Skip to main content
SpringerLink
Log in

Characteristics of hafnium oxide grown on silicon by atomic-layer deposition using tetrakis(ethylmethylamino)hafnium and water vapor as precursors

  • Published:
Journal of Materials Research Aims and scope Submit manuscript

Abstract

The growth of HfO2 thin films on a HF-dipped p-Si(100) substrate at 200 °C by atomic-layer deposition (ALD) using Hf[N(C2H5)(CH3)]4 and H2O vapor as precursors is demonstrated. Uniform HfO2 thin films are obtained on a 4-in. silicon wafer, and the energy-band gap and band offset are determined by x-ray photoelectron spectroscopy analysis. The as-deposited HfO2 thin film is amorphous and able to crystallize at 500 ~ 600 °C with only the monoclinic phase. As for the electrical performance of Au–Ti–HfO2–Si metal oxide semiconductor capacitors, a dielectric constant of ~17.8 and an equivalent oxide thickness value of ~1.39 nm are obtained from the 40-cycle ALD film after annealing at 500 °C. In addition, the breakdown field is in the range of 5 ~ 5.5 MV/cm, and the fixed charge density is on the order of 1012 cm−2, depending on the annealing temperatures. The interface quality of HfO2 thin films on silicon is satisfactory with an interface-trap charge density of ~3.7 × 1011 cm−2 eV−1.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

FIG. 1
FIG. 2
FIG. 3
FIG. 4
FIG. 5
FIG. 6
FIG. 7
FIG. 8
FIG. 9
FIG. 10

Similar content being viewed by others

References

  1. B. Cheng, M. Cao, R. Rao, A. Inani, P. Vande Voorde, W.M. Greene, J.M.C Stork, Z. Yu, P.M. Zeitzoff J.C.S. Woo: The impact of high-κ gate dielectrics and metal gate electrodes on sub-100 nm MOSFETs. IEEE Trans. Electron Devices 46(7), 1537 1999

    Article  Google Scholar 

  2. R.A. McKee, F.J. Walker M.F. Chisholm: Crystalline oxides on silicon: The first five monolayers. Phys. Rev. Lett. 81, 3014 1998

    Article  CAS  Google Scholar 

  3. K. Eisenbeiser, J.M. Finder, Z. Yu, J. Ramdani, J.A. Curless, A.A. Hallmark, R. Droopad, W.J. Ooms, L. Slame, S. Bradshaw C.D. Overgaard: Field effect transistors with SrTiO3 gate dielectric on Si. Appl. Phys. Lett. 76, 1324 2000

    Article  CAS  Google Scholar 

  4. L. Kang, K. Onishi, Y. Jeon, B.H. Lee, C. Kang, W.-J. Qi, R. Nieh, S. Gopalan, R. Choi J.C. Lee: MOSFET devices with polysilicon on single-layer HfO2 high-K dielectrics. Tech. Dig. Int. Electron Devices Meet. 35, 2000

  5. K.J. Choi, J.B. Park S.G. Yoon: Control of the interfacial layer thickness in hafnium oxide gate dielectric grown by PECVD. J. Electrochem. Soc. 150(4), F75 2005

    Google Scholar 

  6. G.D. Wilk, R.M. Wallace J.M. Anthony: High-κ gate dielectrics: Current status and materials properties considerations. J. Appl. Phys. 89, 5243 2001

    Article  CAS  Google Scholar 

  7. J. Schaeffer, N.V. Edwards, R. Liu, D. Roan, A.B. Hradsky, R. Gregory, J. Kulik, E. Duda, L. Contreras, J. Christiansen, S. Zollner, P. Tobin, B-Y. Nguyen, A.R. Nieh, A.M. Ramon, R. Rao, R. Hegde, R. Rai, J. Baker S. Voight: HfO2 gate dielectrics deposited via tetrakis diethylamido hafnium. J. Electrochem. Soc. 150(4), F67 2003

    Article  Google Scholar 

  8. T. Suntola J. Antson: Method for producing compound thin films. U.S. Patent No. 4058430, Nov. 15, 1977

    Google Scholar 

  9. J. Aarik, A. Aidla, A. Kikas, T. Käämbre, R. Rammula, P. Ritslaid, T. Uustare V. Sammelselg: Effects of precursors on nucleation in atomic layer deposition of HfO2. Appl. Surf. Sci. 230, 292 2004

    Article  CAS  Google Scholar 

  10. K. Forsgren, A. Hårsta, J. Aarik, A. Aidla, J. Westlinder J. Olsson: Deposition of HfO2 thin films in HfI4-based processes. J. Electrochem. Soc. 149, F139 2002

    Article  CAS  Google Scholar 

  11. H.S. Chang, S-K. Baek, H. Park, H. Hwang, J.H. Oh, W.S. Shin, J.H. Yeo, K.H. Hwang, S.W. Nam, H.D. Lee, C.L. Song, D.W. Moon M-H. Cho: Electrical and physical properties of HfO2 deposited via ALD using Hf(OtBu)4 and ozone atop Al2O3. Electrochem. Solid-State Lett. 7(6), F42 2004

    Article  Google Scholar 

  12. W. Cho, K-S. An, T-M. Chung, C.G. Kim, B-S. So, Y-H. You, J-H. Hwang, D. Jung Y. Kim: ALD of hafnium dioxide thin films using the new alkoxide precursor hafnium 3-methyl-3-pentoxide, Hf(mp)4. Chem. Vap. Deposition 12, 665 2006

    Article  CAS  Google Scholar 

  13. S. Choi, J. Koo, H. Jeon Y. Kim: Plasma-enhanced atomic-layer deposition of a HfO2 gate dielectric. J. Korean Phys. Soc. 44, 35 2004

    CAS  Google Scholar 

  14. M. Cho, D.S. Jeong, J. Park, H.B. Park, S.W. Lee, T.J. Park, C.S. Hwang, G.H. Jang J. Jeong: Comparison between atomic-layer-deposited HfO2 films using O3 or H2O oxidant and Hf[N(CH3)2]4 precursor. Appl. Phys. Lett. 85, 5953 2004

    Article  CAS  Google Scholar 

  15. X. Liu, S. Ramanathan, A. Longdergan, A. Srivastava, E. Lee, T.E. Seidel, J.T. Barton, D. Pang R.G. Gordon: ALD of hafnium oxide thin films from tetrakis(ethylmethylamino)hafnium and ozone. J. Electrochem. Soc. 152, G213 2005

    Article  CAS  Google Scholar 

  16. Y. Kim, J. Koo, J. Han, S. Choi, H. Jeon C. Park: Characteristics of ZrO2 gate dielectric deposited using Zr t–butoxide and Zr(NEt2)4 precursors by plasma enhanced atomic layer deposition method. J. Appl. Phys. 92, 5443 2002

    Article  CAS  Google Scholar 

  17. M.L. Huang, Y.C. Chang, C.H. Chang, Y.J. Lee, P. Chang, J. Kwo, T.B. Wu M. Hong: Surface passivation of III-V compound semiconductors using atomic-layer-deposition-grown Al2O3.Appl. Phys. Lett. 87, 252104 2005

    Article  Google Scholar 

  18. J. Robertson P.W. Peacock: Electronic structure and band offsets of high-dielectric constant gate oxides, in High-k Gate Dielectrics edited by Michel Houssa Institute of Physics Publishing, Beijing 2004 P372–P396

    Google Scholar 

  19. M.L. Huang, Y.C. Chang, C.H. Chang, T.D. Lin, J. Kwo, T.B. Wu, M. Hong: Energy-band parameters of atomic-layer-deposition Al2O3/InGaAs heterostructure. Appl. Phys. Lett. 89, 012903 2006

    Article  Google Scholar 

  20. H. Itokawa, T. Maruyama, S. Miyazaki M. Hirose: Determination of bandgap and energy band alignment for high-dielectric-constant gate insulators using high-resolution x-ray photoelectron spectroscopy, in Int. Conf. on Solid State Devices and Materials, Tokyo Japan Society of Applied Physics, Japan 1999 158

  21. P.W. Peacock J. Robertson: Band offsets and Schottky barrier heights of high-dielectric constant oxides. J. Appl. Phys. 92, 4712 2002

    Article  CAS  Google Scholar 

  22. S. Sayan, E. Grafunkel S. Suzer: Soft x-ray photoemission studies of the HfO2/SiO2/Si system. Appl. Phys. Lett. 80, 2135 2002

    Article  CAS  Google Scholar 

  23. R. Puthenkovilakam J.P. Chang: An accurate determination of barrier heights at the HfO2/Si interfaces. J. Appl. Phys. 96, 2701 2004

    Article  CAS  Google Scholar 

  24. K. Kukli, M. Ritala, T. Sajavaara, J. Keinonen M. Leskela: Comparison of hafnium oxide films grown by atomic layer deposition from iodide and chloride precursors. Thin Solid Films 416, 72 2002

    Article  CAS  Google Scholar 

  25. K. Kukli, M. Ritala, J. Lu, A. Harsta M. Leskela: Properties of HfO2 thin films grown by ALD from hafnium tetrakisethylmethylamide and water. J. Electrochem. Soc. 151, F189 2004

    Article  CAS  Google Scholar 

  26. J.R. Hauser K. Ahmed: Characterization of ultrathin oxides using electrical C–V and I–V measurements, in Characterization and Metrology for ULSI Technology 1998 235

    Google Scholar 

  27. M. Houssa, V.V. Afanas’ev, A. Stesmans M.M. Heyns: Variation in the fixed charge density of SiOx/ZrO2 gate dielectric stacks during postdeposition oxidation. Appl. Phys. Lett. 77, 1885 2000

    Article  CAS  Google Scholar 

  28. W.F.A. Besling, E. Young, T. Conard, C. Zhao, R. Carter, W. Vandervorst, M. Caymax, S. De Gendt, M. Heyns, J. Maes, M. Tuominen S. Haukka: Characterisation of ALCVD Al2O3–ZrO2 nanolaminates, link between electrical and structural properties. J. Non-Cryst. Solids 303, 123 2002

    Article  CAS  Google Scholar 

  29. M.M. Frank, Y.J. Chabal G.D. Wilk: Nucleation and interface formation mechanisms in atomic layer deposition of gate oxides. Appl. Phys. Lett. 82, 4758 2003

    Article  CAS  Google Scholar 

  30. E.H. Nicollian A. Goetzberger: The Si-SiO2 interface electrical properties as determined by the metal-insulator-silicon conductance technique. Bell Syst. Tech. J. 46, 1055 1967

    Article  CAS  Google Scholar 

  31. E.H. Nicollian J.R. Brews: MOS Physics and Technology Wiley, New York 1981

    Google Scholar 

  32. T.P. Ma R.C. Barker: Surface-state spectra from thick-oxide MOS tunnel junctions. Solid-State Electron. 17, 913 1974

    Article  CAS  Google Scholar 

  33. S. Kar W.E. Dahlke: Interface states in MOS structures with 20-40 Å thick SiO2 films on nondegenerate Si. Solid-State Electron. 15, 221 1972

    Article  CAS  Google Scholar 

  34. E.M. Vogel, W. Kirklen Henson, C.A. Richter J.S. Suehle: Limitations of conductance to the measurement of the interface state density of MOS capacitors with tunneling gate dielectrics. IEEE Trans. Electron Devices 47(3), 601 2000

    Article  Google Scholar 

  35. Y-K. Chiou, C-H. Chang, C-C. Wang, K-Y. Lee, T-B. Wu, R. Kwo M. Hong: Effect of Al incorporation in the thermal stability of atomic-layer-deposited HfO2 for gate dielectric applications. J. Electrochem. Soc. 154, G99 2007

    Article  CAS  Google Scholar 

Download references

ACKNOWLEDGMENTS

The authors gratefully acknowledge the support from the Ministry of Economic Affairs (under Contract No. 95-EC-17-A-01-S1-047) and the National Science Council (under Contract No. NSC95-2120-M-007-005), Taiwan, Republic of China.

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan

    Yan-Kai Chiou, Che-Hao Chang & Tai-Bor Wu

Authors
  1. Yan-Kai Chiou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Che-Hao Chang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tai-Bor Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Tai-Bor Wu.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chiou, YK., Chang, CH. & Wu, TB. Characteristics of hafnium oxide grown on silicon by atomic-layer deposition using tetrakis(ethylmethylamino)hafnium and water vapor as precursors. Journal of Materials Research 22, 1899–1906 (2007). https://doi.org/10.1557/jmr.2007.0242

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/jmr.2007.0242

Search

Navigation