Optical nanocrystallography with tip-enhanced phonon Raman spectroscopy

Abstract

Conventional phonon Raman spectroscopy is a powerful experimental technique for the study of crystalline solids1,2,3,4,5 that allows crystallography, phase and domain identification6,7 on length scales down to 1 µm. Here we demonstrate the extension of tip-enhanced Raman spectroscopy to optical crystallography on the nanoscale by identifying intrinsic ferroelectric domains of individual BaTiO3 nanocrystals through selective probing of different transverse optical phonon modes in the system. The technique is generally applicable for most crystal classes, and for example, structural inhomogeneities, phase transitions, ferroic order and related finite-size effects occurring on nanometre length scales can be studied with simultaneous symmetry selectivity, nanoscale sensitivity and chemical specificity.

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Figure 1: Experimental setup and crystal symmetry.
Figure 2: Phonon TERS of BaTiO3.
Figure 3: Spatially resolved TERS for ferroelectric domain imaging.

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Acknowledgements

S. Berweger acknowledges support from the University of Washington Center for Nanotechnology with funding from NSF-IGERT. Funding from the National Science Foundation (NSF CAREER grant CHE 0748226) is gratefully acknowledged.

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S.B., C.C.N., and M.B.R. conceived the experiments. S.B. and C.C.N. carried out the experiments. S.B. performed the data analysis. Y.M., H.Z. and S.S.W. synthesized the sample materials. S.B. wrote the manuscript with contributions from C.C.N. and M.B.R.

Corresponding author

Correspondence to Markus B. Raschke.

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Berweger, S., Neacsu, C., Mao, Y. et al. Optical nanocrystallography with tip-enhanced phonon Raman spectroscopy. Nature Nanotech 4, 496–499 (2009). https://doi.org/10.1038/nnano.2009.190

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