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Quantitative chemical analysis of fluorite-to-perovskite transformations in (Pb,La)(Zr,Ti)O3 PLZT thin films

  • Chad M. Parish (a1), Geoff L. Brennecka (a1), Bruce A. Tuttle (a1) and Luke N. Brewer (a1)

Lead loss during processing of solution-derived Pb(Zr,Ti)O3 (PZT)-based thin-films can result in the formation of a Pb-deficient, nonferroelectric fluorite phase that is detrimental to dielectric properties. It has recently been shown that this nonferroelectric fluorite phase can be converted to the desired perovskite phase by postcrystallization treatment. Here, quantitative standard-based energy-dispersive x-ray spectrometry (EDS) in a scanning transmission electron microscope (STEM) is used to study cation distribution before and after this fluorite-to-perovskite transformation. Single-phase perovskite PbZr0.53Ti0.47O3 (PZT 53/47) and Pb0.88La0.12Zr0.68Ti0.29O3 (PLZT 12/70/30) specimens that underwent this treatment were found to be chemically indistinguishable from the perovskite present in the multiphase specimens prior to the fluorite-to-perovskite transformation. Significant Zr–Ti segregation is found in PLZT 12/70/30, but not in PZT 53/47. Slight La-segregation was seen in rapidly crystallized PLZT, but not in more slowly crystallized PLZT.

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1 S. Trolier-McKinstry , P. Muralt : Thin film piezoelectrics for MEMS. J. Electroceram. 12, 72004

2 N. Setter , D. Damjanovic , L. Eng , G. Fox , S. Gevorgian , S. Hong , A. Kingon , H. Kohlstedt , N.Y. Park , G.B. Stephenson , I. Stolitchnov , A.K. Taganstev , D.V. Taylor , T. Yamada , S. Streiffer : Ferroelectric thin films: Review of materials, properties, and applications. J. Appl. Phys. 100, 0516062006

3 J. Sigman , G.L. Brennecka , P.G. Clem , B.A. Tuttle : Fabrication of perovskite-based high-value integrated capacitors by chemical solution deposition. J. Am. Ceram. Soc. 91, 18512008

4 K.H. Hardtl , H. Rau : PbO vapor pressure in the Pb(Ti1−xZrx)O3 system. Solid State Commun. 7, 411969

5 R.L. Holman , R.M. Fulrath : Intrinsic nonstoichiometry in lead zirconate titanate system determined by Knudsen effusion. J. Appl. Phys. 44, 52271973

6 G.S. Snow : Improvements in atmosphere sintering of transparent PLZT ceramics. J. Am. Ceram. Soc. 56, 4791973

7 A.H. Carim , B.A. Tuttle , D.H. Doughty , S.L. Martinez : Microstructure of solution-processed lead zirconate titanate (PZT) thin-films. J. Am. Ceram. Soc. 74, 14551991

8 I.M. Reaney , K. Brooks , R. Klissurska , C. Pawlaczyk , N. Setter : Use of transmission electron-microscopy for the characterization of rapid thermally annealed, solution-gel, lead-zirconate-titanate films. J. Am. Ceram. Soc. 77, 12091994

10 M.A. Subramanian , G. Aravamudan , G.V.S. Rao : Oxide pyrochlores—A review. Prog. Solid State Chem. 15, 551983

11 A.P. Wilkinson , J.S. Speck , A.K. Cheetham , S. Natarajan , J.M. Thomas : In-situ x-ray-diffraction study of crystallization kinetics in PbZr1−xTixO3 (PZT, x = 0.0, 0.55, 1.0). Chem. Mater. 6, 7501994

12 G.L. Brennecka , C.M. Parish , B.A. Tuttle , L.N. Brewer , M.A. Rodriguez : Reversibility of the perovskite-to-fluorite phase transformation in lead-based thin and ultrathin films. Adv. Mater. 20, 14072008

13 Y. Fukuda , K. Aoki : Effects of excess Pb and substrate on crystallization processes of amorphous Pb(Zr,Ti)O3 thin films prepared by RF magnetron sputtering. Jpn. J. Appl. Phys., Part 1 36, 57931997

17 T. Tani , D.A. Payne : Lead-oxide coatings on sol gel-derived lead lanthanum zirconium titanate thin-layers for enhanced crystallization into the perovskite structure. J. Am. Ceram. Soc. 77, 12421994

18 S.Y. Chen , I.W. Chen : Temperature-time texture transition of Pb(Zr1−xTix)O3 thin-films. 1. Role of Pb-rich intermediate phases. J. Am. Ceram. Soc. 77, 23321994

19 S. Aggarwal , S. Madhukar , B. Nagaraj , I.G. Jenkins , R. Ramesh , L. Boyer , J.T. Evans : Can lead nonstoichiometry influence ferroelectric properties of Pb(Zr,Ti)O3 thin films? Appl. Phys. Lett. 75, 7161999

20 D. Kaewchinda , T. Chairaungsri , M. Naksata , S.J. Milne , R. Brydson : TEM characterisation of PZT films prepared by a diol route on platinised silicon substrates. J. Eur. Ceram. Soc. 20, 12772000

21 S.A. Impey , Z. Huang , A. Patel , R. Beanland , N.M. Shorrocks , R. Watton , R.W. Whatmore : Microstructural characterization of sol-gel lead-zirconate-titanate thin films. J. Appl. Phys. 83, 22021998

23 P. Muralt : Texture control and seeded nucleation of nanosize structures of ferroelectric thin films. J. Appl. Phys. 100, 0516052006

24 I. Franke , K. Roleder , J. Klimontko , A. Ratuszna , A. Soszynski : Anomalous piezoelectric and elastic properties of a tetragonal PZT ceramic near morphotropic phase boundary. J. Phys. D: Appl. Phys. 38, 7492005

25 A. Etin , G.E. Shter , S. Baltianski , G.S. Grader , G.M. Reisner : Controlled elemental depth profile in sol-gel-derived PZT films. J. Am. Ceram. Soc. 89, 23872006

27 F. Calame , P. Muralt : Growth and properties of gradient free sol-gel lead zirconate titanate thin films. Appl. Phys. Lett. 90, 0629072007

28 O. Sugiyama , K. Murakami , S. Kaneko : XPS analysis of surface layer of sol-gel-derived PZT thin films. J. Eur. Ceram. Soc. 24, 11572004

30 G. Drazic , M. Kosec : Analytical electron microscopy of ferroelectric ceramic materials. Ferroelectrics 201, 231997

31 A. Dutschke , J. Meinhardt , D. Sporn : Analysis of the phase content and Zr:Ti fluctuation phenomena in PZT sol-gel films with a nominal composition near the morphotropic phase boundary. J. Eur. Ceram. Soc. 24, 15792004

32 R.A. Assink , R.W. Schwartz : H-1 and C-13 NMR investigations of Pb(Zr,Ti)O3 thin-film precursor solutions. Chem. Mater. 5, 5111993

34 G. Cliff , G.W. Lorimer : The quantitative analysis of thin specimens. J. Microsc. 103, 2031975

35 J.I. Goldstein , D.B. Williams , G. Cliff : Quantitative x-ray analysis in Principles of Analytical Electron Microscopy, edited by D.C. Joy, A.D. Romig Jr., and J.I. Goldstein PlenumNew York1986 155

37 D.B. Williams , C.B. Carter : Transmission Electron Microscopy PlenumNew York1996

38 J.I. Goldstein : Principles of thin film x-ray microanalysis in Introduction to Analytical Electron Microscopy, edited by PlenumNew York1979 83

41 M. Huffman , J.P. Goral , M.M. Al-Jassim , C. Echer : Structural and chemical-compositional investigation of thin lead zirconate titanate films. J. Vac. Sci. Technol., A 10, 15841992

43 I. Reaney , D.J. Barber : Transmission electron microscopy of lead scandium tantalate thin-films. J. Microsc. 160, 2131990

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