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Optical Scattering Spectral Thermometry and Refractometry of a Single Gold Nanoparticle under CW Laser Excitation

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Department of Optical Science and Technology, The University of Tokushima, Tokushima 770-8506, Japan
Cite this: J. Phys. Chem. C 2012, 116, 29, 15458–15466
Publication Date (Web):June 26, 2012
https://doi.org/10.1021/jp304271d
Copyright © 2012 American Chemical Society

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    Abstract

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    White light scattering spectra based on dark-field microscopy is a powerful tool for studying localized surface plasmon resonances of single noble metal nanoparticles and for developing their applications in sensing and biomedical therapies. Here we demonstrate the steady-state scattering spectral changes of a single gold nanoparticle under continuous laser heating. The experimental peak shifts allowed the estimation of the particle temperature in the range of 300–700 K with an accuracy of ±20 K on the basis of a spectral calculation exploiting Mie theory. For single gold nanoparticles supported on a glass substrate, progressive red shifts were observed in air, whereas blue shifts were observed in water and glycerol with increasing temperature. The medium has strong influence on peak shifts because of distance-dependent nanoscale medium heating: the shifts strongly depend on the magnitude of the temperature coefficients of a medium refractive index. The laser power-dependent behavior of peak shifts revealed the onset of surface melting occurring at 550–600 K regardless of the medium. Furthermore, experimental shifts also suggested that surface liquid layer grows in thickness with increasing temperature until the whole particle melts: this model has been proposed theoretically as a liquid nucleation and growth hypothesis. Therefore, we showed that the scattering spectral shifts represent an effective measure for the laser-induced morphological alterations of a gold nanoparticle and the nanoscale heating of a medium surrounding the NP.

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    TEM micrographs of Au NPs, calculated and experimental n and κ of bulk gold as a function of wavelength at various temperatures, calculated transient temperature curves for a CW laser-heated 150 nm gold sphere embedded in glass, laser-induced scattering spectral changes of a single 150 nm Au NP on irradiation of 488 nm CW laser, scattering spectral change of a 150 nm diameter Au NP on a glass substrate in air on illumination of 532 nm CW laser light, the calculated spectral peak shift as a function of the temperature of a 150 nm diameter Au NP supported on a glass substrate in air, AFM cross sectional profiles of a 100 nm diameter Au NP before and after laser irradiation and corresponding scattering spectral change, experimental and calculated scattering spectra of 100 nm Au NP in water and glycerol, temperature-dependent refractive index as a function of temperature in water and glycerol measured at 589 nm, and darkfied image and light scattering spectra demonstrating the formation of photothermal bubble. This material is available free of charge via the Internet at http://pubs.acs.org.

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