本研究利用反應式離子束濺鍍法成功地沉積了氧化鎳及氧化鎳摻銅薄膜，並且探討氧氣流量比對於氧化鎳薄膜的光電特性影響。研究結果顯示，在300C下沉積氧化鎳薄膜，當Opf = 0.5時有NiO (200)的單一晶相，半高寬為0.39°有最好的結晶性，而在300C下沉積氧化鎳摻銅薄膜，在較低氬氧流量比例下，繞射峰值與Ni2O3 (102)及NiO (200)的繞射峰值重疊，推測形成CuxNi2-xO3結構，能量散射光譜儀(EDS)分析顯示x = 1，直到Opf = 1.0時剩下單一晶相繞射峰值與NiO (200)位置重疊，半高寬為0.3°有最好的結晶性，推測型成CuxNi1-xO結構，EDS分析顯示x = 0.5。而拉曼分析指出，在不同氬氧比例下，氧化鎳薄膜都只有NiO的單一晶相，而氧化鎳摻銅薄膜在低氧比例環境下類似Ni2O3的拉曼結果；高氧比例環境下為類似NiO拉曼。在能隙方面，在不同氬氧比下，氧化鎳薄膜能隙大約為3.5 eV，經摻銅後隨著氬氧比例上升，薄膜能隙從3.2 eV下降至2.3 eV。

Nickel oxide and copper-nickel oxide thin films have been successfully deposited by reactive ion beam sputter deposition. Experimental results show that nickel oxide deposited at 300C is single phase NiO while best crystalline quality is achieved with an Opf of 0.5. X-ray diffraction (XRD) analysis of nickel-copper oxide deposited at 300C shows a Ni2O3 like crystalline structure at low Opf while changes to NiO like crystalline structure at high Opf. Energy dispersive x-ray spectroscope (EDS) analysis shows that nickel-copper oxide deposited at low Opf is CuxNi2-xO3 with x = 1, while nickel-copper oxide deposited at high Opf is CuxNi1-xO with x = 0.5, which is supported by Raman analysis. The bandgap of NiO is ~ 3.5 eV regardless of Opf while the band gap of nickel-copper oxide decreases from 3.2 to 2.3 eV as Opf reaches 1.0.

[1] H. Sato, T. Minami, S. Takata and T. Yamada, “Transparent conducting p-type NiO thin films prepared by magnetron sputtering,” Thin Solid Films, Vol. 236, pp. 27-31, 1993.
[2] I. Hotovy, J. Huran, J. Janıka and A. P. Kobzev, “Deposition and properties of nickel oxide films　produced by DC reactive magnetron sputtering,” Vacuum, Vol. 51, pp. 157-160, 1998.
[3] Y. Zhou, D. Gu, Y. Geng and F. Gan, “Thermal structural and optical properties of NiOx thin films deposited by reactive dc-magnetron sputtering,” Mater. Sci. Eng., B, Vol. 135, pp.125-128, 2006.
[4] K.S. Kim and N. Winograd, “X-ray photoelectron spectroscopic studies of nickel oxygen surfaces using oxygen and argon ion-bombardment,” Surf. Sci., Vol. 43, pp. 625-643, 1965.
[5] T. Fleisch, N. Winograd and W. N. Delgass, “Chemisorption of oxygen on Ni(100) by SIMS and XPS,” Surf. Scl., Vol. 78, pp. 141-158, 1978.
[6] D. Dong, W. Wang, G. Dong, F. Zhang, Y. He, H. Yu, F. Liu, M. Wang and X. Diao, “Electrochromic properties and performance of NiOx films and their cor-responding all-thin-film flexible devices prepared by reactive DC magnetron sputtering,” Appl. Surf. Sci., Vol. 383, pp. 49-56, 2016.
[7] Y. Huang, Y. Zhang, S. Lin, L. Yan, R. Cao, R. Yang, X. Liang and W. Xiang, “Sol-gel synthesis of NiO nanoparticles doped sodium borosilicate glass with third-order nonlinear optical properties,” J. Alloys Compd., Vol. 686, pp. 564-570, 2016.
[8] T. M. Roffi, S. Nozaki and K. Uchida, “Growth mechanism of single-crystalline NiO thin films grown by metal organic chemical vapor deposition,” J. Cryst. Growth, Vol. 451, pp. 57-64, 2016.
[9] E. Lindahla, J. Lub, M. Ottossona and J. O. Carlssona, “Epitaxial NiO (100) and NiO (111) films grown by atomic layer deposition,” J. Cryst. Growth, Vol. 311, pp. 4082-4088, 2009.
[10] I. Manouchehria, D. Mehrparparvara, M. I. Hamila and R. Moradiana, “Optical properties of zinc doped NiO thin films deposited by RF magnetron sputtering,” Optik, Vol. 127, pp. 9400-9406, 2016.
[11] E. Fujii, A. Tomozawa, H. Torii and R. Takayama, ”Preferred orientations of NiO films prepared by plasma-enhanced metal organic chemical vapor deposition,” Jpn. J. Appl. Phys., Vol. 35, pp. L328-L330, 1996.
[12] K. Yoshimura, T. Miki, and S. Tanemura, “Nickel oxide electrochromic thin films prepared by reactive DC magnetron sputtering,” Jpn. J. Appl. Phys., Vol. 34, pp. 2440-2446, 1995.
[13] M. Bögner, A. Fuchs, K. Scharnagl, R. Winter, T. Doll, and I. Eisele, “Thin (NiO)1−x(Al2O3)x, Al doped and Al coated NiO layers for gas detection with HSGFET,” Sens. Actuator, B, Vol. 47, pp. 145-152, 1998.
[14] I. M. Chan and F. C. Hong, “Improved performance of the single-layer and dou-ble-layer organic light emitting diodes by nickel oxide coated indium tin oxide anode,” Thin Solid Films, Vol. 450, pp. 304-311, 2004.
[15] J. C. Loudon, “Antiferromagnetism in NiO observed by transmission electron diffraction,” Phys. Rev. Lett., Vol. 109, pp.267204-1-267204-5, 2012.
[16] R. C. Tenentz, D. T. Gillaspie, A. Miedaner, P. A. Parilla, C. J. Curtis and A. C. Dillon, “Fast-switching Electrochromic Li+-doped NiO films by ultrasonic Spray Deposition,” J. Electrochem. Soc., Vol. 157, pp. H 318-H 322, 2010.
[17] I. Hotovy, V. Rehacek, P. Sicillano, S. Capone and L. Spiess, “Sensing character-istics of NiO thin films as NO2 gas sensor,” Thin Solid Films, Vol. 418, pp. 9-15, 2002.
[18] H. Kumagai, M. Matsumoto, K. Toyoa and M. Obara, ” Preparation and charac-teristics of nickel oxide thin film by controlled growth with sequential surface chemical reactions,” J. Mater. Sci. Lett., Vol. 15, pp. 1081-1083, 1996.
[19] H. Steinebach, S. Kannan, L. Rieth and F. Solzbacher, “H2 gas sensor perfor-mance of NiO at high temperatures in gas mixtures,” Sens. Actuators, B, Vol. 151, pp. 162-168, 2010.
[20] A. Sawaby, M. S. Selim, S. Y. Marzouk, M. A. Mostafa and A. Hosny, ”Structure, optical and electrochromic properties of NiO thin films,” Physica B, Vol. 405, pp. 3412-3420, 2010.
[21] S. M. Pan, R. C. Tu, Y. M. Fan, R. C. Yeh and J. T. Hsu, “Enhanced output power of InGaN-GaN light-emitting diodes with high-transparency nick-el-oxide-indium-tin-oxide Ohmic contacts,” IEEE, Photonics Technol. Lett., Vol. 15, pp. 646-648, 2003.
[22] J. Bandara and H. Weerasinghe, “Solid-state dye-sensitized solar cell with p-type NiO as a hole collector,” Sol. Energy Mater. Sol. Cells., Vol. 85, pp. 385-390, 2005.
[23] I. M. Chan, T. Y. Hsu and F. C. Hong, “Enhanced hole injections in organic light-emitting devices by depositing nickel oxide on indium tin oxide anode,” Appl. Phys. Lett., Vol. 81, pp. 1899-1091, 2002.
[24] C. C. Lee, J. C. Hsu, D. T. Wei and J. H. Lin, “Morphology of dual beam ion sputtered films investigate by atomic force microscopy,” Thin Solid Films, Vol. 308-309, pp. 74-78, 1997.
[25] C. G. Granqvist, “Chapter 19–Nickel Oxide Films,” Handb. Inorg. Electroceram. Mater., pp. 339–377, 1995.
[26] D. Adler and J. Feinleib, “Electrical and optical properties of narrow-band mate-rials,” Phys. Rev. B: Condens. Matter, Vol. 2, pp. 3112-3134, 1970.
[27] L. Tonks and I. Langmuir, “Oscillations in ionized gas,” Proc. Natl. Acad. Sci. USA, Vol. 14, pp. 627-637, 1929.
[28] W. R. Grove, “On the electro-chemical polarity of gases,” Phil. Trans. Roy. Soc., Vol. 142, pp. 87-101, 1852.
[29] C. C. Lee, J. C. Hsu and D. H. Wong, “The characteristics of some metallic ox-ides prepare in high vacuum by ion beam sputtering,” Appl. Surf. Sci., Vol. 171, pp. 151-156, 2001.
[30] L. Davis, “Properties of transparent conducting oxides deposited at room tem-perature,” Thin Solid films, Vol. 236, pp. 1-5, 1993.
[31] J. A. Nieminen and K. Kaski, “Criteria for different growth modes of thin films,” Surf. Sci. Lett., Vol. 185, pp. L489-L496, 1987.
[32] N. Ohshima, M. Naka and Y. Tsukamoto, “Structural an magnetic properties of Ni-O/Ni-Fe bilayer films,” Jpn. J. Appl. Phys., Vol. 35, pp. L1585-L1588, 1996.
[33] O. Kohmoto, H. Nakagawa, F. Ono and A. Chayahara, “Ni-defective value and resistivity of sputtered NiO films,” J. Magn. Magn. Mater, Vol. 226-230, pp. 1627-1628, 2001.
[34] H. Wu and L. S. Wang, “A study of nickel monoxide (NiO), nickel dioxide (ONiO), and Ni(O2) complex by anion photoelectron spectroscopy,” J. Chem. Phys., Vol. 107, pp. 16-21, 1997.
[35] G. P. Sykora and T. O. Mason, “Defect studies above 1 atm oxygen: NiO and CoO,” J. Am. Ceram. Soc., Vol. 23, pp. 45-53, 1987.
[36] B. Sasi, K. G. Gopchandran, P. K. Manoj and P. Koshy, “Preparation of trans-parent and semiconducting NiO films,” J. Vac. Sci. Technol., A, Vol. 68, pp. 149-154, 2003.
[37] H. L. Chen and Y. S. Yang, “Effect of crystallographic orientations on electrical properties of sputter-deposited nickel oxide thin films,” Thin Solid Films, Vol. 516, pp. 5590-5596, 2008.
[38] Š. Masys and V. Jonauskas, “Elastic properties of rhombohedral, cubic, and monoclinic phases of LaNiO3 by first principles calculations,” Comput. Mater. Sci., Vol. 108, pp. 153-159, 2015.
[39] H. J. Kim, J. W. Bae, J. S. Kim, K. S. Kim, Y. C. Jang, G. Y. Yeom and N. E. Lee, “Electrical, optical, and structural characteristics of ITO thin films by krypton and oxygen dual ion-beam assisted evaporation at room temperature,” Thin Solid Films, Vol. 377-378, pp. 115-121, 2000.
[40] W. C. Yeh and M. Matsumura, “Chemical vapor deposition of nickel oxide films from bis-π-cyclopentadienyl-nickel,” Jpn. J. Appl. Phys., Vol. 36, pp. 6884-6887, 1997.
[41] I. Hotový and D. Búc, “Characterization of NiO thin films deposited by reactive sputtering,” J. Vac. Sci. Technol. A, Vol. 50, pp. 41-44, 1998.
[42] W. Wang, Y. Liu, C. Xu, C. Zheng and G. Wang, “Synthesis of NiO nanorods by a novel simple precursor thermal decomposition approach,” Chem. Phys. Lett., Vol. 362, pp. 119-122, 2002.
[43] M. Guziewicz, J. Grochowski, M. Borysiewicz, E. Kaminska, J. Z. Domagala, W. Rzodkiewicz, B. S. Witkowski, K. Golaszewska, R. Kruszka, M. Ekielski and A. Piotrowska, “Electrical and optical properties of NiO films deposited by magnetron sputtering,” Opt. Appl., Vol. 9, pp. 431-440, 2011.
[44] M. Kitao, K. Izawa and S. Yamada, “Electrochromic properties of nickel oxide films prepared by introduction of hydrogen into sputtering atmosphere,” Sol. Energy Mater. Sol. Cells, Vol. 39, pp.115-122, 1995.
[45] B. Sasia, K.G. Gopchandrana, P. K. Manoja, P. Koshyb, P. P. Raob and V. K. Vaidyana, “Preparation of transparent and semiconducting NiO films,” Vac., Vol. 68, pp. 149-154, 2003.
[46] N. M. Ulmane, A. Kuzmin, I. Steins, J. Grabis, I. Sildos and M. Pärs, “Raman scattering in nanosized nickel oxide NiO,” J. Phys.: Conf. Ser., Vol. 93, pp.341-344, 2007.
[47] Y. Zhou, Y. Geng, D. Gu, W. Gu and Z. Jiang, “Effect of film thickness on the optical constants and optical absorption properties of NiOx thin films,” Physica B, Vol. 405, pp. 3875-3878, 2010.
[48] I. G. Austin and N. F. Mott, “Polarons in crystalline an non-crystalline materials,” Adv. Phys., Vol. 18, pp.41-102, 1969.
[49] H. Kawazoe, H. Yanagi, K. Ue and H. Hosono, “Transparent p-type conducting oxide: design and fabrication of p-n heterojunctions,” MRS Bull., Vol. 25, pp. 28-36, 2000.
[50] Z. P. He, Z. G. Ji, S. C. Zhao, C. Wang, K. Liu and Z. Z. Ye, “Characterization and eletro-chromic properties of CuxNi1-xO films prepared by sol-gel dip-coating,” Sol. Energy Mater. Sol. Cells, Vol. 80, pp. 226-230, 2006.
[51] M. Yang, Z. Shi, J. Feng, H. Pu, G. Li, J. Zhou and Q. Zhang, “Copper doped nickel oxide transparent p-type conductive thin films deposited by pulsed plasma deposition,” Thin Solid Films, Vol. 519, pp. 3021-3025, 2011.
[52] Y. A. K. Reddy, A. S. Reddy and P. S. Reddy, “Substrate Temperature Dependent Properties of Cu Dope NiO Films Deposited by DC Reactive Magnetron Sputtering,” J. Mater. Sci. Technol., Vol. 29, pp. 647-651, 2013.
[53] Y. A. K. Reddy, B. Ajitha, and P. S. Reddy, “Influence of thermal annealing on structural, morphological, optical and electrical properties of NiO–Cu composite thin films,” Mater. Express, Vol. 4, pp. 32-40, 2014.
[54] M. Shinoda, T. Nishide, Y. Sawada, M. Hosaka, and T. Matsumoto, ” Solid State Reactions in Cr2O3-ZnO Nanoparticles Synthesized by Triethanolamine Chemical Precipitation,” Jpn. J. Appl. Phys., Vol. 32, pp. 1584-1592 , 1993.
[55] M. M. El-Nahass, M. E. Ismail and M. El-Hagary, “Structural, optical and dis-persion energy parameters of nickel oxide nanocrystalline thin films prepared by electron beam deposition technique,” J. Alloys Compd, Vol. 646, pp. 937-945, 2015.
[56] J. Tauc, R. Griogorovici and A. Vaucu, “Optical properties and electronic struc-ture of amorphous germanium,” Phys. Status Solidi B, Vol. 15, pp. 627-637, 1966.
[57] 張梁興、凌永健, “二次離子質譜儀在微電子工業上的應用,” 電子發展月刊, Vol. 149, pp. 50-59, 1990.
[58] J. Keraudy, J. G. Mollejab, A. Ferreca, B. Corrazeb, M. R. Plouetb, A. Goulletb and P. Y. Jouanb, “Structural, morphological and electrical properties of nickel oxide thin films deposited by reactive sputtering,” Appl. Surf. Sci., Vol. 357, pp. 838-844, 2015.
[59] J. Pelleg, L. Z. Zevin and S. Lungo, “Reactive-sputter-deposited TiN films on glass substrates,” Thin Solid Films, Vol. 197, pp. 117-128, 1991.
[60] M. J. Hong, Y. C. Lin, L. C. Chao, P. H. Lin and B. R. Huang, “Cupric and cu-prous oxide by reactive ion beam sputter deposition and the photosensing prop-erties of cupric oxide metal–semiconductor–metal Schottky photodiodes,” Appl. Surf. Sci., Vol. 346, pp. 18–23, 2015.
[61] Z. Fang, E. Robin, E. R. Jiménez, A. Cros, F. Donatini, N. Mollard, J. Pernot and B. Daudin, “Si Donor Incorporation in GaN Nanowires,” Nano Lett., Vol. 15, pp. 6794-6801, 2015.
[62] E. R. Jiménez, A. Cros, S. M. Mascarós, Z. Fang and B. Daudin, “Phonon–plasmon coupling in Si doped GaN nanowires,” Mater. Sci. Semicond. Process., Vol. 55, pp. 63-66, 2016.