From normal diffusion to superdiffusion: Photothermal heating of plasmonic core-shell microgels

The motion of core-shell colloids during laser heating is studied using angle-dependent pump-probe dynamic light scattering. The cores consist of a single spherical gold nanoparticle whose localized surface plasmon resonance has a strong spectral overlap with the wavelength of the pump laser. They are homogeneously encapsulated in thick hydrogel shells composed of either chemically cross-linked poly-N-isopropylacrylamide or poly[2-(2-methoxyethoxy)ethyl methacrylate], both of which exhibit a temperature-dependent volume phase transition. Thus, upon heating beyond the transition temperature, the hydrogel shells shrink. Intensity-time autocorrelation functions are recorded while illuminating the samples with the pump laser and hence heating the gold cores. With increasing laser intensity, the dynamics changes from normal Brownian motion to superdiffusion. Nevertheless, in the high-q limit, the relaxation times can be extracted and used to estimate the temperature increase, which can reach almost 10 K. This causes a significant deswelling of the hydrogel shells, which is also measured.