Cu过量对Cu_(1+x)Al_(1-x)O_2(0≤x≤0.04)薄膜结构与光电性能的影响
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摘要
以单相多晶Cu_(1+x)Al_(1-x)O_2陶瓷做靶材,采用射频磁控溅射方法在石英衬底上沉积了Cu过量的Cu_(1+x)Al_(1-x)O_2(0≤x≤0. 04)薄膜。通过X射线衍射(XRD)、紫外吸收光谱以及电导率的测试,表征了不同含Cu量Cu_(1+x)Al_(1-x)O_2薄膜的结构与光电性能。结果表明,沉积态薄膜经退火处理后,由非晶转变为具有铜铁矿结构的纯相Cu_(1+x)Al_(1-x)O_2;退火态薄膜在可见光区域的平均透过率约为55%,平均可见光透过率不受Cu含量的影响;退火态薄膜样品的室温电导率随Cu含量的增加而增大,Cu_(1.04)Al_(0.96)O_2的室温电导率最高,为1. 22×10~(-2)S/cm;在近室温区(200～300 K),退火态薄膜均很好地符合Arrhenius热激活模式。
Cu-excess Cu_(1+x)Al_(1-x)O_2( 0≤x≤0. 04) thin films were deposited by RF magnetron sputtering technology on quartz substrates with sintered pure phase Cu_(1+x)Al_(1-x)O_2 ceramics as targets. The influence of Cu content on the structural and optoelectronic properties of the films was investigated. X-Ray diffraction( XRD) results reveal that all annealed films have a pure delafossite phase( Cu_(1+x)Al_(1-x)O_2). The average transmittance of annealed films is around 55% in the visible light range,and average transmittance in this region dose not influenced by Cu content. The conductivity of annealed films increases with the increasing Cu concentration,and the highest conductivity reaches 1. 22 × 10~(-2) S/cm for Cu_(1.04)Al_(0.96)O_2 film at room temperature. The temperature dependence of conductivity follows the Arrhenius rule in the range of 200-300 K for all annealed samples,it indicates that the electrical conductivity is ascribe to thermal activation.
Cu-excess Cu_(1+x)Al_(1-x)O_2( 0≤x≤0. 04) thin films were deposited by RF magnetron sputtering technology on quartz substrates with sintered pure phase Cu_(1+x)Al_(1-x)O_2 ceramics as targets. The influence of Cu content on the structural and optoelectronic properties of the films was investigated. X-Ray diffraction( XRD) results reveal that all annealed films have a pure delafossite phase( Cu_(1+x)Al_(1-x)O_2). The average transmittance of annealed films is around 55% in the visible light range,and average transmittance in this region dose not influenced by Cu content. The conductivity of annealed films increases with the increasing Cu concentration,and the highest conductivity reaches 1. 22 × 10~(-2) S/cm for Cu_(1.04)Al_(0.96)O_2 film at room temperature. The temperature dependence of conductivity follows the Arrhenius rule in the range of 200-300 K for all annealed samples,it indicates that the electrical conductivity is ascribe to thermal activation.
引文
[1]Kim S I,Cho S H,Choi S R,et al.Crystallization and Electrical Properties of ITO∶Ce Thin Films for Flat Panel Display Applications[J].Thin Solid Films,2009,517(14):4061-4064.
[2]Yu X M,Yu X,Zhang J J,et al.Efficient Inverted Polymer Solar Cells Based on Surface Modified FTO Transparent Electrodes[J].Solar Energy Materials&Solar Cells,2015,136:142-147.
[3]Ma C H,Lu X S,Xu B,et al.Effects of Sputtering Parameters on Photoelectric Properties of AZO Film for CZTS Solar Cell[J].Journal of Alloys and Compounds,2019,774:201-209.
[4]Kawazoe H,Yasukawa M,Hyodo H,et al.P-Type Electrical Conduction in Transparent Thin Films of CuAlO2[J].Nature,1997,389(6654):939-942.
[5]Ruttanapun C,Prachamon W,Wichainchai A.Optoelectronic Properties of Cu1-xPtxFe O2(0≤x≤0.05)Delafossite for P-Type Transparent Conducting Oxide[J].Current Applied Physics,2012,12(1):166-170.
[6]Dong G B,Zhang M,Lan W,et al.Structural and Physical Properties of Mg-Doped CuAlO2Thin Films[J].Vavuum,2008,82(11):1321-1324.
[7]Zou Y S,Wang H P,Zhang S L,et al.Structural,Electrical and Optical Properties of Mg-Doped CuAlO2Films by Pulsed Laser Deposition[J].RSC Advances,2014,4(78):41294-41300.
[8]Liu R J,Li Y F,Yao B,et al.Shallow Acceptor State in Mg-Doped CuAlO2and Its Effect on Electrical and Optical Properties:An Experimental and First-Principles Study[J].ACS Applied Materials&Interfaces,2017,9(14):12608-12616.
[9]Dong G B,Zhang M,Li T X,et al.Co-doping Effect of Ca and N on the Structure and Properties of CuAlO2Thin Film[J].Journal of the Electrochemical Society,2010,157(1):H127-H130.
[10]Dong P M,Zhang M,Dong G B,et al.The Optical and Electrical Properties of Zn-Doped CuAlO2Thin Films Deposited by RF Magnetron Sputtering[J].Journal of the Electrochemical Society,2008,155(5):H319-H322.
[11]Pan J Q,Guo S K,Zhang X,et al.The Photoconductivity Properties of Transparent Ni Doped CuAlO2Films[J].Materials Letters,2013,96:31-33.
[12]王影,朱满康,马丙闯,等.Cr掺杂CuAlO2陶瓷电学性能的研究[J].人工晶体学报,2016,45(7):1746-1750.
[13]Pan J Q,Lan W,Liu H Q,et al.Preparation and Properties of Transparent Conductive N-Doped CuAlO2Films using N2O as the N Source[J].Journal of Materials Science:Materials in Electronics,2014,25(9):4004-4007.
[14]Zhang Y J,Liu Z T,Feng L P,et al.Effect of Oxygen Partial Pressure on the Structure and Properties of Cu-A-O Thin Films[J].Applied Surface Science,2012,258(14):5354-5359.
[15]Cai J L,Gong H.The Influence of Cu/Al Ratio on Properties of Chemical-Vapor-Deposition-Grown P-Type Cu-Al-O Transparent Semiconducting Films[J].Journal of Applied Physics,2005,98(3):033707.
[16]Deng Z H,Fang X D,Tao R H,et al.Effect of Cu-Excess on the Electrical Properties of CuxAl O2(1≤x≤1.06)[J].Journal of Semiconductors,2008,29(6):1052-1056.
[17]Huang F Q,Liu M L,Yang C Y.Highly Enhanced P-Type Electrical Conduction in Wide Bandgap Cu1+xAl1-xS2Polycrystals[J].Solar Energy Materials&Solar Cells,2011,95:2924-2927.
[18]陈首部,陆轴,兰椿.氧化锌薄膜的微观结构及其结晶性能研究[J].中南民族大学学报,2017,36(4):67-72.
[19]邓赞红,方晓东,陶汝华,等.沉积激光能量对CuAlO2薄膜光学性质的影响[J].无机材料学报,2011,26(3):281-284.
[20]徐继承,谢致薇,杨元政.衬底温度对CuAlO2薄膜的结构与光学性能的影响[J].电子元件与材料,2016,35(7):42-45.
[21]邹友生,汪海鹏,张亦驰,等.PLD制备CuAlO2薄膜的结构与性能研究[J].真空科学与技术学报,2014,34(9):925-930.
[22]Hsieh P H,Lu Y M,Hwang W S.Effects of RF Power on the Growth Behaviors of CuAlO2Thin Films[J].Ceramics International,2014,40:9361-9366.
[23]Liu S L,Wu Z H,Zhang Y K,et al.Strong Temperature-Dependent Crystallization,Phase Transiton,Optical and Electrical Characteristics of P-Type CuAlO2Thin Films[J].Physical Chemistry Chemical Physics,2015,17(1):557-562.
[24]Demichelis F,Kaniadakis G,Tagliaferro A,et al.New Approach to Optical Analysis of Absorbing Thin Solid Films[J].Applied Optics,1987,26(9):1737-1740.
[25]Yu R S,Wu C M.Characteristics of P-Type Transparent Conductive CuCrO2Thin Films[J].Applied Surface Science,2013,282:92-97.
[26]Tauc J,Grigorovici R,Vancu A.Optical Properties and Electronic Structure of Amorphous Gemanium[J].Physica Status Solidi,1966,15(15):627-637.
[27]涂丽敏,郭巧能,江亚晓,等.气相辅助电沉积法低温制备CH3NH3Pb I3钙钛矿薄膜的研究[J].人工晶体学报,2018,47(2):302-307.
[28]Ooi P K,Ng S S,Abdullah M J,et al.Effects of Oxygen Percentage on the Growth of Copper Oxide Thin Films by Reactive Radio Frequency Sputtering[J].Materials Chemistry and Physics,2013,140:243-248.
[29]Kim D S,Park S J,Jeong E K,et al.Optical and Electrical Properties of P-Type Transparent Conducting CuAlO2Thin Film[J].Thin Solid Films,2007,515(12):5103-5108.
[30]Yu R S,Liang S C,Lu C J,et al.Characterization and Optoelectronic Properties of P-Type N-Doped CuAlO2Films[J].Applied Physics Letters,2007,90(19):191117.
[31]Burstein E.Anomalous Optical Absorption Limit in InSb[J].Physical Review,1954,93(3):632-633.
[32]Moss T S.The Interpretation of the Properties of Indium Antimonide[J].Proceeding of the Physical Society.Section B,1954,67(10):775-782.
[33]Mott N F.Conduction in Non-Crystalline Materials[M].New York:Oxford University Press,1987.
[2]Yu X M,Yu X,Zhang J J,et al.Efficient Inverted Polymer Solar Cells Based on Surface Modified FTO Transparent Electrodes[J].Solar Energy Materials&Solar Cells,2015,136:142-147.
[3]Ma C H,Lu X S,Xu B,et al.Effects of Sputtering Parameters on Photoelectric Properties of AZO Film for CZTS Solar Cell[J].Journal of Alloys and Compounds,2019,774:201-209.
[4]Kawazoe H,Yasukawa M,Hyodo H,et al.P-Type Electrical Conduction in Transparent Thin Films of CuAlO2[J].Nature,1997,389(6654):939-942.
[5]Ruttanapun C,Prachamon W,Wichainchai A.Optoelectronic Properties of Cu1-xPtxFe O2(0≤x≤0.05)Delafossite for P-Type Transparent Conducting Oxide[J].Current Applied Physics,2012,12(1):166-170.
[6]Dong G B,Zhang M,Lan W,et al.Structural and Physical Properties of Mg-Doped CuAlO2Thin Films[J].Vavuum,2008,82(11):1321-1324.
[7]Zou Y S,Wang H P,Zhang S L,et al.Structural,Electrical and Optical Properties of Mg-Doped CuAlO2Films by Pulsed Laser Deposition[J].RSC Advances,2014,4(78):41294-41300.
[8]Liu R J,Li Y F,Yao B,et al.Shallow Acceptor State in Mg-Doped CuAlO2and Its Effect on Electrical and Optical Properties:An Experimental and First-Principles Study[J].ACS Applied Materials&Interfaces,2017,9(14):12608-12616.
[9]Dong G B,Zhang M,Li T X,et al.Co-doping Effect of Ca and N on the Structure and Properties of CuAlO2Thin Film[J].Journal of the Electrochemical Society,2010,157(1):H127-H130.
[10]Dong P M,Zhang M,Dong G B,et al.The Optical and Electrical Properties of Zn-Doped CuAlO2Thin Films Deposited by RF Magnetron Sputtering[J].Journal of the Electrochemical Society,2008,155(5):H319-H322.
[11]Pan J Q,Guo S K,Zhang X,et al.The Photoconductivity Properties of Transparent Ni Doped CuAlO2Films[J].Materials Letters,2013,96:31-33.
[12]王影,朱满康,马丙闯,等.Cr掺杂CuAlO2陶瓷电学性能的研究[J].人工晶体学报,2016,45(7):1746-1750.
[13]Pan J Q,Lan W,Liu H Q,et al.Preparation and Properties of Transparent Conductive N-Doped CuAlO2Films using N2O as the N Source[J].Journal of Materials Science:Materials in Electronics,2014,25(9):4004-4007.
[14]Zhang Y J,Liu Z T,Feng L P,et al.Effect of Oxygen Partial Pressure on the Structure and Properties of Cu-A-O Thin Films[J].Applied Surface Science,2012,258(14):5354-5359.
[15]Cai J L,Gong H.The Influence of Cu/Al Ratio on Properties of Chemical-Vapor-Deposition-Grown P-Type Cu-Al-O Transparent Semiconducting Films[J].Journal of Applied Physics,2005,98(3):033707.
[16]Deng Z H,Fang X D,Tao R H,et al.Effect of Cu-Excess on the Electrical Properties of CuxAl O2(1≤x≤1.06)[J].Journal of Semiconductors,2008,29(6):1052-1056.
[17]Huang F Q,Liu M L,Yang C Y.Highly Enhanced P-Type Electrical Conduction in Wide Bandgap Cu1+xAl1-xS2Polycrystals[J].Solar Energy Materials&Solar Cells,2011,95:2924-2927.
[18]陈首部,陆轴,兰椿.氧化锌薄膜的微观结构及其结晶性能研究[J].中南民族大学学报,2017,36(4):67-72.
[19]邓赞红,方晓东,陶汝华,等.沉积激光能量对CuAlO2薄膜光学性质的影响[J].无机材料学报,2011,26(3):281-284.
[20]徐继承,谢致薇,杨元政.衬底温度对CuAlO2薄膜的结构与光学性能的影响[J].电子元件与材料,2016,35(7):42-45.
[21]邹友生,汪海鹏,张亦驰,等.PLD制备CuAlO2薄膜的结构与性能研究[J].真空科学与技术学报,2014,34(9):925-930.
[22]Hsieh P H,Lu Y M,Hwang W S.Effects of RF Power on the Growth Behaviors of CuAlO2Thin Films[J].Ceramics International,2014,40:9361-9366.
[23]Liu S L,Wu Z H,Zhang Y K,et al.Strong Temperature-Dependent Crystallization,Phase Transiton,Optical and Electrical Characteristics of P-Type CuAlO2Thin Films[J].Physical Chemistry Chemical Physics,2015,17(1):557-562.
[24]Demichelis F,Kaniadakis G,Tagliaferro A,et al.New Approach to Optical Analysis of Absorbing Thin Solid Films[J].Applied Optics,1987,26(9):1737-1740.
[25]Yu R S,Wu C M.Characteristics of P-Type Transparent Conductive CuCrO2Thin Films[J].Applied Surface Science,2013,282:92-97.
[26]Tauc J,Grigorovici R,Vancu A.Optical Properties and Electronic Structure of Amorphous Gemanium[J].Physica Status Solidi,1966,15(15):627-637.
[27]涂丽敏,郭巧能,江亚晓,等.气相辅助电沉积法低温制备CH3NH3Pb I3钙钛矿薄膜的研究[J].人工晶体学报,2018,47(2):302-307.
[28]Ooi P K,Ng S S,Abdullah M J,et al.Effects of Oxygen Percentage on the Growth of Copper Oxide Thin Films by Reactive Radio Frequency Sputtering[J].Materials Chemistry and Physics,2013,140:243-248.
[29]Kim D S,Park S J,Jeong E K,et al.Optical and Electrical Properties of P-Type Transparent Conducting CuAlO2Thin Film[J].Thin Solid Films,2007,515(12):5103-5108.
[30]Yu R S,Liang S C,Lu C J,et al.Characterization and Optoelectronic Properties of P-Type N-Doped CuAlO2Films[J].Applied Physics Letters,2007,90(19):191117.
[31]Burstein E.Anomalous Optical Absorption Limit in InSb[J].Physical Review,1954,93(3):632-633.
[32]Moss T S.The Interpretation of the Properties of Indium Antimonide[J].Proceeding of the Physical Society.Section B,1954,67(10):775-782.
[33]Mott N F.Conduction in Non-Crystalline Materials[M].New York:Oxford University Press,1987.
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