衬底温度对CuCrO_2薄膜结构及光电性能的影响
|
摘要
采用射频磁控溅射方法,在石英衬底上制备CuCrO_2薄膜。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外吸收光谱以及电导率的测定,表征不同衬底温度沉积薄膜样品的结构与光电性能。结果表明:薄膜的结晶度、可见光透过率与室温电导率均随衬底温度的升高而增大。衬底温度升高至923 K后,薄膜由非晶转变为具有铜铁矿结构的单相CuCrO_2。1023 K沉积的薄膜光电性能最佳,其平均可见光透过率为50%,室温电导率为0.33 S/cm。在近室温区(150～300 K),1023 K沉积薄膜导电规律符合半导体热激活模式,激活能为0.04 eV。
CuCrO_2 thin films were prepared by radio frequency magnetron sputtering on quartz substrates. The influence of substrate temperature on the structural and optoelectronic properties was investigated. XRD and XPS results show that923 K and 1023 K deposited films has a delafossite structure without other phases. The electrical conductivity and optical transmittance increase with the increase of substrate temperature. When the substrate temperature is 1023 K, the film has a higher optical transmittance and electrical conductivity. Its transparence in visible light is 50%, and the conductivity at room temperature is 0.33 S/cm. The temperature dependence of electrical conductivity agrees well with the Arrhenius rule in the temperature range of 150-300 K for the 1023 K deposited sample, and the activation energy is 0.04 eV.
CuCrO_2 thin films were prepared by radio frequency magnetron sputtering on quartz substrates. The influence of substrate temperature on the structural and optoelectronic properties was investigated. XRD and XPS results show that923 K and 1023 K deposited films has a delafossite structure without other phases. The electrical conductivity and optical transmittance increase with the increase of substrate temperature. When the substrate temperature is 1023 K, the film has a higher optical transmittance and electrical conductivity. Its transparence in visible light is 50%, and the conductivity at room temperature is 0.33 S/cm. The temperature dependence of electrical conductivity agrees well with the Arrhenius rule in the temperature range of 150-300 K for the 1023 K deposited sample, and the activation energy is 0.04 eV.
引文
[1]KOSEOGLU H,TURKOGLU F,KURTA M,YAMAN M D,AKCA F G AYGUN G,OZYUZER L.Improvement of optical and electrical properties of ITO thin films by electro-annealing[J].Vacuum,2015,120:8-13.
[2]YAN X,LI W M,ABERLE A G,VENKATARAJ S.Investigation of the thickness effect on material and surface texturing properties of sputtered Zn O:Al films for thin-film Si solar cell applications[J].Vacuum,2016,123:151-159.
[3]ZHEN M D,NI J M,LIANG F,WANG M C,ZHAO X J.Effect of annealing temperature on the crystalline structure,growth behaviour and properties of SnO2:Sb thin films prepared by radio frequency(RF)-magnetron sputtering[J].Journal of Alloys and Compounds,2016,663:371-378.
[4]KAWAZOE H,YASUKAWA M,HYODO H,KURITA M,YANAGI H,HOSONO H.P-type electrical conduction in transparent thin films of CuAlO2[J].Nature,1997,389:939-942.
[5]YANAGI H,HASE T,IBUKI S,UEDA K,HOSONO H.Bipolarity in electrical conduction of transparent oxide semiconductor CuInO2 with delafossite structure[J].Applied Physics Letters,2001,78:1583-1585.
[6]UEDA K,HASE T,YANAGI H,KAWAZOE H,HOSONO H.Epitaxial growth of transparent p-type conducting CuGaO2 thin films on sapphire(001)substrates by pulsed laser deposition[J].Journal of Applied Physics,2001,89:1790-1793.
[7]DUAN N,SLEIGHT A W,JAYARAJ M K,TATE J.Transparent p-type conducting CuScO2+x Films[J].Applied Physics Letters,2000,77:1325-1326.
[8]NAGARAJAN R,DRAESEKE A D,SLEIGHT A W,TATE J.P-type conductivity in CuCr1-x Mgx O2 films and powders[J].Journal of Applied Physics,2001,89:8022-8025.
[9]李杨超,张铭,董国波,赵学平,严辉.CuCr1-xMgx O2(0≤x≤0.09)薄膜的光电性能研究[J].中国有色金属学报.2010,20(5):898-902.LI Yang-chao,ZHANG Ming,DONG Guo-bo,ZHAO Xue-ping,YAN Hui.Optical and electrical properties of CuCr1-x Mgx O2(0≤x≤0.09)thin films[J].The Chinese Journal of Nonferrous Metals,2010,20(5):898-902.
[10]YU R S,WU C M.Characteristics of p-type transparent conductive CuCrO2 thin films[J].Applied Surface Science,2013,282:92-97.
[11]SUN H,YAZDI M A P,SANCHETTE F,BILLARD A.Optoelectronic properties of delafossite structure CuCr0.93Mg0.07O2 sputter deposited coatings[J].Journal of Physics D:Applied Physics,2016,19:185105.
[12]LI D,FANG X D,DENG Z H,ZHOU S,TAO R H,DONG WW,WANG T,ZHAO Y P,MENG G,ZHU X B.Electrical,optical and structural properties of CuCrO2 films prepared by pulsed laser deposition[J].Journal of Physics D:Applied Physics,2007,40:4912-4915.
[13]LIU R J,LI Y F,YAO B,DING Z H,JIANG Y H,MENG L,DENG R,ZHANG L G,ZHANG Z Z,ZHAO H F,LIU L.Shallow acceptor state in Mg-doped CuAlO2 and its effect on electrical and optical properties:An experimental and first-principles study[J].Applied Materials and Interfaces,2017,9:12608-12616.
[14]LI D,FANG X D,DONG W W,DENG Z H,TAO R H,ZHOUS,WANG J M,WANG T,ZHAO Y P,ZHU X B.Magnetic and electrical properties of p-type Mn-doped CuCrO2semiconductors[J].Journal of Physics D:Applied Physics,2009,42:055009.
[15]DENG L Y,LIN F T,ZHANG Z J.Room-temperature ferromagnetism in Mn-doped CuCrO2 nanopowders[J].Journal of Shanghai Normal University(Natural Sciences),2015,44:399-400.
[16]WAGNER C D,RIGGS W M,DAVIS G E.Handbook of X-Ray photoelectron spectroscopy[M].Eden Prairie:Perkin-Elmer Corporation,1979.
[17]LANGFORD J I,WILSON A J C.Scherrer after sixty years:Asurvey and some new results in the determination of crystallite size[J].Journal of Applied Crystallography,1978,11:102-113.
[18]SUN C H,TSAI D C,CHANG Z C,CHEN E C,SHIEU F S.Structural,optical,and electrical properties of conducting p-type transparent Cu-Cr-O thin films[J].Ceramics International,2016,42:13697-13703.
[19]王星星,张福勤,周俊,郑吉祥,黎炳前,刘怡.电子束蒸镀法制备CuIn0.7Ga0.3Se2薄膜太阳能电池的性能[J].中国有色金属学报,2016,26(1):103-111.WANG Xing-xing,ZHANG Fu-qin,ZHOU Jun,ZHENGJi-xiang,LI Bing-qian,LIU Yi.Characterization of CuIn0.7Ga0.3Se2 films prepared by electron-beam evaporation for thin film solar cell[J].The Chinese Journal of Nonferrous Metals,2016,26(1):103-111.
[20]CHIU T W,TSAI S W,WANG Y P,HSU K H.Preparation of p-type conductive transparent CuCrO2:Mg thin films by chemical solution deposition with two-step annealing[J].Ceramics International,2012,38S:s673-s676.
[21]董国波,张铭,兰伟,朱满康,严辉.CuxAlO2(0.92≤x≤1.0)陶瓷电输运性能[J].中国有色金属学报,2007,17(9):1470-1474.DONG Guo-bo,ZHANG Ming,LAN Wei,ZHU Man-kang,YAN Hui.Electrical transport properties of Cux AlO2(0.92≤x≤1.0)ceramics[J].The Chinese Journal of Nonferrous Metals,2007,17(9):1470-1474.
[22]INGRAM B J,BERTONI M I,POEPPELMEIER K R,MASONT O.Point defects and transport mechanisms in transparent conducting oxide of intermediate conductivity[J].Thin Solid Films,2005,486:86-93.
[2]YAN X,LI W M,ABERLE A G,VENKATARAJ S.Investigation of the thickness effect on material and surface texturing properties of sputtered Zn O:Al films for thin-film Si solar cell applications[J].Vacuum,2016,123:151-159.
[3]ZHEN M D,NI J M,LIANG F,WANG M C,ZHAO X J.Effect of annealing temperature on the crystalline structure,growth behaviour and properties of SnO2:Sb thin films prepared by radio frequency(RF)-magnetron sputtering[J].Journal of Alloys and Compounds,2016,663:371-378.
[4]KAWAZOE H,YASUKAWA M,HYODO H,KURITA M,YANAGI H,HOSONO H.P-type electrical conduction in transparent thin films of CuAlO2[J].Nature,1997,389:939-942.
[5]YANAGI H,HASE T,IBUKI S,UEDA K,HOSONO H.Bipolarity in electrical conduction of transparent oxide semiconductor CuInO2 with delafossite structure[J].Applied Physics Letters,2001,78:1583-1585.
[6]UEDA K,HASE T,YANAGI H,KAWAZOE H,HOSONO H.Epitaxial growth of transparent p-type conducting CuGaO2 thin films on sapphire(001)substrates by pulsed laser deposition[J].Journal of Applied Physics,2001,89:1790-1793.
[7]DUAN N,SLEIGHT A W,JAYARAJ M K,TATE J.Transparent p-type conducting CuScO2+x Films[J].Applied Physics Letters,2000,77:1325-1326.
[8]NAGARAJAN R,DRAESEKE A D,SLEIGHT A W,TATE J.P-type conductivity in CuCr1-x Mgx O2 films and powders[J].Journal of Applied Physics,2001,89:8022-8025.
[9]李杨超,张铭,董国波,赵学平,严辉.CuCr1-xMgx O2(0≤x≤0.09)薄膜的光电性能研究[J].中国有色金属学报.2010,20(5):898-902.LI Yang-chao,ZHANG Ming,DONG Guo-bo,ZHAO Xue-ping,YAN Hui.Optical and electrical properties of CuCr1-x Mgx O2(0≤x≤0.09)thin films[J].The Chinese Journal of Nonferrous Metals,2010,20(5):898-902.
[10]YU R S,WU C M.Characteristics of p-type transparent conductive CuCrO2 thin films[J].Applied Surface Science,2013,282:92-97.
[11]SUN H,YAZDI M A P,SANCHETTE F,BILLARD A.Optoelectronic properties of delafossite structure CuCr0.93Mg0.07O2 sputter deposited coatings[J].Journal of Physics D:Applied Physics,2016,19:185105.
[12]LI D,FANG X D,DENG Z H,ZHOU S,TAO R H,DONG WW,WANG T,ZHAO Y P,MENG G,ZHU X B.Electrical,optical and structural properties of CuCrO2 films prepared by pulsed laser deposition[J].Journal of Physics D:Applied Physics,2007,40:4912-4915.
[13]LIU R J,LI Y F,YAO B,DING Z H,JIANG Y H,MENG L,DENG R,ZHANG L G,ZHANG Z Z,ZHAO H F,LIU L.Shallow acceptor state in Mg-doped CuAlO2 and its effect on electrical and optical properties:An experimental and first-principles study[J].Applied Materials and Interfaces,2017,9:12608-12616.
[14]LI D,FANG X D,DONG W W,DENG Z H,TAO R H,ZHOUS,WANG J M,WANG T,ZHAO Y P,ZHU X B.Magnetic and electrical properties of p-type Mn-doped CuCrO2semiconductors[J].Journal of Physics D:Applied Physics,2009,42:055009.
[15]DENG L Y,LIN F T,ZHANG Z J.Room-temperature ferromagnetism in Mn-doped CuCrO2 nanopowders[J].Journal of Shanghai Normal University(Natural Sciences),2015,44:399-400.
[16]WAGNER C D,RIGGS W M,DAVIS G E.Handbook of X-Ray photoelectron spectroscopy[M].Eden Prairie:Perkin-Elmer Corporation,1979.
[17]LANGFORD J I,WILSON A J C.Scherrer after sixty years:Asurvey and some new results in the determination of crystallite size[J].Journal of Applied Crystallography,1978,11:102-113.
[18]SUN C H,TSAI D C,CHANG Z C,CHEN E C,SHIEU F S.Structural,optical,and electrical properties of conducting p-type transparent Cu-Cr-O thin films[J].Ceramics International,2016,42:13697-13703.
[19]王星星,张福勤,周俊,郑吉祥,黎炳前,刘怡.电子束蒸镀法制备CuIn0.7Ga0.3Se2薄膜太阳能电池的性能[J].中国有色金属学报,2016,26(1):103-111.WANG Xing-xing,ZHANG Fu-qin,ZHOU Jun,ZHENGJi-xiang,LI Bing-qian,LIU Yi.Characterization of CuIn0.7Ga0.3Se2 films prepared by electron-beam evaporation for thin film solar cell[J].The Chinese Journal of Nonferrous Metals,2016,26(1):103-111.
[20]CHIU T W,TSAI S W,WANG Y P,HSU K H.Preparation of p-type conductive transparent CuCrO2:Mg thin films by chemical solution deposition with two-step annealing[J].Ceramics International,2012,38S:s673-s676.
[21]董国波,张铭,兰伟,朱满康,严辉.CuxAlO2(0.92≤x≤1.0)陶瓷电输运性能[J].中国有色金属学报,2007,17(9):1470-1474.DONG Guo-bo,ZHANG Ming,LAN Wei,ZHU Man-kang,YAN Hui.Electrical transport properties of Cux AlO2(0.92≤x≤1.0)ceramics[J].The Chinese Journal of Nonferrous Metals,2007,17(9):1470-1474.
[22]INGRAM B J,BERTONI M I,POEPPELMEIER K R,MASONT O.Point defects and transport mechanisms in transparent conducting oxide of intermediate conductivity[J].Thin Solid Films,2005,486:86-93.