Speciation in nanosecond laser ablation of zinc in water

Abstract

In situ experimental methods have been applied to resolve mass flow and chemical speciation in the pulsed laser ablation of zinc in water. The chemical speciation has been resolved by time-resolved μ-X-ray absorption spectroscopy and mapped onto the macroscopic mass flow during material ejection from the metallic target and bubble dynamics of evaporated water. Large particles and agglomerates have been detected via dark-field X-ray imaging with a Shack-Hartmann sensor. The characteristic of the dynamics is that the vapor bubble is nearly homogeneously filled with ablated material. This persists during bubble collapse, which means that the ablated particles are captured and retracted towards the target. Limited mass escape is indicated by the X-ray absorption signal. Importantly, the near-edge structure at the Zn-Kα transition delivers information on the chemical state of the ejected material. It clearly confirms that oxidation is not present within the bubble phase and the following sub-millisecond time scale. The oxidation proceeds on Zn nanoparticles in suspension on a second to minute course. Within the first microseconds, a Zn atom phase is detected that resembles Zn vapor. The addition of either reductive NaBH4 or oxidative HAuCl4 to the water phase influences the quantity of the atom contribution moderately, but does not influence the initial atom phase. Such behavior must be understood in terms of the nanosecond pulse excitation. After ejected material and a plasma is formed within the pulse duration of 7 ns the laser is able to further heat the ejecta and transform it partly into vapor. Correspondingly, the coupling of energy into the ablation zone as followed by plasma intensity and bubble size follows a threshold behavior as a function of laser fluence, marking the onset of laser-plasma heating. The reaction conditions inside the bubble are probably reductive due to the concomitant formation of excess hydrogen.