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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References
Cardona, M. (ed.) Light Scattering in Solids I (Springer, 1983).
Bustarret, E. et al. Superconductivity in doped cubic silicon. Nature 444, 465–468 (2006).
Fleury, P. A. & Worlock, J. M. Electric-field-induced Raman scattering in SrTiO3 and KTaO3 . Phys. Rev. 174, 613–623 (1968).
Leite, R. C. C., Scott, J. F. & Damen, T. C. Multiple-phonon resonant raman scattering in CdS. Phys. Rev. Lett. 22, 780–782 (1969).
Cerdeira, F., Buchenauer, C. J., Pollak, F. H. & Cardona, M. Stress-induced shifts of first-order Raman frequencies of diamond- and zinc-blende-type semiconductors. Phys. Rev. B 5, 580–593 (1972).
Deluca, M., Higashino, M. & Pezzotti, G. Raman tensor elements for tetragonal BaTiO3 and their use for in-plane domain texture assessments. Appl. Phys. Lett. 91, 091906 (2007).
Lagos, P. L. et al. Identification of ferroelectric domain structure in BaTiO3 for Raman spectroscopy. Surf. Sci. 532, 493–500 (2003).
Bailo, E. & Deckert, V. Tip-enhanced raman spectroscopy of single RNA strands: towards a novel direct-sequencing method. Angew. Chem. Int. Ed. 47, 1658–1661 (2008).
Hartschuh, A., Sánchez, E. J., Xie, X. S. & Novotny, L. High-resolution near-field Raman microscopy of single-walled carbon nanotubes. Phys. Rev. Lett. 90, 095503 (2003).
Neacsu, C. C., Dreyer, J., Behr, N. & Raschke, M. B. Scanning-probe Raman spectroscopy with single-molecule sensitivity. Phys. Rev. B 73, 193406 (2006).
Zhang, W., Yeo, B. S., Schmid, T. & Zenobi, R. Single molecule tip-enhanced Raman spectroscopy with silver tips. J. Phys. Chem. C 111, 1733–1738 (2007).
Steidtner, J. & Pettinger, B. Tip-enhanced Raman spectroscopy and microscopy on single dye molecule with 15 nm resolution. Phys. Rev. Lett. 100, 236101 (2008).
Ossikovski, R., Nguyen, Q. & Picardi, G. Simple model for the polarization effects in tip-enhanced Raman spectroscopy. Phys. Rev. B 75, 045412 (2007).
Motahashi, M., Hayazawa, N., Tarun, A. & Kawata, S. Depolarization effect in reflection-mode tip-enhanced Raman scattering for Raman active crystals. J. Appl. Phys. 103, 034309 (2008).
Matsui, R., Verma, P., Ichimura, T., Inouye, Y. & Kawata, S. Nanoanalysis of crystalline properties of GaN thin film using tip-enhanced Raman spectroscopy. Appl. Phys. Lett. 90, 061906 (2007).
Setter, N. et al. Ferroelectric thin films: review of materials, properties and applications. J. Appl. Phys. 100, 051606 (2006).
Zalar, B., Laguta, V. V. & Blinc, R. NMR evidence for the coexistence of order-disorder and displacive components in barium titanate. Phys. Rev. Lett. 90, 037601 (2003).
Maksimov, E. G., Matsko, N. L., Ebert, S. V. & Magnitskaya, M. V. Some problems in the theory of perovskite ferroelectrics. Ferroelectrics 354, 19–38 (2007).
Jang, M.-S., Takashige, M., Kojima, S. & Nakamura, T. Oblique phonons with special concern to the soft phonon mode in tetragonal BaTiO3 . J. Phys. Soc. Jpn 52, 1025–1033 (1983).
Perry, C. H. & Hall, D. B. Temperature dependence of the Raman spectrum of BaTiO3 . Phys. Rev. Lett. 15, 700–702 (1965).
Neacsu, C. C., Steudle, G. A. & Raschke, M. B. Plasmonic light scattering from nanoscopic metal tips. Appl. Phys. B 80, 295–300 (2005).
Le Ru, E. C. et al. Experimental verification of the SERS electromagnetic model beyond the |E|4 approximation: polarization effects. J. Phys. Chem. C 112, 8117–8121 (2008).
Gucciardi, P. G. et al. Light depolarization induced by metallic tips in apertureless near-field optical microscopy and tip-enhanced Raman spectroscopy. Nanotechnology 19, 215702 (2008).
Lines, M. & Glass, A. Principles and Applications of Ferroelectric and Related Materials (Oxford Univ. Press, 2001).
Munoz-Saldana, J., Schneider, G. A. & Eng, L. M. Stress induced movement of ferroelastic domain walls in BaTiO3 single crystals evaluated by scanning force microscopy. Surf. Sci. 480, L402–L410 (2001).
Kalinin, S. V. & Bonnell, D. A. Effect of phase transition on the surface potential of the BaTiO3 (100) surface by variable temperature scanning surface potential microscopy. J. Appl. Phys. 87, 3950–3957 (2000).
Sackrow, M., Stanciu, C., Lieb, M. A. & Meixner, A. J. Imaging nanometer-sized hot spots on smooth Au films with high-resolution tip-enhanced luminescence and Raman near-field optical microscopy. Chem Phys Chem 9, 316–320 (2008).
Kehr, S. C. et al. Anisotropy contrast in phonon-enhanced apertureless near-field microscopy using a free-electron laser. Phys. Rev. Lett. 100, 256403 (2008).
Mao, Y., Banerjee, S. & Wong, S. S. Large-scale synthesis of single-crystalline perovskite nanostructures. J. Am. Chem. Soc. 125, 15718–15719 (2003).
Yun, W. S., Urban, J. J., Gu, Q. & Park, H. Ferroelectric properties of individual barium titanate nanowire investigated by scanned probe microscopy. Nano Lett. 2, 447–450 (2002).
Ren, B., Picardi, G. & Pettinger, B. Preparation of gold tips suitable for tip-enhanced Raman spectroscopy and light emission by electrochemical etching. Rev. Sci. Instrum. 75, 837–841 (2004).
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.
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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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DOI: https://doi.org/10.1038/nnano.2009.190
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