Journal of Electronic Materials

, Volume 44, Issue 10, pp 3677–3686 | Cite as

Molybdenum Oxides Deposited by Modulated Pulse Power Magnetron Sputtering: Stoichiometry as a Function of Process Parameters

  • Neil R. Murphy
  • Lirong Sun
  • John T. Grant
  • John G. Jones
  • Rachel Jakubiak
Article
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Accepted:

Abstract

Molybdenum oxide films were deposited using modulated pulse power magnetron sputtering (MPPMS) from a molybdenum target in a reactive environment where the flow rate of oxygen was varied from 0 sccm to 2.00 sccm. By varying the amount of reactive oxygen available during deposition, the composition of the films ranged from metallic Mo to fully stoichiometric MoO3, when the molybdenum target became poisoned, due to the formation of a dielectric surface oxide coating. Film compositions were verified using high energy resolution x-ray photoelectron spectroscopy. Target poisoning occurred at an oxygen flow rate of 1.25 sccm and reversed when the flow rate decreased to about 1.00 sccm. MoO3 films deposited via MPPMS had densities of 3.8 g cm−3, 81% of the density of crystalline α-MoO3 as determined by x-ray reflectivity (XRR). In addition, XRR and atomic force microscopy data showed sub-nanometer surface roughness values. From spectroscopic ellipsometry, the measured refractive index of the MoO3 films at 589 nm was 1.97 with extinction coefficient values <0.02 at wavelengths above the measured absorption edge of 506 nm (2.45 eV).

Keywords

Molybdenum oxide reactive magnetron sputtering MPPMS XPS MoO3 
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References

  1. 1.
    R. Sundararaman and C. Song, Ind. Eng. Chem. Res. 53, 1890 (2014).CrossRefGoogle Scholar
  2. 2.
    J.G. Choi and L. Thompson, Appl. Surf. Sci. 93, 143 (1996).CrossRefGoogle Scholar
  3. 3.
    I.E. Wachs, Catal. Today 27, 437 (1996).CrossRefGoogle Scholar
  4. 4.
    D.S. Kim, I.E. Wachs, and K. Segawa, J. Catal. 149, 268 (1994).CrossRefGoogle Scholar
  5. 5.
    T. He and J. Yao, J. Photochem. Photobiol. C 4, 125 (2003).CrossRefGoogle Scholar
  6. 6.
    S. Kubota, K. Kanomata, K. Momiyama, T. Suzuki, and F. Hirose, IEICE Trans. Electron. 96, 604 (2013).CrossRefGoogle Scholar
  7. 7.
    M. Zhang, Z. Chen, L. Xiao, B. Qu, and Q. Gong, J. Appl. Phys. 113, 113105 (2013).CrossRefGoogle Scholar
  8. 8.
    G. Nazri and G. Pistoia, Lithium Batteries: Science and Technology (New York: Springer, 2003), p. 92.CrossRefGoogle Scholar
  9. 9.
    S. Mohamed, O. Kappertz, J. Ngaruiya, T.L. Pedersen, R. Drese, and M. Wuttig, Thin Solid Films 429, 135 (2003).CrossRefGoogle Scholar
  10. 10.
    J. Besenhard, J. Heydecke, and H. Fritz, Solid State Ion. 6, 215 (1982).CrossRefGoogle Scholar
  11. 11.
    J. Besenhard, J. Heydecke, E. Wudy, H. Fritz, and W. Foag, Solid State Ion. 8, 61 (1983).CrossRefGoogle Scholar
  12. 12.
    X. Haitao and Z. Xiang, J. Appl. Phys. 114, 244505 (2013).CrossRefGoogle Scholar
  13. 13.
    P. Qin, G. Fang, W. Ke, F. Cheng, Q. Zheng, J. Wan, H. Lei, and X. Zhao, J. Mater. Chem. A 110, 63 (2014).Google Scholar
  14. 14.
    Y. Sun, J. Wang, B. Zhao, R. Cai, R. Ran, and Z. Shao, J. Mater. Chem. A 1, 4736 (2013).CrossRefGoogle Scholar
  15. 15.
    H. Simchi, B.E. McCandless, T. Meng, and W.N. Shafarman, J. Appl. Phys. 115, 033514 (2014).CrossRefGoogle Scholar
  16. 16.
    M. Ferroni, V. Guidi, G. Martinelli, P. Nelli, M. Sacerdoti, and G. Sberveglieri, Thin Solid Films 307, 148 (1997).CrossRefGoogle Scholar
  17. 17.
    E. Comini, L. Yubao, Y. Brando, and G. Sberveglieri, Chem. Phys. Lett. 407, 368 (2005).CrossRefGoogle Scholar
  18. 18.
    D. Mutschall, K. Holzner, and E. Obermeier, Sens. Actuators B 36, 320 (1996).CrossRefGoogle Scholar
  19. 19.
    W. Moshier, G. Davis, and G. Cote, J. Electrochem. Soc. 136, 356 (1989).CrossRefGoogle Scholar
  20. 20.
    V. Nirupama, K. Gunasekhar, B. Sreedhar, and S. Uthanna, Curr. Appl. Phys. 10, 272 (2010).CrossRefGoogle Scholar
  21. 21.
    T.S. Sian and G. Reddy, Sol. Energy Mater. Sol. Cells 82, 375 (2004).CrossRefGoogle Scholar
  22. 22.
    M. Al-Kuhaili, S. Durrani, I. Bakhtiari, and A. Al-Shukri, Opt. Commun. 283, 2857 (2010).CrossRefGoogle Scholar
  23. 23.
    F. Werfel and E. Minni, J. Phys. C 16, 6091 (2000).CrossRefGoogle Scholar
  24. 24.
    D.O. Scanlon, G.W. Watson, D. Payne, G. Atkinson, R. Egdell, and D. Law, J. Phys. Chem. C 114, 4636 (2010).CrossRefGoogle Scholar
  25. 25.
    O. Marin-Flores, L. Scudiero, and S. Ha, Surf. Sci. 603, 2327 (2009).CrossRefGoogle Scholar
  26. 26.
    J. Horkans and M. Shafer, J. Electrochem. Soc. 124, 1202 (1977).CrossRefGoogle Scholar
  27. 27.
    Y. Shi, B. Guo, S.A. Corr, Q. Shi, Y. Hu, K.R. Heier, L. Chen, R. Seshadri, and G.D. Stucky, Nano Lett. 9, 4215 (2009).CrossRefGoogle Scholar
  28. 28.
    Y. Sun, X. Hu, C.Y. Jimmy, Q. Li, W. Luo, L. Yuan, W. Zhang, and Y. Huang, Energy Environ. Sci. 4, 2870 (2011).CrossRefGoogle Scholar
  29. 29.
    Y. Sun, X. Hu, W. Luo, and Y. Huang, ACS Nano 5, 7100 (2011).CrossRefGoogle Scholar
  30. 30.
    Y. Xu, R. Yi, B. Yuan, X. Wu, M. Dunwell, Q. Lin, L. Fei, S. Deng, P. Andersen, and D. Wang, J. Phys. Chem. Lett. 3, 309 (2012).CrossRefGoogle Scholar
  31. 31.
    H. Zhang, K. Wang, X. Wu, Y. Jiang, Y. Zhai, C. Wang, X. Wei, and J. Chen, Adv. Funct. Mater. 11, 1328 (2014).Google Scholar
  32. 32.
    H. Martínez, J. Torres, M. Rodríguez-García, and L.L. Carreño, Physica B 407, 3199 (2012).CrossRefGoogle Scholar
  33. 33.
    H. Martínez, J. Torres, L. López-Carreño, and M. Rodríguez-García, J. Supercond. Nov. Magn. 26, 2485 (2013).CrossRefGoogle Scholar
  34. 34.
    A. Bouzidi, N. Benramdane, H. Tabet-Derraz, C. Mathieu, B. Khelifa, and R. Desfeux, Mater. Sci. Eng. B 97, 5 (2003).CrossRefGoogle Scholar
  35. 35.
    S. Chuang, C. Battaglia, A. Azcatl, S. McDonnell, J.S. Kang, X. Yin, M. Tosun, R. Kapadia, H. Fang, and R.M. Wallace, Nano Lett. 14, 1337 (2014).CrossRefGoogle Scholar
  36. 36.
    C. Battaglia, X. Yin, M. Zheng, I.D. Sharp, T.L. Chen, A. Azcatl, S. McDonell, C. Carraro, R. Maboudian, and R.M. Wallace, Nano Lett. 14, 967 (2014).CrossRefGoogle Scholar
  37. 37.
    C. Ramana, V. Atuchin, L. Pokrovsky, U. Becker, and C. Julien, J. Vac. Sci. Technol. A 25, 1166 (2007).CrossRefGoogle Scholar
  38. 38.
    C. Ramana and C. Julien, Chem. Phys. Lett. 428, 114 (2006).CrossRefGoogle Scholar
  39. 39.
    S. Sunu, E. Prabhu, V. Jayaraman, K. Gnanasekar, and T. Gnanasekaran, Sens. Actuators B 94, 189 (2003).CrossRefGoogle Scholar
  40. 40.
    N. Miyata and S. Akiyoshi, J. Appl. Phys. 58, 1651 (1985).CrossRefGoogle Scholar
  41. 41.
    M. Rouhani, Y.L. Foo, J. Hobley, J. Pan, G.S. Subramanian, X. Yu, A. Rusydi, and S. Gorelik, Appl. Surf. Sci. 273, 150 (2013).CrossRefGoogle Scholar
  42. 42.
    J.-. Faou, E. Barthel, and S.Y. Grachev, Thin Solid Films 527, 222 (2013).CrossRefGoogle Scholar
  43. 43.
    V. Nirupama and S. Uthanna, J. Mater. Sci. 21, 45 (2010).Google Scholar
  44. 44.
    J. Lin, W.D. Sproul, J.J. Moore, S. Lee, and S. Myers, Surf. Coat. Technol. 205, 3226 (2011).CrossRefGoogle Scholar
  45. 45.
    L. Meng, T. Cho, S. Jung, and D. Ruzic, IEEE ICOPS 1, 1 (2011).Google Scholar
  46. 46.
    M. Hála, J. Čapek, O. Zabeida, J. Klemberg-Sapieha, and L. Martinu, J. Phys. D 45, 055204 (2012).CrossRefGoogle Scholar
  47. 47.
    J. Lin, W.D. Sproul, J.J. Moore, Z. Wu, S. Lee, R. Chistyakov, and B. Abraham, JOM 63, 48 (2011).CrossRefGoogle Scholar
  48. 48.
    J. Lin, J.J. Moore, W.D. Sproul, S.L. Lee, and J. Wang, IEEE Trans. Plasma Sci. 38, 3071 (2010).CrossRefGoogle Scholar
  49. 49.
    J. Lin, J. Moore, W. Sproul, B. Mishra, J. Rees, Z. Wu, R. Chistyakov, and B. Abraham, Surf. Coat. Technol. 203, 3676 (2009).CrossRefGoogle Scholar
  50. 50.
    B. Liebig, N.S.J. Braithwaite, P. Kelly, R. Chistyakov, B. Abraham, and J. Bradley, Surf. Coat. Technol. 205, S312 (2011).CrossRefGoogle Scholar
  51. 51.
    K. Sarakinos, J. Alami, and M. Wuttig, J. Phys. D 40, 2108 (2007).CrossRefGoogle Scholar
  52. 52.
    S. Konstantinidis, J. Dauchot, and M. Hecq, Thin Solid Films 515, 1182 (2006).CrossRefGoogle Scholar
  53. 53.
    V. Kouznetsov, K. Macák, J.M. Schneider, U. Helmersson, and I. Petrov, Surf. Coat. Technol. 122, 290 (1999).CrossRefGoogle Scholar
  54. 54.
    D. Depla and R. De Gryse, Surf. Coat. Technol. 183, 184 (2004).CrossRefGoogle Scholar
  55. 55.
    D. Guttler, B. Abendroth, R. Grotzschel, W. Moller, and D. Depla, Appl. Phys. Lett. 85, 6134 (2004).CrossRefGoogle Scholar
  56. 56.
    T. Lange, W. Njoroge, H. Weis, M. Beckers, and M. Wuttig, Thin Solid Films 365, 82 (2000).CrossRefGoogle Scholar
  57. 57.
    D. Depla and R. De Gryse, Surf. Coat. Technol. 183, 184 (2004).CrossRefGoogle Scholar
  58. 58.
    W.D. Sproul, J. Lin, and J.J. Moore, SVC Spring Bulletin 28, 1 (2009).Google Scholar
  59. 59.
    S. Berg and T. Nyberg, Thin Solid Films 476, 215 (2005).CrossRefGoogle Scholar
  60. 60.
    J. Lin, J.J. Moore, W.D. Sproul, B. Mishra, Z. Wu, and J. Wang, Surf. Coat. Technol. 204, 2230 (2010).CrossRefGoogle Scholar
  61. 61.
    D. Depla and R. De Gryse, Surf. Coat. Technol. 183, 190 (2004).CrossRefGoogle Scholar
  62. 62.
    D. Depla, S. Heirwegh, S. Mahieu, J. Haemers, and R. De Gryse, J. Appl. Phys. 101, 013301 (2007).CrossRefGoogle Scholar
  63. 63.
    N. Fairley, Casa Software Ltd CasaXPS 2.3.16 (1999–2011).Google Scholar
  64. 64.
    S. Dushman, Rev. Sci. Instrum. 20, 139 (1949).CrossRefGoogle Scholar
  65. 65.
    A. Phelps and Z.L. Petrovic, Plasma Sources Sci. Technol. 8, R21 (1999).CrossRefGoogle Scholar
  66. 66.
    J. Alami, P. Persson, D. Music, J. Gudmundsson, J. Bohlmark, and U. Helmersson, J. Vac. Sci. Technol. A 23, 278 (2005).CrossRefGoogle Scholar
  67. 67.
    W.D. Sproul, D.J. Christie, and D.C. Carter, Thin Solid Films 491, 1 (2005).CrossRefGoogle Scholar
  68. 68.
    V. Nirupama, M.C. Sekhar, T. Subramanyam, and S. Uthanna, J. Phys. 208, 012101 (2010).Google Scholar
  69. 69.
    J.F. Moulder, J. Chastain, and R.C. King, Handbook of X-ray Photoelectron Spectroscopy: A Reference Book of Standard Spectra for Identification and Interpretation of XPS Data (Eden Prairie, MN: Physical Electronics, 1995), p. 65.Google Scholar
  70. 70.
    C.R. Clayton and Y.C. Lu, Surf. Interface Anal. 14, 66 (1989).CrossRefGoogle Scholar
  71. 71.
    C.V. Ramana, V.V. Atuchin, V. Kesler, V. Kochubey, L. Pokrovsky, V. Shutthanandan, U. Becker, and R.C. Ewing, Appl. Surf. Sci. 253, 5368 (2007).CrossRefGoogle Scholar
  72. 72.
    Y.C. Liu, J.H. Hsieh, and S.K. Tung, Thin Solid Films 510, 32 (2006).CrossRefGoogle Scholar
  73. 73.
    J.I. Pankove, Absorption (New York: Dover Publications, 1971), p. 34.Google Scholar
  74. 74.
    C.G. Granqvist, Handbook of Inorganic Electrochromic Materials (New York: Elsevier Science, 1995), p. 217.Google Scholar
  75. 75.
    B.W. Faughnan and R.S. Crandall, Appl. Phys. Lett. 31, 834 (1977).CrossRefGoogle Scholar
  76. 76.
    M.A.P.B. Barna, Thin Solid Films 317, 27 (1998).CrossRefGoogle Scholar
  77. 77.
    I. Petrov, P. Barna, L. Hultman, and J. Greene, J. Vac. Sci. Technol. A 21, S117 (2003).CrossRefGoogle Scholar

Copyright information

© The Minerals, Metals & Materials Society (outside the USA) 2015

Authors and Affiliations

  • Neil R. Murphy
    • 1
  • Lirong Sun
    • 1
    • 2
  • John T. Grant
    • 1
    • 3
  • John G. Jones
    • 1
  • Rachel Jakubiak
    • 1
  1. 1.Air Force Research Laboratory, Materials and Manufacturing DirectorateWright-Patterson Air Force Base (WPAFB)DaytonUSA
  2. 2.General Dynamics Information TechnologyDaytonUSA
  3. 3.Research InstituteUniversity of DaytonDaytonUSA

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