SpringerLink
Log in

Piezoelectric, ferroelectric Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films with compositions around the morphotropic phase boundary prepared by a sol-gel process of reduced thermal budget

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

Abstract

Single perovskite polycrystalline Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN-PT) thin films with PMN to PT ratios around the morphotropic phase boundary composition (070PMN-0.30PT, 0.65PMN-0.35PT, and 0.60PMN-0.40PT) have been prepared by chemical solution deposition (CSD). Air-stable and precipitate-free PMN and PT precursor sols were separately synthesized, and PMN-PT sols were obtained by the simple mixture in air of the former. The PMN-PT sols were deposited onto Pt-coated Si substrates and dried on a hot-plate. Crystallization of the films was carried out by rapid thermal processing (RTP) in oxygen, using different temperatures, soaking times, and heating rates. Single perovskite PMN-PT thin films were obtained at low temperatures (650 °C) with short soaking times (6s) and rapid heating rates (200 °C/s). The films show a columnar growth and a uniform thickness. Both the evolution of the perovskite distortion and the electrical properties with the PMN to PT ratio indicate the correct formation of the solid solution. The temperature and frequency dependences of the permittivity and the ferroelectric loops also indicate an increase of the relaxor characteristic of the films as compared with bulk materials. Piezoelectric coefficients were measured across the ferroelectric loop by optical interferometry, and an enhancement of piezoelectricity at the MPB composition was found. A piezoelectric d33 coefficient of ∼55 pC/N was measured in ∼300-nm-thick films of this composition with a saturation polarisation of Ps ∼25 μC/cm2.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (France)

Instant access to the full article PDF.

Institutional subscriptions

FIG. 1.
FIG. 2.
FIG. 3.
FIG. 4.
FIG. 5.
FIG. 6.
FIG. 7.

Similar content being viewed by others

References

  1. S. Nomura, K. Uchino: Recent applications of PMN-based electrostrictors. Ferroelectrics 50, 197 (1983)

    Article  Google Scholar 

  2. S.E. Park, T.R. Shrout: Characteristics of relaxor-based piezoelectric single crystals for ultrasonic transducers. IEEE Trans. Ultr. Ferr. Freq. Contr. 44, 1140 (1997)

    Article  Google Scholar 

  3. S.E. Park, T.R. Shrout: Relaxor based ferroelectric single crystals for electro-mechanical actuators. Mater. Res. Innov. 1, 20 (1997)

    Article  CAS  Google Scholar 

  4. S.W. Choi, T.R. Shrout, S.J. Jang, A. Bhalla: Dielectric and pyroelectric properties in the Pb(Mg1/3Nb2/3)O3–PbTiO3 system. Ferroelectrics 100, 29 (1989)

    Article  CAS  Google Scholar 

  5. S.E. Park, T.R. Shrout: Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals. J. Appl. Phys. 82, 1804 (1997)

    Article  CAS  Google Scholar 

  6. J. Kelly, M. Leonard, C. Tantigate, A. Safari: Effect of composition on the electromechanical properties of (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 ceramics. J. Am. Ceram. Soc. 80, 957 (1997)

    Article  CAS  Google Scholar 

  7. S. Kwon, E.M. Sabolsky, G.L. Messing, S. Trolier McKinstry: High strain, T001Y textured 0.675Pb(Mg1/3Nb2/3)O3–0.325PbTiO3 ceramics: Templated grain growth and piezoelectric properties. J. Am. Ceram. Soc. 88, 312 (2005)

    Article  CAS  Google Scholar 

  8. Semiconductor Industry Association: International Technology Roadmap for Semiconductors (International SEMATECH, Austin TX, 2006). Available at http://www.itrs.net/Links/2006Update/2006UpdateFinal.htm

    Google Scholar 

  9. D.L. Polla, L.F. Francis: Processing and characterization of piezoelectric materials and integration into microelectromechanical systems. Ann. Rev. Mater. Sci. 28, 563 (1998)

    Article  CAS  Google Scholar 

  10. S.L. Swartz, T.R. Shrout: Fabrication of perovskite lead magnesium niobate. Mater. Res. Bull. 17, 1245 (1982)

    Article  CAS  Google Scholar 

  11. D. Kuscer, J. Holc, M. Kosec: Mechano-synthesis of lead-magnesium-niobate ceramics. J. Am. Ceram. Soc. 89, 3081 (2006)

    Article  CAS  Google Scholar 

  12. J.W. Zhai, B. Shen, L.Y. Zhang, X. Yao: Preparation and dielectric properties by sol-gel derived PMN-PT powder and ceramic. Mater. Chem. Phys. 64, 1 (2000)

    Article  Google Scholar 

  13. L.F. Francis, D.A. Payne: Thin-layer dielectrics in the Pb[(Mg1/3Nb2/3)1−xTix]O3 system. J. Am. Ceram. Soc. 74, 3000 (1991)

    Article  CAS  Google Scholar 

  14. V. Nagarajan, C.S. Ganpule, B. Nagaraj, S. Aggarwal, S.P. Alpay, A.L. Roytburd, E.D. Williams, R. Ramesh: Effect of mechanical constraint on the dielectric and piezoelectric behavior of epitaxial Pb(Mg1/3Nb2/3)O3(90%)–PbTiO3(10%) relaxor thin films. Appl. Phys. Lett. 75, 4183 (1999)

    Article  CAS  Google Scholar 

  15. J. Ouyang, D.H. Kim, C.B. Eom, R. Ramesh, A.L. Roythbourd: Orientation dependence of the intrinsic converse longitudinal piezoelectric constant for 0.67Pb(Mg1/3Nb2/3)O3–0.33PbTiO3 ferroelectric films with a rhombohedral structure. Smart Mater. Struct. 14, 524 (2005)

    Article  CAS  Google Scholar 

  16. J.H. Park, S. Trolier-McKinstry: Dependence of dielectric and piezoelectric properties on film thickness for highly {100}-oriented lead magnesium niobate-lead titanate (70/30) thin films. J. Mater. Res. 16, 268 (2001)

    Article  CAS  Google Scholar 

  17. J.H. Park, F. Xu, S. Trolier-McKinstry: Dielectric and piezoelectric properties of sol-gel derived lead magnesium niobium titanate films with different textures. J. Appl. Phys. 89, 568 (2001)

    Article  CAS  Google Scholar 

  18. Z. Kighelman, D. Dramjanovic, N. Setter: Dielectric and electromechanical properties of ferroelectric-relaxor 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 thin films. J. Appl. Phys. 90, 4682 (2001)

    Article  CAS  Google Scholar 

  19. M.L. Calzada, I. Bretos, R. Jiménez, H. Guillon, L. Pardo: Low-temperature processing of ferroelectric thin films compatible with silicon integrated circuit technology. Adv. Mater. 16, 1620 (2004)

    Article  CAS  Google Scholar 

  20. European Union Directive 2002/95/EC on the Restriction of the use of certain hazardous substances in electrical and electronic equipment (RoHS directive). Available at http://www.crouzet-usa.com/RoHS.pdf

  21. N.J. Phillips, M.L. Calzada, S.J. Milne: Sol gel-derived lead titanate films. J. Non-Cryst. Solids 147–148, 285 (1992)

    Article  Google Scholar 

  22. M.L. Calzada, R. Jiménez, A. González, J. Mendiola: Air-stable solutions for the low-temperature crystallization of strontium bismuth tantalate ferroelectric films. Chem. Mater. 13, 3 (2001)

    Article  CAS  Google Scholar 

  23. M.L. Calzada, M. Algueró, J. Ricote, A. Santos, L. Pardo: Preliminary results on sol-gel processing of T100Y oriented Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films using diol-based solutions. J. Sol-Gel Sci. Technol. 42, 331 (2007)

    Article  CAS  Google Scholar 

  24. S.J. Milne, S.H. Pyke: Modified sol-gel process for the production of lead titanate films. J. Am. Ceram. Soc. 74, 1407 (1991)

    Article  CAS  Google Scholar 

  25. M.G. Cain, M.J. Lowe, A. Cuenat, M. Stewart, J. Blackburn: Quantification of properties of ferroelectric thin film using piezoresponse force microscopy, Proceedings Nanotech 2005, edited by M. Laudon and B. Romanowicz. (Nanoscience & Technology Institute, Cambridge, MA, 2004)362

  26. Y.L. Tu, M.L. Calzada, N.J. Phillips, S.J. Milne: Synthesis and electrical characterization of thin films of PT and PZT made from a diol-based sol-gel route. J. Am. Ceram. Soc. 79, 441 (1996)

    Article  CAS  Google Scholar 

  27. M.L. Calzada, A. González: Tantalum penta-glycolate sol as a precursor of strontium bismuth tantalate ferroelectric thin films. J. Am. Ceram. Soc. 88, 2702 (2005)

    Article  CAS  Google Scholar 

  28. R.C. Mehrotra, P.N. Kapoor: Organic compounds of niobium V. Reaction of niobium pentaethoxide with glycols. J. Less Common Met. 8, 419 (1965)

    Article  CAS  Google Scholar 

  29. R.N. Kapoor, S. Prakash, P.N. Kapoor: Reactions of niobium and tantalum pentaethoxides with glycols. Z. Anorg. Allg. Chem. 351, 219 (1967)

    Article  CAS  Google Scholar 

  30. H. Beltrán, E. Cordoncillo, P. Escribano, J.B. Carda, A. Cotas, A.R. West: Sol-gel synthesis-and characterization of Pb(Mg1/3Nb2/3)O3 (PMN) ferroelectric perovskite. Chem. Mater. 12, 400 (2000)

    Article  CAS  Google Scholar 

  31. M.L. Calzada, R. Sirera, F. Carmona, B. Jiménez: Investigations of a diol-based sol-gel process for the preparation of lead titanate materials. J. Am. Ceram. Soc. 78, 1802 (1995)

    Article  CAS  Google Scholar 

  32. H. Fan, G.T. Park, J.J. Choi, H.E. Kim: Preparation and characterization of sol-gel-derived lead magnesium niobium titanate thin films with pure perovskite phase and lead oxide cover coat. J. Am. Ceram. Soc. 85, 2001 (2002)

    Article  CAS  Google Scholar 

  33. M.L. Calzada, A. González, R. Jiménez, C. Alemany, J. Mendiola: Rapid thermal processing of strontium bismuth tantalate ferroelectric thin films prepared by a novel chemical solution deposition method. J. Eur. Ceram. Soc. 21, 1517 (2001)

    Article  CAS  Google Scholar 

  34. A.K. Singh, D. Pandey: Evidence for M-B and M-C phases in the morphotropic phase boundary region of (1 − x)[Pb(Mg1/3Nb2/3)O3]–xPbTiO3: A Rietveld study. Phys. Rev. B 67, 064102 (2003)

    Article  CAS  Google Scholar 

  35. Z.J. Wang, Y. Aoki, H. Kokawa, R. Maeda: Crystal structure and microstructure of lead zirconate titanate (PZT) thin films with various Zr/Ti ratios grown by hybrid processing. J. Cryst. Growth 267, 92 (2004)

    Article  CAS  Google Scholar 

  36. R.J. Ong, D.A. Payne: Processing effects for integrated PZT: Residual stress, thickness, and dielectric properties. J. Am. Ceram. Soc. 88, 2839 (2005)

    Article  CAS  Google Scholar 

  37. R. Jiménez, A. González, M.L. Calzada, J. Mendiola: Study of electrolytic laminated ferroelectric thin films from electroded substrates. J. Mater. Res. 15, 1041 (2000)

    Article  Google Scholar 

  38. J. Zhao, Q.M. Zhang, N. Kim, T. Shrout: Electromechanical properties of relaxor ferroelectric lead magnesium niobate-lead titanate ceramics. Jpn. J. Appl. Phys. 34, 5658 (1995)

    Article  CAS  Google Scholar 

  39. M. Algueró, A. Moure, L. Pardo, J. Holc, M. Kosec: Processing by mechanosynthesis and properties of piezoelectric Pb(Mg1/3Nb2/3)O3–PbTiO3 with different compositions. Acta Mater. 54, 501 (2006)

    Article  CAS  Google Scholar 

  40. C.B. Parker, J.P. Maria, A.I. Kingon: Temperature and thickness dependent permittivity of (Ba,Sr)TiO3 thin films. Appl. Phys. Lett. 81, 340 (2002)

    Article  CAS  Google Scholar 

  41. A.L. Kholkin, E.K. Akdogan, A. Safari, P.F. Chauvy, N. Setter: Characterization of the effective electrostriction coefficients in ferroelectric thin films. J. Appl. Phys. 89, 8066 (2001)

    Article  CAS  Google Scholar 

  42. R. Guo, L.E. Cross, S.E. Park, B. Noheda, D.E. Cox, G. Shirane: Origin of the high piezoelectric response in PbZr1−xTixO3. Phys. Rev. Lett. 84, 5423 (2000)

    Article  CAS  Google Scholar 

  43. H. Arndt, F. Sauerbier, G. Schmidt, L.A. Shebanov: Field-induced phase-transition in Pb(Mg1/3Nb2/3)O3 single-crystals. Ferroelectrics 79, 439 (1988)

    Google Scholar 

  44. M. Algueró, J. Ricote, R. Jiménez, P. Ramos, J. Carreaud, B. Dkhill, J.M. Kiat, J. Holc, M. Kosec: Size effect in morphotropic phase boundary Pb(Mg1/3Nb2/3)O3–PbTiO3. Appl. Phys. Lett. 91, 112905 (2007)

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This work has been financed by the European Network of Excellence on Multifunctional & Integrated Piezoelectric Devices (NoE-MIND CE FP6 515757-2), the Spanish Project MAT2007-61409, and the UK DIUS Materials Program.

Author information

Authors and Affiliations

  1. Instituto Ciencia de Materiales de Madrid (CSIC), 28049, Madrid, Spain

    M.L. Calzada, M. Algueró, A. Santos & L. Pardo

  2. National Physical Laboratory (NPL), Teddington, TW11 0LW, United Kingdom

    M. Stewart & M.G. Cain

Authors
  1. M.L. Calzada
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Algueró
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. Santos
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Stewart
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. M.G. Cain
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. L. Pardo
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M.L. Calzada.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Calzada, M., Algueró, M., Santos, A. et al. Piezoelectric, ferroelectric Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films with compositions around the morphotropic phase boundary prepared by a sol-gel process of reduced thermal budget. Journal of Materials Research 24, 526–533 (2009). https://doi.org/10.1557/JMR.2009.0045

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/JMR.2009.0045

Search

Navigation