Nonlinear spectroscopy near-field

For near-field imaging based on nonlinear or ultrafast spectroscopy, light pulses from a femtosecond Ti sapphire laser (pulse width ca. 100 fs, repetition rate ca. 

Biomolecular Imaging by Near-Field Nonlinear Spectroscopy and Microscopy... 

In this chapter, we showed the capability of near-field optical spectroscopy combined with vibrational spectroscopy and nonlinear optics for biochemical applications. The evanescent field localized at the nanoscale tip realized the extremely small light source for various spectroscopes in the near-field. Especially when the tip is made... 

To date, a number of chemically selective near-field imaging methods have been demonstrated. Near-field contrast mechanisms that rely on electronic spectroscopy (UV-visible absorption and fluorescence),204 vibrational spectroscopy (IR absorption and Raman spectroscopies), dielectric spectroscopy (microwave dispersion), and nonlinear spectroscopy (second harmonic generation) have all been demonstrated at length scales well below the diffraction limit of light. 

Ichimura T, Hayazawa N, Hashimoto M, Inouye Y, Kawata S (2004) Application of tip-enhanced microscopy for nonlinear Raman spectroscopy. Appl Phys Lett 84 1768 Ichimura T, Hayazawa N, Hashimoto M, Inouye Y, Kawata S (2004) Tip-enhanced coherent anti-stokes raman scattering for vibrational nanoimaging. Phys Rev Lett 92 220801 Tanaka S, Maeda Y, Cai L, Tabata H, Kawai T (2001) Application of tip-enhanced microscopy for nonlinear Raman spectroscopy. Jpn J Appl Phys 40 4217 Watanabe H, Ishida Y, Hayazawa N, Inouye Y, Kawata S (2004) Tip-enhanced near-field Raman analysis of tip-pressurized adenine molecule. Phys Rev B 69 155418 Yano T, Verma P, Saito Y, Ichimura T, Kawata S (2009) Pressure-assisted tip-enhanced Raman imaging at a resolution of a few nanometres. Nature Photon 3 473 Yano T, Inouye Y, Kawata S (2006) Nanoscale uniaxial pressure effect of a carbon nanotube bundle on tip-enhanced near-field Raman spectra. Nano Lett 6 1269 Downes A, Salter D, Elfick A (2006) Heating effects in tip-enhanced optical microscopy. Opt Exp 14 5216... 

In principle, all kinds of spectroscopic techniques lend themselves to on-line measurements. Only a very few are practical. Although low-field NMR has been used to measure various material properties by applying empirical relationships, NMR is still not a realistic proposition for on-line measurements. Ironically, ETIR spectroscopy suffers from too much sensitivity. Typically, good spectra can be obtained only from very thin polymeric films (or solutions). Attenuated total reflection (ATR) probes, in which only a fraction of the IR light penetrates a very short distance into the sample, reduce the problem of excessive sensitivity. However, they aggravate the problems of variations in the baseline and nonlinear response. The latter problem also obstructs the use of UV spectrometry for monitoring polymerization reactions. Of the remaining options, near-infrared (NIR) and Raman spectroscopy are the most attractive. 

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