Suitability of Raman Spectroscopy for Assessing Anisotropic Strain in Thin Films of Doped Ceria

• Published in: Advanced functional materials 2019-03, Vol.29 (11), p.n/a
• Main Authors: Kraynis, Olga, Makagon, Evgeniy, Mishuk, Eran, Hartstein, Michal, Wachtel, Ellen, Lubomirsky, Igor, Livneh, Tsachi
• Format: Article
• Language: English
• Subjects: anelastic relaxation; Anisotropy; Cerium oxides; Compressive properties; Diffraction patterns; doped ceria; Gruneisen parameter; Grüneisen parameter; Isostatic pressure; Materials science; Membranes; Raman spectra; Raman spectroscopy; Spectrum analysis; Strain relaxation; Substrates; Thin films; Unit cell; X-ray diffraction
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.201804433

A protocol for characterizing relaxation of anisotropic strain in thin films of 10 mol% Eu‐ or Sm‐doped ceria is described. The method is based on comparison of Raman spectra and X‐ray diffraction patterns from substrate‐supported films, displaying in‐plane compressive strain (initial state), with analogous data from 2 mm diameter self‐supported films (i.e., membranes), prepared by partial substrate removal (final state). These membranes are found to be relaxed, i.e., approximately unstrained, but with increased unit cell volume. The effective (i.e., 2‐state) Grüneisen parameter of the F2g Raman active mode for these films is calculated to be 0.4 ± 0.1, which is ≈30% of the literature value for the corresponding ceramics under isostatic pressure. On this basis, it is found that the observed red‐shift of the F2g mode frequency following isothermal strain relaxation of the doped ceria thin films cannot be determined solely by the increase in average unit cell volume. The study presented here may shed light on the suitability of Raman spectroscopy as a technique for characterizing strain in lanthanide‐doped ceria thin films. Raman mode‐Grüneisen parameters are often used to assess strain in thin films. The Raman F2g mode‐Grüneisen parameter measured for thin films of Eu‐ and Sm‐doped ceria is ≈30% of the literature value for the corresponding ceramics under isostatic pressure. This discrepancy is attributed to defect‐related properties of Eu‐ and Sm‐doped ceria.