不同氟源对FTO薄膜结构和性能的影响
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摘要
采用喷雾热解法制备了氟掺杂的二氧化锡(fluorine-doped tin oxide,FTO)薄膜,氟源分别为NH_4F、SnF_2、CF_3COOH和HF。采用X射线衍射仪、扫描电子显微镜对薄膜微观结构和表面形貌进行了表征;用四探针电阻仪、霍尔效应仪和紫外分光光度计对薄膜的光电性能进行了分析。结果表明,不同氟源制备的FTO薄膜均为沿(200)方向择优生长的四方金红石结构,掺杂后薄膜的表面形貌较未掺杂时变化较大,由多角状和棱柱状颗粒相间分布变为完全由类金字塔状颗粒堆积而成。四种氟源中,以SnF_2为氟源制备的FTO薄膜的光电性能优于其它氟源,薄膜的最佳电阻率达5.06×10~(-4)Ωcm,载流子浓度为4.850×10~(20)cm~(-3),光学带隙为4.03 eV。不同氟源对FTO薄膜可见光区透过率影响不大,薄膜的平均透过率均大于83%。不同氟源FTO薄膜的性能差异主要由氟的掺杂量决定的。
Tin oxide thin films doped with fluorine were deposited by spray pyrolysis. NH_4F,SnF_2,CF_3COOH and HF were used as fluorine sources,respectively. The evolution of the microstructure and surface morphology of the films were characterized by X-ray diffraction( XRD) and scanning electron microscopy( SEM). The photoelectric properties of the films were analyzed by the fourpoint probe,Hall measurements and UV-Vis spectroscopy. The results show that the FTO thin films exhibit a tetragonal cassiterite structure with( 200) orientation. The morphology of films has a great change by doping with F. The undoped SnO_2 thin film is mainly comprised of polygonal particles and prismatic particles,while the FTO thin film is completely composed by pyramidal particles.Among the four fluorine sources,the SnO_2 thin film doped with SnF_2 obtains better photoelectric properties than others,the values of resistivity,carrier concentration and optical band gap are 5. 06 × 10~(-4)Ω cm,4. 850 × 1 0~(20) cm~(-3) and 4. 03,respectively. the effect of fluorine sources on transmittance of the FTO films is trivial with the average transmittance of above 83%. The performance of the FTO films are mainly determined by the doping amount of fluorine.
Tin oxide thin films doped with fluorine were deposited by spray pyrolysis. NH_4F,SnF_2,CF_3COOH and HF were used as fluorine sources,respectively. The evolution of the microstructure and surface morphology of the films were characterized by X-ray diffraction( XRD) and scanning electron microscopy( SEM). The photoelectric properties of the films were analyzed by the fourpoint probe,Hall measurements and UV-Vis spectroscopy. The results show that the FTO thin films exhibit a tetragonal cassiterite structure with( 200) orientation. The morphology of films has a great change by doping with F. The undoped SnO_2 thin film is mainly comprised of polygonal particles and prismatic particles,while the FTO thin film is completely composed by pyramidal particles.Among the four fluorine sources,the SnO_2 thin film doped with SnF_2 obtains better photoelectric properties than others,the values of resistivity,carrier concentration and optical band gap are 5. 06 × 10~(-4)Ω cm,4. 850 × 1 0~(20) cm~(-3) and 4. 03,respectively. the effect of fluorine sources on transmittance of the FTO films is trivial with the average transmittance of above 83%. The performance of the FTO films are mainly determined by the doping amount of fluorine.
引文
[1]姜辛,孙超,洪瑞江,等.透明导电氧化物薄膜[M].北京:高等教育出版社,2008.
[2]KIM C Y,RIU D H.Texture control of fluorine-doped tin oxide thin film[J].Thin Solid Films,2011,519(10):3081-3085.
[3]KADHIM I H,HASSAN H A,ABDULLAH Q N.Hydrogen gas sensor based on nanocrystalline Sn O2,thin film grown on bare si substrates[J].Nano-Micro Letters,2016,8(1):1-9.
[4]GURAKAR S,SERIN T,SERIN N.Studies on optical properties of antimony doped Sn O2films[J].Applied Surface Science,2015,352:16-22.
[5]SUZUKI A Y,NOSE K,UENO A,et al.High transparency and electrical conductivity of Sn O2:Nb thin films formed through(001)-oriented Sn O:Nb on glass substrate[J].Applied Physics Express,2012,5(1):1103.
[6]LEKSHMY S S,DANIEL G P,JOY K.Microstructure and physical properties of sol gel derived Sn O2:Sb thin films for optoelectronic applications[J].Applied Surface Science,2013,274(6):95-100.
[7]CONSONNI V,REY G,ROUSSEL H,et al.Preferential orientation of fluorine-doped Sn O2,thin films:The effects of growth temperature[J].Acta Materialia,2013,61(1):22-31.
[8]杨静凯,赵洪力,董立中,等.钢化过程中低辐射玻璃Sn Ox:F薄膜氧含量的变化及其影响[J].燕山大学学报,2012,36(6):482-485.
[9]吴绍航,张楠,郭晓阳,等.Sr-F共掺杂的Sn O2基透明导电薄膜[J].发光学报,2015(7):829-833.
[10]MOKARIPOOR E,BAGHERI-MOHAGHEGHI M M.Study of structural,electrical and photoconductive properties of F and P co-doped Sn O2transparent semiconducting thin film deposited by spray pyrolysis[J].Materials Science in Semiconductor Processing,2015,30:400-405.
[11]CHANTARAT N,HSU S H,LIN C C,et al.Mechanism of an AZO-coated FTO film in improving the hydrogen plasma durability of transparent conducting oxide thin films for amorphous-silicon based tandem solar cells[J].Journal of Materials Chemistry,2012,22(16):8005-8012.
[12]刘宏燕,颜悦,望咏林,等.透明导电氧化物薄膜材料研究进展[J].航空材料学报,2015,35(4):63-82.
[13]JOSEPH D P,RENUGAMBAL P,SARAVANAN M,et al.Effect of Li doping on the structural,optical and electrical properties of spray deposited Sn O2,thin films[J].Thin Solid Films,2009,517(21):6129-6136.
[14]BENOUIS C E,BENHALILIBA M,MOUFFAK Z,et al.The low resistive and transparent Al-doped Sn O2,films:p-type conductivity,nanostructures and photoluminescence[J].Journal of Alloys&Compounds,2014,603(603):213-223.
[15]范志新,陈玖琳,孙以材.二氧化锡薄膜的最佳掺杂含量理论表达式[J].电子器件,2001,24(2):132-135.
[16]THANGARAJU B.Structural and electrical studies on highly conducting spray deposited fluorine and antimony doped Sn O2,thin films from Sn Cl2,precursor[J].Thin Solid Films,2002,402(1/2):71-78.
[17]SERIN T,SERIN N,KARADENIZ S,et al.Electrical,structural and optical properties of Sn O2,thin films prepared by spray pyrolysis[J].Journal of Non-Crystalline Solids,2006,352(3):209-215.
[18]TURGUT G,KESKENLER E F,AYDIN S,et al.An investigation of the Nb doping effect on structural,morphological,electrical and optical properties of spray deposited F doped Sn O2films[J].Physica Scripta,2013,87(3):035602.
[19]李静,郭米艳.探究掺杂对Zn O薄膜禁带宽度的影响因素[J].江西化工,2011(3):4-7.
[20]BELANGER D,DODELET J P,LOMBOS B A,et al.Thickness dependence of transport properties of doped polycrystalline tin oxide films[J].Journal of the Electrochemical Society,1985,132(6):1398-1405.
[21]KOROTKOV R Y,RICOU P,FARRAN A J E.Preferred orientations in polycrystalline Sn O2,films grown by atmospheric pressure chemical vapor deposition[J].Thin Solid Films,2006,502(1/2):79-87.
[22]SMITH A.Pyrosol deposition of Zn O and Sn O2based thin films:the interplay between solution chemistry,growth rate and film morphology[J].Thin Solid Films,2000,376(1):47-55.
[23]SMITH A,LAURENT J M,SMITH D S,et al.Relation between solution chemistry and morphology of Sn O2-based thin films deposited by a pyrosol process[J].Thin Solid Films,1995,266(1):20-30.
[2]KIM C Y,RIU D H.Texture control of fluorine-doped tin oxide thin film[J].Thin Solid Films,2011,519(10):3081-3085.
[3]KADHIM I H,HASSAN H A,ABDULLAH Q N.Hydrogen gas sensor based on nanocrystalline Sn O2,thin film grown on bare si substrates[J].Nano-Micro Letters,2016,8(1):1-9.
[4]GURAKAR S,SERIN T,SERIN N.Studies on optical properties of antimony doped Sn O2films[J].Applied Surface Science,2015,352:16-22.
[5]SUZUKI A Y,NOSE K,UENO A,et al.High transparency and electrical conductivity of Sn O2:Nb thin films formed through(001)-oriented Sn O:Nb on glass substrate[J].Applied Physics Express,2012,5(1):1103.
[6]LEKSHMY S S,DANIEL G P,JOY K.Microstructure and physical properties of sol gel derived Sn O2:Sb thin films for optoelectronic applications[J].Applied Surface Science,2013,274(6):95-100.
[7]CONSONNI V,REY G,ROUSSEL H,et al.Preferential orientation of fluorine-doped Sn O2,thin films:The effects of growth temperature[J].Acta Materialia,2013,61(1):22-31.
[8]杨静凯,赵洪力,董立中,等.钢化过程中低辐射玻璃Sn Ox:F薄膜氧含量的变化及其影响[J].燕山大学学报,2012,36(6):482-485.
[9]吴绍航,张楠,郭晓阳,等.Sr-F共掺杂的Sn O2基透明导电薄膜[J].发光学报,2015(7):829-833.
[10]MOKARIPOOR E,BAGHERI-MOHAGHEGHI M M.Study of structural,electrical and photoconductive properties of F and P co-doped Sn O2transparent semiconducting thin film deposited by spray pyrolysis[J].Materials Science in Semiconductor Processing,2015,30:400-405.
[11]CHANTARAT N,HSU S H,LIN C C,et al.Mechanism of an AZO-coated FTO film in improving the hydrogen plasma durability of transparent conducting oxide thin films for amorphous-silicon based tandem solar cells[J].Journal of Materials Chemistry,2012,22(16):8005-8012.
[12]刘宏燕,颜悦,望咏林,等.透明导电氧化物薄膜材料研究进展[J].航空材料学报,2015,35(4):63-82.
[13]JOSEPH D P,RENUGAMBAL P,SARAVANAN M,et al.Effect of Li doping on the structural,optical and electrical properties of spray deposited Sn O2,thin films[J].Thin Solid Films,2009,517(21):6129-6136.
[14]BENOUIS C E,BENHALILIBA M,MOUFFAK Z,et al.The low resistive and transparent Al-doped Sn O2,films:p-type conductivity,nanostructures and photoluminescence[J].Journal of Alloys&Compounds,2014,603(603):213-223.
[15]范志新,陈玖琳,孙以材.二氧化锡薄膜的最佳掺杂含量理论表达式[J].电子器件,2001,24(2):132-135.
[16]THANGARAJU B.Structural and electrical studies on highly conducting spray deposited fluorine and antimony doped Sn O2,thin films from Sn Cl2,precursor[J].Thin Solid Films,2002,402(1/2):71-78.
[17]SERIN T,SERIN N,KARADENIZ S,et al.Electrical,structural and optical properties of Sn O2,thin films prepared by spray pyrolysis[J].Journal of Non-Crystalline Solids,2006,352(3):209-215.
[18]TURGUT G,KESKENLER E F,AYDIN S,et al.An investigation of the Nb doping effect on structural,morphological,electrical and optical properties of spray deposited F doped Sn O2films[J].Physica Scripta,2013,87(3):035602.
[19]李静,郭米艳.探究掺杂对Zn O薄膜禁带宽度的影响因素[J].江西化工,2011(3):4-7.
[20]BELANGER D,DODELET J P,LOMBOS B A,et al.Thickness dependence of transport properties of doped polycrystalline tin oxide films[J].Journal of the Electrochemical Society,1985,132(6):1398-1405.
[21]KOROTKOV R Y,RICOU P,FARRAN A J E.Preferred orientations in polycrystalline Sn O2,films grown by atmospheric pressure chemical vapor deposition[J].Thin Solid Films,2006,502(1/2):79-87.
[22]SMITH A.Pyrosol deposition of Zn O and Sn O2based thin films:the interplay between solution chemistry,growth rate and film morphology[J].Thin Solid Films,2000,376(1):47-55.
[23]SMITH A,LAURENT J M,SMITH D S,et al.Relation between solution chemistry and morphology of Sn O2-based thin films deposited by a pyrosol process[J].Thin Solid Films,1995,266(1):20-30.