退火温度对溅射法沉积Cu-Cr-O薄膜性能的影响
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摘要
使用Cu Cr O2陶瓷靶材,利用射频磁控溅射方法在石英衬底上沉积了Cu-Cr-O薄膜,研究了退火温度对Cu-Cr-O薄膜结构及光电性能的影响。X射线衍射分析显示,退火温度为973 K时薄膜即已晶化并形成单相铜铁矿结构CuCrO2,随着退火温度的升高,薄膜结晶性逐渐提高。紫外-可见光谱与电学性能测量结果表明:薄膜可见光透过率随退火温度升高呈上升趋势,电导率则呈下降趋势,在973～1273K退火薄膜的可见光透过率最高为50%,电导率最高为0.12 S/cm。扫描电子显微镜照片显示,Cu-Cr-O薄膜电导率的下降主要与退火产生的微裂纹有关。
Cu-Cr-O thin films were prepared by the RF magnetron sputtering technology on quartz substrates with a sintered Cu Cr O2 ceramic as a target. The influence of annealing temperature on the structural and optoelectronic properties of the Cu-Cr-O thin films was investigated. The X-ray diffraction analysis reveals that the Cu-Cr-O film annealed at 973 K has a delafossite structure without other phases, and the crystallinity of the film increases with the increase of the annealing temperature. Based on the measurements by ultraviolet–visible spectroscopy and the electrical property, the optical transmittance increases and the conductivity decreases as the annealing temperature increases. The maximum optical transmittance and conductivity of the film annealed at 973-1 273 K are 50% and 0.12 S/cm, respectively. The results by scanning electron microscopy indicate that presence of micro-cracks in the film could be the main reason for the decreased electrical conductivity.
Cu-Cr-O thin films were prepared by the RF magnetron sputtering technology on quartz substrates with a sintered Cu Cr O2 ceramic as a target. The influence of annealing temperature on the structural and optoelectronic properties of the Cu-Cr-O thin films was investigated. The X-ray diffraction analysis reveals that the Cu-Cr-O film annealed at 973 K has a delafossite structure without other phases, and the crystallinity of the film increases with the increase of the annealing temperature. Based on the measurements by ultraviolet–visible spectroscopy and the electrical property, the optical transmittance increases and the conductivity decreases as the annealing temperature increases. The maximum optical transmittance and conductivity of the film annealed at 973-1 273 K are 50% and 0.12 S/cm, respectively. The results by scanning electron microscopy indicate that presence of micro-cracks in the film could be the main reason for the decreased electrical conductivity.
引文
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[4]KAWAZOE H,YANAGI H,UEDA K,et al.Transparent p-type conducting oxides:design and fabrication of p-n heterojunctions[J].MRS Bull,2000,25(8):28?36.
[5]TATE J,JAYARAJ M K,DRAESEKE A D,et al.P-type oxides for use in transparent diodes[J].Thin Solid Films,2002,411(1):119?124.
[6]NAGARAJAN R,DRAESEKE A D,SLEIGHT A W,et al.P-type conductivity in CuCr1?x Mgx O2 films and powders[J].J Appl Phys,2001,89(12):8022?8025.
[7]LI D,FANG X D,DENG Z H,et al.Electrical,optical and structural properties of CuCrO2 films prepared by pulsed laser deposition[J].JPhys D:Appl Phys,2007,40(16):4912?4915.
[8]SUN H,YAZDI M A P,SANCHETTE F,et al.Optoelectronic properties of delafossite structure CuCr0.93Mg0.07O2 sputter deposited coatings[J].J Phys D:Appl Phys,2016,49(18):185105.
[9]WU S Z,DENG Z H,DONG W W,et al.Effect of deposition atmosphere on the structure and properties of Mg doped CuCrO2 thin films prepared by direct current magnetron sputtering[J].Thin Solid Films,2015,595(part A):124?128.
[10]YU R S,WU C M.Characteristics of p-type transparent conductive CuCrO2 thin films[J].Appl Surf Sci,2013,282(10):92?97.
[11]黄斯楷,杨元政,谢致微.退火温度对p型CuCrO2薄膜结构与光学性能的影响[J].电子元件与材料,2015,34(7):38?41.HUANG Sikai,YANG Yuanzheng,XIE Zhiwei.Electron Compon Mater(in Chinese),2015,34(7):38?41.
[12]CHIU T W,TSAI S W,WANG Y P,et al.Preparation of p-type conductive transparent CuCrO2:Mg thin films by chemical solution deposition with two-step annealing[J].Ceram Int,2012,38(S1):S673-S676.
[13]JCPDS Card File:39?0247.
[14]SUN C H,TSAI D C,CHANG Z C,et al.Structural,optical,and electrical properties of conducting p-type transparent Cu-Cr-O thin films[J].Ceram Int,2016,42(1):13697?13703.
[15]自兴发,杨雯,杨培志,等.溅射功率对脉冲磁控溅射沉积Cu2O薄膜结构和光学性能的影响[J].人工晶体学报,2014,43(4):1003?1008.ZI Xingfa,YANG Wen,YANG Peizhi,et al.J Synth Cryst(in Chinese),2014,43(4):1003?1008.
[16]赵颖,杨洋.铟掺杂调控氧化锌纳米柱的密度与光学带隙[J].硅酸盐学报,2017,45(10):1439?1445.ZHAO Ying,YANG Yang.J Chin Ceram Soc,2017,45(10):1439?1445.
[17]DEMICHELIS F,KANIADAKIS G,TAGLIAFERRO A,et al.New approach to optical analysis of absorbing thin solid films[J].Appl Opt,1987,26(9):1737?1740.
[18]INGRAM B J,BERTONI M I,POEPPELMEIER K R,et al.Point defects and transport mechanisms in transparent conducting oxide of intermediate conductivity[J].Thin Solid Films,2005,486(1):86?93.
[19]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.
[20]?agla?,Hasan A.Production and characterization of CuCrO2nanofibers[J].Mater Chem Phys,2016,170(1):138?144.
[21]DUAN N,SLEIGHT A W,JAYARAJ M K,et al.Transparent p-type conducting CuScO2+x Films[J].Appl Phys Lett,2000,77(9):1325?1326.