AMPC  Vol.2 No.3 , September 2012
Phase Transformations in PZT Thin Films Prepared by Polymeric Chemical Method
ABSTRACT
Lead zirconate titanate Pb(Zr0.50Ti0.50)O3 (PZT) thin films were deposited by a polymeric chemical method on Pt(111)/ Ti/SiO2/Si substrates to understand the mechanisms of phase transformations in these films. PZT films pyrolyzed at temperatures higher than 350℃ present a coexistence of pyrochlore and perovskite phases, while only perovskite phase is present in films pyrolyzed at temperatures lower than 300℃. For films where the pyrochlore and perovskite phase coexists the amount of pyrochlore phase decreases from top surface to the bottom film-electrode interface and the PZT structure near top surface are Ti-rich compositions while near the bottom film-electrode interface the compositions are Zr-rich. For pyrochlore-free PZT thin film, a small (100) orientation tendency near the film-electrode interface was observed.

Cite this paper
E. Lima and E. Araújo, "Phase Transformations in PZT Thin Films Prepared by Polymeric Chemical Method," Advances in Materials Physics and Chemistry, Vol. 2 No. 3, 2012, pp. 178-184. doi: 10.4236/ampc.2012.23027.
References
[1]   B. Jaffe, W. R. Cook, H. Jaffe, Piezoelectric Ceramics, Academic Press, New York, 1971, pp. 135-183.

[2]   G.H. Heartling, Electronic Ceramics, edited by L.M. Levinson, Marcel and Dekker, New York, 1988.

[3]   M. Miyake, J.F. Scott, X J. Lou, F.D. Morrison, T. Nonaka, S. Motoyama, T. Tatsuta and O. Tsuji, “Submicron three-dimensional trenched electrodes and capacitors for DRAMs and FRAMs: Fabrication and electrical testing”, Journal of Applied Physics, Vol. 104, No. 6, 2008, 064112. doi:10.1063/1.2981197

[4]   C.H. Ahn, K.M. Rabe and J.-M. Triscone, “Ferroelectricity at the nanoscale: local polarization in oxide thin films and heterostructures”, Science, Vol. 303, No. 5657, 2004, 488-491. doi:10.1126/science.1092508

[5]   J. F. Scott and C. A. P. de Araujo, “Ferroelectric memories”, Science, Vol. 246, No. 4936, 1989, 1400-1405. doi:10.1126/science.246.4936.1400

[6]   K. Sreenivas and M. Sayer, P. Garret, “Properties of D.C. magnetron-sputtered lead zirconate titanate thin films”, Thin Solid Films, Vol. 172, No. 2, 1989, 251-267. doi:10.1016/0040-6090(89)90653-6

[7]   O. Auciello, L. Mantese, J. Duarte, X. Chen, S. H. Rou, A. I. Kingon, A. F. Schreiner and A. R. Krauss, “Synthesis and characterization of Pb (ZrxTi1?x)O3 thin films produced by an automated laser abla-tion deposition technique”, Journal of Applied Physics, Vol. 73, No. 10, 1993, 5197. doi:10.1063/1.353746

[8]   I. M. Reaney, D. V. Taylor and K. G. Brooks,” Ferroelectric PZT thin films by sol-gel deposition”, Journal of Sol-Gel Science and Technology, Vol. 13, No. 1-3, 1998, 813-820. doi:10.1023/A:1008690316261

[9]   A.P. Wilkinson, J.S. Speck, A.K. Cheetham, S. Natarajan and J.M. Thomas, “In situ x-ray diffraction study of crystallization kinetics in PbZr1-xTixO3, (PZT, x = 0.0, 0.55, 1.0)”, Chemistry of Materials, Vol. 6, No. 6, 1994, 750-754. doi:10.1021/cm00042a009

[10]   C. K. Kwok and S. B. Desu, “Pyrochlore to perovskite phase transformation in sol-gel derived lead-zirconate- titanate thin films”, Applied Physics Letters, Vol. 60, No. 12, 1992, 1430. doi:10.1063/1.107312

[11]   V. S. Tiwari, A. Kumar, V. K. Wadhawan and D. Pandey, “Kinetics of formation of the pyrochlore and perovskite phases in sol-gel derived lead zir-conate titanate powder”, Journal of Materials Research, Vol. 13, No. 8, 1998, 2170-2173. doi:10.1557/JMR.1998.0303

[12]   K.G. Brooks, I.M. Reaney, R. Klissurska, Y. Huang, L. Bursill and N. Setter, “Orientation of rapid thermally annealed lead-zirconate-titanate thin-films on (111) Pt substrates”, Journal of Materials Research, Vol. 9, No. 10, 1994, 2540-2553. doi:10.1557/JMR.1994.2540

[13]   S.Y. Chen and I.W. Chen, “Temperature-time texture transition of Pb(Zr1-xTix)O3 thin films: I, Role of Pb-rich intermediate phases”, Journal of the American Ceramic Society, Vol. 77, No. 9, 1994, 2332-2336. doi:10.1111/j.1151-2916.1994.tb04602.x

[14]   S.Y. Chen and I.W. Chen, “Temperature-Time texture transition of Pb(Zr1-xTix)O3 thin films: II, Heat treatment and compositional effects”, Journal of the American Ceramic Society, Vol. 77, No. 9, 1994, 2337-2344. doi:10.1111/j.1151-2916.1994.tb04603.x

[15]   A. Etin, G. E. Shter, S. Baltianski, G. S. Grader and G. M. Reisner, “Con-trolled elemental depth profile in sol-gel-derived PZT films”, Journal of the American Ceramic Society, Vol. 89, No. 8, 2006, 2387-2393. doi:10.1111/j.1551-2916.2006.01078.x

[16]   C. M. Parish, G. L. Brennecka, B. A. Tuttle and L. N. Brewer, “Quantitative X-ray spectrum imaging of lead lanthanum zirconate titanate PLZT thin-films”, Journal of the American Ceramic Society, Vol. 91, No. 11, 2008, 3690-3697. doi:10.1111/j.1551-2916.2008.02708.x

[17]   G. L. Brennecka, C. M. Parish, B. A. Tuttle, L. N. Brewer and M. A. Rodriguez, “Reversibility of the perovskite-to-fluorite phase transformation in lead-based thin and ultrathin films”, Advanced Materials, Vol. 20, No. 8, 2008, 1407-1411. doi:10.1002/adma.200702442

[18]   K. Nittala, G. L. Brennecka, B. A. Tuttle and J. L. Jones, “Phase evolution in solution de-posited Pb-deficient PLZT thin films”, Journal of Materials Science, Vol. 46, No. 7, 2011, 2148-2154. doi:10.1007/s10853-010-5051-x

[19]   M. Pechini, U.S. Pat. N° 3 330 697, July 11 (1967).

[20]   E. B. Araújo and J. A. Eiras, “PZT thin films obtained from oxide precursors”, Journal of Materials Science Letters, Vol. 17, No. 10, 1998, 833-835. doi:10.1023/A:1006698708601

[21]   P. A. Lessing, “Mixed-cation oxide powders via polymeric precursors”, Ce-ramic Bulletin, Vol. 68, No. 5, 1989, 1002-1007.

[22]   H. M. Rietveld, “Line profiles of neutron powder-diffraction peaks for structure refinement”, Acta Crystallographica, Vol. 22, No. 1, 1967, 151-152. doi:10.1107/S0365110X67000234

[23]   A. C. Larson and R. B. Von Dreele, Los Alamos National Laboratory Report LAUR 86 (1994).

[24]   B. H. Toby, “EXPGUI, a graphical user interface for GSAS”, Journal of Applied Crystallography, Vol. 34, No. 2, 2001, 210-213. doi:10.1107/S0021889801002242

[25]   P. Thompson, D. E. Cox and J. B. Hastings, “Rietveld refinement of Debye-Scherrer synchrotron X-ray data from Al2O3”, Journal of Applied Crystallography, Vol. 20, No. 2, 1987, 79-83. doi:10.1107/S0021889887087090

[26]   G. K. Williamson and W. H. Hall, “X-ray line broadening from filed aluminium and wolfram”, Acta Mettallurgica, Vol. 1, No. 1, 1953, 22-31. doi:10.1016/0001-6160(53)90006-6

[27]   R. Lal, R. Krishnan and P. Ramakrishnan, “Transition between tetragonal and rhombohedral phases of PZT ceramics prepared from spray-dried powders”, British Ceramic Transactions and Journal, Vol. 87, No. 3, 1988, 99-102.

[28]   E. M. Griswold, L. Weaver, M. Sayer and I. D. Calder, “Phase-transformations in rapid thermal processed lead-zirconate-titanate”, Journal of Materials Research, Vol. 10, No. 12, 1995, 3149-3159. doi:10.1557/JMR.1995.3149

[29]   B. Noheda, J. A. Gonzalo, L. E. Cross, R. Guo, S. E. Park, D. E. Cox and G. Shirane, “Te-tragonal-to-monoclinic phase transition in a ferroelectric perovskite: The structure of PbZr0.52Ti0.48O3”, Physical Review B, Vol. 61, No. 13, 2000, 8687-8695. doi:10.1103/PhysRevB.61.8687

[30]   L.B. McCusker, R.B. Von Dreele, D.E. Cox, D. Lou?r, and P. Scardi, “Rietveld re-finement guidelines”, Journal of Applied Crystallography, Vol. 32, No. 1, 1999, 36-50. doi:10.1107/S0021889898009856

[31]   B. Noheda, D. E. Cox, G. Shirane, R. Guo, B. Jones and L. E. Cross, “Stability of the monoclinic phase in the ferroelectric perovskite PbZr1-xTixO3”, Physical Review B, Vol. 63, No. 1, 2001, 014103. doi:10.1103/PhysRevB.63.014103

[32]   J. Lappalainen, V. Lantto, J. Frantti and J. Hiltunen, “X-ray diffraction and Raman investigations of thickness dependent stress effects on Pb(ZrxTi1-x)O3 thin films” Applied Physics Letters, Vol. 88, No. 25, 2006, 252901. doi:10.1063/1.2216895

[33]   D. Kwon, B. Kim, B. G. Kim and C. H. Chang, “Strain relaxation and formation of a-domains for PbZr0.2Ti0.8O3 thin films epitaxially grown on SrTiO3 substrates”, Journal of Korean Physical Society, Vol. 55, No. 4, 2009, L1327-L1330. doi:10.3938/jkps.55.1327

[34]   X. Y. Wen, J. Yu, Y. B. Wang, W. L. Zhou, J. X. Gao,” Stress analysis and ferroelectric properties of Pb(Zr0.52Ti0.48)0.96Nb0.04O3 thin film grown on different thickness of BaPbO3 electrodes”, Journal of Applied Physics, Vol. 108, No. 11, 2010, 114103. doi:10.1063/1.3518516

[35]   P. E. Janolin, “Strain on ferroe-lectric thin films Example of Pb(Zr1-xTix)O3”, Journal of Materials Science, Vol. 44, No. 19, 2009, 5025-5048. doi:10.1007/s10853-009-3553-1

[36]   I. M. Reaney, K. Brooks, R. Klissurska, C. Pawlaczyk and N. Setter, “Use of transmission electron microscopy for the characterization of rapid thermally annealed, solution-gel, lead zirconate titanate films”, Journal of the American Ceramic Society, Vol. 77, No. 5, 1994, 1209-1216. doi:10.1111/j.1151-2916.1994.tb05394.x

[37]   W. Gong, J. F. Li, X. Chu, Z. Gui and L. Li, “Preparation and characterization of sol-gel derived (100)-textured Pb(Zr,Ti)O3 thin films: PbO seeding role in the formation of preferential orientation”, Acta Materialia, Vol. 52, No. 9, 2004, 2787-2793. doi:10.1016/j.actamat.2004.02.025

 
 
Top