350 rub
Journal №4 for 2015 г.
Article in number:
The use of back skattering electron diffraction for nanophase analysis of thin Pb(Zr,Ti)O<sub>3</sub> films
Authors:
D.M. Dolginzev - Research Engineer, Russian State Pedagogical University. A. I. Herzen (St. Petersburg). Е-mail: thphys@herzen.spb.ru A.G. Kanareikin - Post-Graduate Student, Russian State Pedagogical University. A. I. Herzen (St. Petersburg). Е-mail: thphys@herzen.spb.ru V.P. Pronin - Dr.Sc. (Phys.-Math.), Professor, Russian State Pedagogical University. A. I. Herzen (St. Petersburg). Е-mail: thphys@herzen.spb.ru E.Yu. Kaptelov - Dr.Sc. (Phys.-Math.), Senior Research Scientist, Russian State Pedagogical University. A. I. Herzen (St. Petersburg). Е-mail: Kaptelov@mail.ioffe.ru S.V. Senkevich - Dr.Sc. (Phys.-Math.), Research Scientist, Russian State Pedagogical University. A. I. Herzen (St. Petersburg). Е-mail: SenkevichSV@mail.ioffe.ru I.P. Pronin - Dr.Sc. (Phys.-Math.), Senior Research Scientist, Russian State Pedagogical University. A. I. Herzen (St. Petersburg). Е-mail: Petrovich@mail.ioffe.ru
Abstract:
Backscattering electron nanoscale diffraction is used to detect monoclinic phase in ferroelectric thin films of lead zirconate titanate PZT, the compositions of which correspond to the practically significant region of morphotropic phase boundary (MPB). PZT thin films were prepared by two-stage technology. In the first stage, PZT layers of Zr/Ti = 54/46 composition were deposited on a «cold» substrate Pt/SiO2/Si using RF magnetron sputtering, and at the second one were annealed in air or in a lead atmosphere at 530-650 °C. Elemental composition of the layers was revealed using scanning electron microscopy (EVO-40, Zeiss), equipped with energy dispersive X-ray analyzer INCA. To scan the composition of PZT layer the working gas pressure was varied from 2-8 Pa, allowing to vary layers composition in the concentration range of Zr/Ti = 55/45-52,5/47.5, corresponding to a region MPB. The physical model is suggested, in according to which the atomic ratio Zr/Ti and content of the lead atoms may be strongly changed during magnetron sputtering. Determination of the monoclinic phase (also available other phases in the surface nanolayers PZT thickness of about 10 lattice constants) was carried out by computer-aided comparison (overlay) obtained diffraction patterns with similar patterns from the database ICSD (Inorganic Crystal Structure Database), deciphering the crystal parameters is carried out on the basis of the results of measurements of the neutron and X-ray diffraction for the solid solution composition PZT, close to the investigated. The phase analysis of the results indicates the presence of two modifications of the ferroelectric phase  monoclinic and tetragonal, the ratio of which depends on a number of factors such as the content of lead atoms, the ratio of atoms of Zr/Ti, the annealing temperature of the films, the temperature of the samples. The paper presents a discussion of the laws.
Pages: 21-28
References

 

  1. JAffe B., Kuk U., JAffe G.Pezoehlektricheskaja keramika. M.: Mir. 1974. 288 s.
  2. Xu Yu. Ferroelectric materials and their applications. N. Holland-Amsterdam-London-New-York-Tokyo. 1991. 391 p.
  3. Gufan JU.M., Sakhnenko V.P.Termodinamicheskoe opisanie kristallov pri fazovykh perekhodakh vtorogo roda vblizi N-faz­nykh tochek // ZHEHTF. 1975. T. 69. Vyp. 4.S. 1423-1439.
  4. Isupov V.A. Sosushhestvovanie faz v tverdykh rastvorakh cirkonata-titanata svinca // FTT. 2001. T. 43. Vyp. 12. S. 2166-2169.
  5. Isupov V.A. Phase coexistence in lead zirconate titanate solid solutions. // Physics of the Solid State. 2001. V. 43. R. 2262-2266.
  6. Noheda B., Cox D.E., Shirane G.; Gonzalo J. A., Cross L.E., Park S.-E. A monoclinic ferroelectric phase in the Pb(Zr1-xTix)O3 solid solution // Appl. Phys. Lett. 1999. V. 74, № 14. P. 2059-2061.
  7. Sergeenko I.A., Gufan Yu. M., Urazhdin S.  Phenomenological theory of phase trantuions in highly piezoelectric perovskites // Phys. Rev. B. 2002. V. 65. R 144104.
  8. Wada S., Muraishi T., Yokoh K., Yako K., Kamemoto H., Tsurumi T. Domain wall engineering in lead-free piezoelectric crystals // Ferroelectrics. 2007. V. 355. P. 37-49.
  9. Noheda B., Cox D. E., Shirane G., Guo R., Jones B., Cross L. E. Stability of the monoclinic phase in the ferroelectric perovskite PbZr1-xTixO3 // Phys. Rev. B. 2001. V. 63. R. 014103.
  10. Noheda B., Wu L., Zhu Y. Low-temperature superlattice in monoclinic Pb(Zr0,52Ti0,48)O3// Phys. Rev. B. 2002. V. 66. R. 060103(R).
  11. Noheda B., Cox D. E. Bridging phases at the morphotropic boundaries of lead oxide solid solutions // Phase Transitions. 2006. V. 79. is. 1-2. P. 5-20.
  12. Scott J.F. Application of modern ferroelectrics // Science. 2007. V. 315. R. 954-961.
  13. Izyumskaya N., Alivov Y.-I., Cho S.-J., Morkoç H., Lee H., Kang Y.-S. Processing, structure, properties, and applications of PZT thin films // Critical Reviews in Solid State and Materials Sciences. 2007. V. 32. P. 111-202.
  14. Yan L., Li J., Cao H., Viehland D. Low symmetry phase in Pb(Zr0,52Ti0,48)O3. epitaxial thin films with enhanced ferroelectric properties // Appl. Phys. Lett. 2006. V. 89. R 262905.
  15. Randle V., Engler O. Electron Backscatter Diffraction in Materials Science. New York: Springer. 2009.
  16. Fox G.R. Han X., Maitland T.M., Vaudin M.D. Nanometer scale crystallographic texture mapping of platinum and lead zirconate titanate thin films by electron backscatter diffraction // J. Mater. Sci. 2010. V. 45. P. 2991-2994.
  17. Pronin I.P., Kaptelov E.JU., Senkevich S.V., Klimov V.A., Zajjceva N.V., SHaplygina T.A., Pronin V.P., Kukushkin S.A. Osobennosti kristallizacii polikristallicheskikh tonkikh plenok PZT, sformirovannykh na podlozhke Si/SiO2/Pt // FTT. 2010. T. 52. Vyp. 1. S. 124-128.
  18. Pronin I.P., Kaptelov E.JU., Senkevich S.V., Flegontova E.JU., Pronin V.P., Dolgincev D.M. Vozmozhnosti metoda ehlektronno-zondovogo rentgenovskogo mikroanaliza dlja opredelenija sostava nanorazmernykh plenok cirkonata-titanata svinca // Nanomaterialy i nanostruktury - XXI vek. 2011. T. 2. № 4. S. 48-55.
  19. Frantti J., Lappalainen J., Eriksson S., Lantto V., Nishio S., Kakihana M., Ivanov S., Rundlof H. Neutron Diffraction Studies of Pb(ZrxTi1-x)O3 Ceramics // Jpn. J. Appl. Phys. 2000. V. 39. Pt. 1. № 9B. P. 5697-5703.
  20. Volpjas V.A., Kozyrev A.B. Termalizacija atomnykh chastic v gazakh // ZHEHTF. 2011. T. 140. Vyp. 1(7). S. 196-204.