Correlation spectroscopy based on non-linear response of silver colloids (including SEHRS)

The correlation curves of both types of colloid show one step (τ1/2∼10 ms) which can be associated with lateral diffusion of the individual particles. Its τ1/2-value is larger for the poly-disperse colloid, which contains larger particles. In addition, we find a second step, its relative amplitude being dependent on experimental parameters, whose τ1/2-value is, however, essentially the same for all samples investigated (τ′1/2∼50 μs). We assign this correlation time to processes that lead to a restructuring of the surface and the formation and destruction of so-called 'hot spots'. Under optimum condition, the efficiency for all non-linear processes connected with one such 'hot spot' is extremely high. 'Hot particles' contain at least one hot spot and can therefore dominate the non-linear signal without the need of aggregation (field enhancement in the gap between particles).