Dielectric property and self-repairing capability of silicon and titanium co-doped amorphous alumina thin films prepared by sol–gel technology

  • Qian Feng
  • Manwen Yao
  • Zhen Su
  • Xi Yao


In this article, (Al1−0.02−xSi0.02Tix)2Oy (x = 0.2, 0.9 and 2%) thin films were prepared on Pt/Ti/SiO2/Si substrates using sol–gel technique. The dielectric properties of undoped and Si–Ti co-doped Al2O3 thin films were investigated. The leakage current of (Al0.971Si0.02Ti0.009)2Oy thin film is reduced by 2 orders of magnitude compared with Al2O3 film. Meanwhile, the modified sample exhibits the ultrahigh energy density of 14.01 J/cm3 under the breakdown strength of 647 MV/m, which is an enhancement of 11.26 J/cm3 over that of the undoped Al2O3 film. The improvement of dielectric properties is ascribed to the forming of Al–O–Si, Al–O–Ti bonds and the anodic oxidation of Ti3+, which could strengthen the stability of Al2O3 structure and self-repair the defects of the films under applied electric field. Another reason is that cation vacancies generated by Si–Ti co-doping could effectively prevent the formation of oxygen vacancies and decrease the breakdown probability of the films. This work provides a promising route to dielectric thin films materials for electrical energy storage applications.



This work is supported by the National Natural Science Foundation of China (Grant No. 61761136004) and the Ministry of Science and Technology of China through 973-project (Grant No. 2015CB654601). 

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    C. Liu, F. Li, L. Ma, H. Cheng, Advanced materials for energy storage. Adv. Mater. 22, 28–62 (2010)CrossRefGoogle Scholar
  2. 2.
    Z. Xie, Z. Yue, B. Peng, J. Zhang, C. Zhao, X. Zhang, G. Ruehl, L. Li, Large enhancement of the recoverable energy storage density and piezoelectric response in relaxor-ferroelectric capacitors by utilizing the seeding layers engineering. Appl. Phys. Lett. 106, 202901 (2015)CrossRefGoogle Scholar
  3. 3.
    Y. Wang, J. Cui, Q. Yuan, Y. Niu, Y. Bai, H. Wang, Significantly enhanced breakdown strength and energy density in sandwich-structured barium titanate/poly(vinylidene fluoride) nanocomposites. Adv. Mater. 27, 6658–6663 (2015)CrossRefGoogle Scholar
  4. 4.
    H. Zhu, Z. Liu, F. Wang (2017) Improved dielectric properties and energy storage density of poly(vinylidene fluoride-cotrifluoroethylene-co-chlorotrifluoroethylene) composite films with aromatic polythiourea. J. Mater. Sci. CrossRefGoogle Scholar
  5. 5.
    X. Zhang, Y. Shen, B. Xu, Q. Zhang, L. Gu, J. Jiang, J. Ma, Y. Lin, C.W. Nan, Giant energy density and improved discharge efficiency of solution-processed polymer nanocomposites for dielectric energy storage. Adv. Mater. 28, 2055–2061 (2016)CrossRefGoogle Scholar
  6. 6.
    Q.K. Muhammad, M. Waqar, M.A. Rafiq, Structural, dielectric, and impedance study of ZnO-doped barium zirconium titanate (BZT) ceramics. J. Mater. Sci. 51, 1–11 (2016). CrossRefGoogle Scholar
  7. 7.
    Z. Su, M. Yao, F. Li, Y. Peng, Q. Feng, X. Yao (2017) Microstructural transitions and dielectric properties of boron-doped amorphous alumina thin film. J. Mater. Sci. CrossRefGoogle Scholar
  8. 8.
    M. Yao, Z. Su, P. Zou, J. Chen, F. Li, Q. Feng, X. Yao, Dielectric properties under high electric field for silicon doped alumina thin film with glass-like structure derived from sol-gel process. J. Alloys Compd. 690, 249–255 (2017)CrossRefGoogle Scholar
  9. 9.
    A.B. Khatibani, S.M. Rozati, Growth and molarity effects on properties of alumina thin films obtained by spray pyrolysis. Mater. Sci. Semicond. Process. 18, 80–87 (2014)CrossRefGoogle Scholar
  10. 10.
    P. Katiyar, C. Jin, R.J. Narayan, Electrical properties of amorphous aluminum oxide thin films. Acta Mater. 53, 2617–2622 (2005)CrossRefGoogle Scholar
  11. 11.
    Z. Pan, J. Zhai, B. Shen, Multilayer hierarchical interfaces with high energy density in polymer nanocomposites composed of BaTiO3@TiO2@Al2O3 nanofibers. J. Mater. Chem. A 5, 15217–15226 (2017)CrossRefGoogle Scholar
  12. 12.
    M. Yao, Y. Peng, R. Xiao, Q. Li, X. Yao, Enhanced self-repairing capability of sol-gel derived SrTiO3/nano Al2O3 composite films. Appl. Phys. Lett. 109, 092904 (2016)CrossRefGoogle Scholar
  13. 13.
    Y. Peng, M. Yao, R. Xiao, X. Yao, Electrical properties of sol-gel derived Mg-doped Al2O3 films. J. Mater. Sci. Mater. Electron. 27, 11495–11501 (2016)CrossRefGoogle Scholar
  14. 14.
    M. Yao, R. Xiao, Y. Peng, J. Chen, B. Hu, X. Yao, The influence of titanium doping on the electric properties of amorphous alumina films prepared by sol-gel technology. J. Sol-Gel. Sci. Technol. 74, 39–44 (2015)CrossRefGoogle Scholar
  15. 15.
    M. Yao, P. Zou, Z. Su, J. Chen, X. Yao, The influence of yttrium on leakage current and dielectric properties of amorphous Al2O3 thin film derived by sol-gel. J Mater Sci Mater Electron 27, 7788–7794 (2016)CrossRefGoogle Scholar
  16. 16.
    P.K. Sharma, M.H. Jilavi, D. Burgard, R. Nass, H. Schmidt, Hydrothermal synthesis of nanosize α-Al2O3 from seeded aluminum hydroxide. J. Am. Ceram. Soc. 81, 2732–2734 (1998)CrossRefGoogle Scholar
  17. 17.
    V.A. Zeitler, C.A. Brown, The infrared spectra of some Ti-O-Si, Ti-O-Ti and Si-O-Si compounds. J. Phys. Chem. C 61, 1174–1177 (1957)CrossRefGoogle Scholar
  18. 18.
    L. Stoch, M. Środa, Infrared spectroscopy in the investigation of oxide glasses structure. J. Mol. Struct. 511–512, 77–84 (1999)CrossRefGoogle Scholar
  19. 19.
    T.M.H. Costa, M.R. Gallas, E.V. Benvenutti, J.A.H. Jornada, Study of nanocrystalline γ-Al2O3 produced by high-pressure compaction. J. Phys. Chem. B 103, 4278–4284 (1999)CrossRefGoogle Scholar
  20. 20.
    NIST X-ray photoelectron spectroscopy database (2012),
  21. 21.
    S. Seal, A. Kale, K.B. Sundaram, D. Jimenez, Oxidation and chemical state analysis of polycrystalline magnetron sputtered (Ti, Al)N films at ambient and liquid N2 temperatures. J. Vac. Sci. Technol. A 18, 1571 (2000)CrossRefGoogle Scholar
  22. 22.
    F.H. ElBatal, M.A. Marzouk, H.A. ElBatal, Optical and crystallization studies of titanium dioxide doped sodium and potassium silicate glasses. J. Mol. Struct. 1121, 54–59 (2016)CrossRefGoogle Scholar
  23. 23.
    M. Yao, J. Chen, Z. Su, Y. Peng, P. Zou, X. Yao, Anodic oxidation in aluminum electrode by using hydrated amorphous aluminum oxide film as solid electrolyte under high electric field. ACS Appl. Mater. Interfaces 8, 11100–11107 (2016)CrossRefGoogle Scholar
  24. 24.
    D. Liu, S.J. Clark, J. Robertson, Oxygen vacancy levels and electron transport in Al2O3. Appl. Phys. Lett. 96, 032905 (2010)CrossRefGoogle Scholar
  25. 25.
    K. Ganesan, S. Ilango, M. Shanmugam, M.F. Baroughi, M. Kamruddin, A.K. Tyagi, Pre- and post-breakdown electrical studies in ultrathin Al2O3 films by conductive atomic force microscopy. Curr. Appl. Phys. 13, 1865–1869 (2013)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Functional Materials Research Laboratory, School of Materials Science and EngineeringTongji UniversityShanghaiChina

Personalised recommendations