Journal of Sol-Gel Science and Technology

, Volume 77, Issue 2, pp 430–436 | Cite as

Thickness-dependent phase evolution and dielectric property of Hf0.5Zr0.5O2 thin films prepared with aqueous precursor

  • Yong Yan
  • Dayu Zhou
  • Chunxia Guo
  • Jin Xu
  • Xirui Yang
  • Hailong Liang
  • Fangyang Zhou
  • Shichao Chu
  • Xiaoying Liu
Original Paper


Hf0.5Zr0.5O2 thin films were prepared on silicon substrates by sol–gel method. The crystallization temperature, thickness, density, surface morphology, crystalline structure, and chemical bonding features of the films were investigated using TGA, DSC, XRR, AFM, GIXRD, and XPS techniques. The results showed that the crystallization temperature was 496 °C, the film surfaces were smooth and flat, and no pores and micro-cracks were discernable. The density increased significantly from 5.1 to 8.0 g/cm3 after annealing at 700 °C. The crystalline structure depends strongly on the film thickness. The tetragonal phase could be stabilized in Hf0.5Zr0.5O2 films thinner than 12.9 nm. An increase in the thickness led to a gradual appearance of the monoclinic phase, which ultimately became the dominant phase for films thicker than 46.1 nm. The results could be explained by the surface energy effect. Measured at 1 MV/cm, the leakage current density was about 3.5 × 10−6 A/cm2, further indicating high quality of the thin films derived from aqueous solution precursor.

Graphical Abstract


Hf0.5Zr0.5O2 thin films Aqueous precursor Phase transition Thickness dependence Dielectric property 



This work was supported by the National Natural Science Foundation of China (Grant No. NSFC 51272034) and the Open Research Fund of State Key Laboratory of Electronic Thin Films and Integrated Devices (UESTC) (No. KFJJ201101). The authors are responsible for the content of the paper.


  1. 1.
    Robertson J (2004) High dielectric constant oxides. Eur Phys J Appl Phys 28:265–291CrossRefGoogle Scholar
  2. 2.
    Choi JH, Mao Y, Chang JP (2011) Development of hafnium based high-k materials—a review. Mater Sci Eng R 72:97–136CrossRefGoogle Scholar
  3. 3.
    Akbar MS, Cho HJ, Choi R, Kang CS, Kang CY, Choi CH, Rhee SJ, Kim YH, Lee JC (2004) Optimized NH3 annealing process for high-quality HfSiON gate oxide. IEEE Electron Device Lett 25:465–467CrossRefGoogle Scholar
  4. 4.
    Tomida K, Kita K, Toriumi A (2006) Dielectric constant enhancement due to Si incorporation into HfO2. Appl Phys Lett 89:2902CrossRefGoogle Scholar
  5. 5.
    Park PK, Kang SW (2006) Enhancement of dielectric constant in HfO2 thin films by the addition of Al2O3. Appl Phys Lett 89:2905Google Scholar
  6. 6.
    Mereu B, Dimoulas A, Vellianitis G, Apostolopoulos G, Scholz R, Alexe M (2005) Interface trap density in amorphous La2Hf2O7/SiO2 high-k gate stacks on Si. Appl Phys A 80:253–257CrossRefGoogle Scholar
  7. 7.
    Müller J, Böscke TS, Schröder U, Reinicke M, Oberbeck L, Zhou D, Weinreich W, Kücher P, Lemberger M, Frey L (2009) Improved manufacturability of ZrO2 MIM capacitors by process stabilizing HfO2 addition. Microelectron Eng 86:1818–1821CrossRefGoogle Scholar
  8. 8.
    Aarik J, Aidla A, Kiisler AA, Uustare T, Sammelselg V (1999) Influence of substrate temperature on atomic layer growth and properties of HfO2 thin films. Thin Solid Films 340:110–116CrossRefGoogle Scholar
  9. 9.
    Aarik J, Aidla A, Mandar H, Uustare T, Kukli K, Schuisky M (2001) Phase transformations in hafnium dioxide thin films grown by atomic layer deposition at high temperatures. Appl Surf Sci 173:15–21CrossRefGoogle Scholar
  10. 10.
    Balog M, Schieber M, Patai S, Michman M (1972) Thin films of metal oxides on silicon by chemical vapor deposition with organometallic compounds. I. J Cryst Growth 17:298–301CrossRefGoogle Scholar
  11. 11.
    Williams PA, Jones AC, Tobin NL, Chalker PR, Taylor S, Marshall PA, Critchlow GW (2003) Growth of hafnium dioxide thin films by liquid-injection MOCVD using alkylamide and hydroxylamide precursors. Chem Vap Depos 9:309–314CrossRefGoogle Scholar
  12. 12.
    Jones AC, Chalker PR (2003) Some recent developments in the chemical vapour deposition of electroceramic oxides. J Phys D Appl Phys 36:R80CrossRefGoogle Scholar
  13. 13.
    Pereira L, Barquinha P, Fortunato E, Martins R (2005) Influence of the oxygen/argon ratio on the properties of sputtered hafnium oxide. Mater Sci Eng B118:210–213CrossRefGoogle Scholar
  14. 14.
    Hu H, Zhu C, Lu YF, Wu YH, Liew T, Li MF, Cho BJ, Choi WK, Yakovlev N (2003) Physical and electrical characterization of HfO2 metal–insulator–metal capacitors for Si analog circuit applications. J Appl Phys 94:551–557CrossRefGoogle Scholar
  15. 15.
    Jiang K, Anderson JT, Hoshino K, Li D, Wager JF, Keszler DA (2011) Low-energy path to dense HfO2 thin films with aqueous precursor. Chem Mater 23:945–952CrossRefGoogle Scholar
  16. 16.
    Zaharescu M, Teodorescu VS, Gartner M, Blanchin MG, Barau A, Anasescu M (2008) Correlation between the method of preparation and the properties of the sol–gel HfO2 thin films. J Non-Cryst Solids 354:409–415CrossRefGoogle Scholar
  17. 17.
    Wang KJ, Cheong KY (2008) Investigation of sol–gel derived HfO2 on 4H-SiC. Appl Surf Sci 254:1981–1985CrossRefGoogle Scholar
  18. 18.
    Shimizu H, Nemoto D, Ikeda M, Nishide T (2010) Characteristics of sol–gel-derived and crystallized HfO2 thin films dependent on sol solution. Jpn J Appl Phys 49:121502CrossRefGoogle Scholar
  19. 19.
    Müller J, Böscke TS, Schröder U, Mueller S, Bräuhaus D, Böttger U, Mikolajick T (2012) Ferroelectricity in simple binary ZrO2 and HfO2. Nano Lett 12:4318–4323CrossRefGoogle Scholar
  20. 20.
    Park MH, Kim HJ, Kim YJ, Lee W, Moon T, Hwang CS (2013) Evolution of phases and ferroelectric properties of thin Hf0.5Zr0.5O2 films according to the thickness and annealing temperature. Appl Phys Lett 102:242905CrossRefGoogle Scholar
  21. 21.
    Triyoso DH, Hegde RI, Schaeffer JK, Roan D, Tobin PJ, Samavedam SB, White JBE (2006) Impact of Zr addition on properties of atomic layer deposited HfO2. Appl Phys Lett 88:2901CrossRefGoogle Scholar
  22. 22.
    Shandalov M, Mclntyre PC (2009) Size-dependent polymorphism in HfO2 nanotubes and nanoscale thin films. J Appl Phys 106:084322CrossRefGoogle Scholar
  23. 23.
    Böscke TS, Hung PY, Kirsch PD, Quevedo-Lopez MA, Ramírez-Bon R (2009) Increasing permittivity in HfZrO thin films by surface manipulation. Appl Phys Lett 95:052904CrossRefGoogle Scholar
  24. 24.
    Garvie RC (1965) The occurence of metastable tetragonal zirconia as a crystalline size effect. J Phys Chem 69:1238–1243CrossRefGoogle Scholar
  25. 25.
    Wang C, Zinkevich M, Aldinger F (2006) The zirconia–hafnia system: DTA measurements and thermodynamic. J Am Ceram Soc 89:3751–3758CrossRefGoogle Scholar
  26. 26.
    Navrotsky A (2005) Thermochemical insights into refractory ceramic materials based on oxides with large tetravalent cations. J Mater Chem 15:1883–1890CrossRefGoogle Scholar
  27. 27.
    Brezesinski T, Smarsly B, Iimura KI, Grosso D, Boissière C, Amenitsch H, Sanchez C (2005) Self-assembly and crystallization behavior of mesoporous, crystalline HfO2 thin films: a model system for the generation of mesostructured Transition–Metal Oxides. Small 1:889–898CrossRefGoogle Scholar
  28. 28.
    Shimizu H, Nishide T (2012) Characterization of sol–gel-derived and crystallized HfO2, ZrO2, ZrO2–Y2O3 thin films on Si (001) wafers with high dielectric constant. In: Mastai Y (ed) Advances in crystallization processes, chap. 13. InTech, RijekaGoogle Scholar
  29. 29.
    Zhao Xinyuan, Vanderbilt David (2002) First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide. Phys Rev B 65:233106CrossRefGoogle Scholar
  30. 30.
    Wang ZJ, Kumagai T, Kokawa H, Tsuaur J, Ichiki M, Maeda R (2005) Crystalline phases, microstructures and electrical properties of hafnium oxide films deposited by sol–gel method. J Cryst Growth 281:452–457CrossRefGoogle Scholar
  31. 31.
    Yu JJ, Fang Q, Zhang JY, Wang ZM, Boyd IW (2003) Hafnium oxide layers derived by photo-assisted sol–gel processing. Appl Surf Sci 208:676–681CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Yong Yan
    • 1
  • Dayu Zhou
    • 1
    • 2
  • Chunxia Guo
    • 1
  • Jin Xu
    • 3
  • Xirui Yang
    • 1
  • Hailong Liang
    • 1
  • Fangyang Zhou
    • 1
  • Shichao Chu
    • 1
  • Xiaoying Liu
    • 1
  1. 1.Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams (Ministry of Education)Dalian University of TechnologyDalianChina
  2. 2.State Key Laboratory of Electronic Thin Films and Integrated DevicesUniversity of Electronic Science and Technology of ChinaChengduChina
  3. 3.Department of Electronic EngineeringDalian Neusoft University of InformationDalianChina

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