and Properties of Indium Doped Tin Oxide Film(ITO)[D].Shanghai:East China Normal University,2010.(in Chinese)
[4]李玉,郑其经.二氧化锡薄膜的制备、特性及应用[J].材料科学与工程,1992,10(2):21-27LI Y,ZHENG Q J.The preparation,properties and applications of tin oxide thin films[J].Mater.Sci.Eng.,1992,10(2):21-27.(in Chinese)
[5]梁凯.超声喷雾法制备大面积二氧化锡绒面导电膜及性能研究[D].天津:南开大学,2009.LIANG K.Preparation of Large-area Sn O2Conductive Films by Ultrasonic Spraying and Its Properties[D].Tianjin:Nankai University,2009.(in Chinese)
[6]CHOI M S,LEE Y J,KWON J D,et al..Effects of hydrogen plasma treatment on Sn O2∶F substrates for amorphous Si thin film solar cells[J].Curr.Appl.Phys.,2013,13(8):1589-1593.
[7]GUILLéN C,MONTERO J,HERRERO J M.Transparent and conductive electrodes combining AZO and ATO thin films for enhanced light scattering and electrical performance[J].Appl.Surf.Sci.,2013,264:448-452.
[8]YANG T Y,QIN X B,WANG H H,et al.Preparation and application in p-n homojunction diode of p-type transparent conducting Ga-doped Sn O2thin films[J].Thin Solid Films,2010,518(19):5542-5545.
[9]丁啸雄.磁控溅射法制备氮掺杂二氧化锡薄膜及其性能评价[D].南京:东南大学,2012.DING X X.The Deposition of Nitrigen-doped Tin Oxide Films by Magnetron Sputtering and Analysis of Properties[D].Nanjing:Southeast University,2012.(in Chinese)
[10]JIMéNEZ V M,ESPINS J P,CABALLERO A,et al..Sn O2thin films prepared by ion beam induced CVD:preparation and characterization by X-ray absorption spectroscopy[J].Thin Solid Films,1999,353(1-2):113-123.
[11]SHEU J K,SU Y K,CHI G C,et al..Effects of thermal annealing on the indium tin oxide Schottky contacts of n-Ga N[J].Appl.Phys.Lett.,1998,72(25):3317-3319.
[12]HAMD W,WU Y C,BOULLE A,et al..Microstructural study of Sn O2thin layers deposited on sapphire by sol-gel dipcoating[J].Thin Solid Films,2009,518(1):1-5.
[13]KUANTAMA E,HAN D W,SUNG Y M,et al..Structure and thermal properties of transparent conductive nanoporous F∶Sn O2films[J].Thin Solid Films,2009,517(14):4211-4214.
[14]潘庆谊,张剑平,董晓雯,等.溶胶-凝胶法制备二氧化锡薄膜[J].硅酸盐通报,2001,20(1):6-9.PAN Q Y,ZHANG J P,DONG X W,et al..Preparation of Sn O2thin films by sol-gel method[J].Bull.Chin.Ceram.Soc.,2001,20(1):6-9.(in Chinese)
[15]姚红,张占文,黄勇,等.聚酰亚胺薄膜表面粗糙度的影响因素[J].强激光与粒子束,2011,23(7):1861-1866.YAO H,ZHANG Z W,HUANG Y,et al..Factors influencing surface roughness of polyimide film[J].High Power Laser Part.Beams,2011,23(7):1861-1866.(in Chinese)
[16]姚宏燚,袁志钟,熊志高,等.反应磁控溅射制备Sn O2薄膜及其微观形貌与光致发光性能研究[J].材料导报,2016,30(18):1-5.YAO H Y,YUAN Z Z,XIONG Z G,et al..Microstructure and photoluminescence of Sn O2thin films prepared by reactive magnetron sputtering[J].Mater.Rev.,2016,30(18):1-5.(in Chinese)
[17]秦苏梅,童梓洋,邓红梅,等.快速热退火对纳米晶粒Sn O2薄膜性质的影响[J].红外与毫米波学报,2008,27(2):101-104.QIN S M,TONG Z Y,DENG H M,et al..Effect of rapid thermal annealing on property of nano-Sn O2thin film[J].J.Infrared Millim.Waves,2008,27(2):101-104.(in Chinese)
[18]陈博,徐海燕,张欣,等.膜厚对Sn O2∶Sb薄膜红外光学性能的影响[J].材料导报,2016,30(S2):266-268.CHEN B,XU H Y,ZHANG X,et al..Influence of film thickness on infrared optical properties of Sn O2:Sb thin film[J].Mater.Rev.,2016,30(S2):266-268.(in Chinese)
[19]梁斐,赵修建,倪佳苗,等.热处理对Sb∶Sn O2透明导电薄膜光电性能的影响[J].硅酸盐通报,2017,36(9):2951-2957.LIANG F,ZHAO X J,NI J M,et al..Effect of heat treatment on the optical and electrical properties of Sb∶Sn O2transparent conduction films[J].Bull.Chin.Ceram.Soc.,2017,36(9):2951-2957.(in Chinese)
[20]刘绰,马蕾,彭英才.Sn O2薄膜的制备及其光电特性[J].河北大学学报(自然科学版),2017,37(2):123-127.LIU C,MA L,PENG Y C.Preparation of Sn O2thin film and photoelectric properties[J].J.Hebei Univ.(Nat.Sci.Ed.),2017,37(2):123-127.(in Chinese)
[21]林殷茵,汤庭鳌,姚熹.二氧化锡薄膜的MOD法制备和表征[J].功能材料,2001,32(3):277-279.LIN Y Y,TANG T A,YAO X.Preparation and characterization of Sn O2thin film by MOD method[J].J.Funct.Mater.,2001,32(3):277-279.(in Chinese)
[22]何瑞英,魏长平,王国栋,等.Ni/Sn O2复合薄膜的制备与光电性能[J].发光学报,2015,36(8):888-892.HE R Y,WEI C P,WANG G D,et al..Preparation and photoelectric properties of Ni/Sn O2composite thin films[J].Chin.J.Lumin.,2015,36(8):888-892.(in Chinese)
[23]李文英,钟建,张柯,等.退火对Zn O/Cu/Zn O透明导电薄膜性能的影响[J].材料工程,2015,43(1):44-48.LI W Y,ZHONG J,ZHANG K,et al..Effects of annealing on properties of Zn O/Cu/Zn O transparent conductive film[J].J.Mater.Eng.,2015,43(1):44-48.(in Chinese)
[24]ZHENG H R,LI L X,SUN Z,et al..Preferential orientation,microstructure and functional properties of Sn O2∶Sb thin film:the effects of post-growth annealing[J].Appl.Surf.Sci.,2016,362:230-236.
[25]EZEMA F I,EKWEALOR A B C,OSUJI R U.Effect of thermal annealing on the band GAP and optical properties of chemical bath deposited Zn Se thin films[J].Turk.J.Phys.,2006,30(3):157-163.
[26]UYSAL B?,ARIERü?A.Structural and optical properties of Sn O2nano films by spin-coating method[J].Appl.Surf.Sci.,2015,350:74-78.
[27]周向东,李子亨,李志有.化学沉积法制备Cd S纳米薄膜及成膜机理[J].吉林大学学报(理学版),2007,45(1):116-120.ZHOU X D,LI Z H,LI Z Y.Preparation and formation mechanism of Cd S Nano-films via chemical bath deposition technique[J].J.Jilin Univ.(Sci.Ed.),2007,45(1):116-120.(in Chinese)
[28]汤猛,李勇男,殷波,等.H2O2对溶液法制备a-IGZO薄膜光学特性的影响[J].液晶与显示,2016,31(12):1124-1130.TANG M,LI Y N,YIN B,et al..Influence of hydrogen peroxide on optical properties of a-IGZO thin films by solution process[J].Chin.J.Liq.Cryst.Disp.,2016,31(12):1124-1130.(in Chinese)