Irradiation of aqueous [AuCl4]− with 532 nm nanosecond (ns) laser pulses produces monodisperse (PDI = 0.04) 5-nm Au nanoparticles (AuNPs) without any additives or capping agents via a plasmon-enhanced photothermal autocatalytic mechanism. Compared with 800 nm femtosecond (fs) laser pulses, the AuNP growth kinetics under ns laser irradiation follow the same autocatalytic rate law, but with a significantly lower sensitivity to laser pulse energy. The results are explained using a simple model for simulating heat transfer in liquid water and at the interface with AuNPs. While the extent of water superheating with the ns laser is smaller compared to the fs laser, its significantly longer duration can provide sufficient energy to dissociate a small fraction of the [AuCl4]− present, resulting in the formation of AuNPs by coalescence of the resulting Au atoms. Irradiation of initially formed AuNPs at 532 nm results in plasmon-enhanced superheating of water, which greatly accelerates the rate of thermal dissociation of [AuCl4]− and accounts for the observed autocatalytic kinetics. The plasmon-enhanced heating under ns laser irradiation fragments the AuNPs and results in nearly uniform 5-nm particles, while the lack of particles’ heating under fs laser irradiation results in the growth of the particles as large as 40 nm.

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