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Infrared spectra of nanometre granular zirconia

High-quality Fourier-transform infrared reflectance spectra of nanometre grains with particle sizes ranging from 5 nm to 120 nm have been recorded at room temperature. The results show that, even for very small grain sizes (5-10 nm), the samples retain the main features of monoclinic symmetry, although the lowering of the crystal symmetry has led to the broadening of the infrared bands. Two surface phonons have been identified. The processes of strain removal above the annealing temperature have been revealed by the appearance of two doublets at around and ; at the same time the particle sizes increase rapidly. As the particle size decreases, the doubly degenerate infrared-active modes, such as at , redshift while the non-degenerate modes, such as at , blueshift. This phenomenon is tentatively explained in terms of the internal-external classification of the lattice vibrations.