Dissociation processes involving phosphorus cations were investigated during laser-assisted atom probe tomography of crystalline indium phosphide (InP). This technique not only allows the formation of medium-sized phosphorus cations by means of femtosecond laser pulses under ultrahigh vacuum and high electric field conditions but also allows one to study the time-resolved dissociation dynamics. Data reveal the formation of cations up to P232+ and their subsequent dissociation into two smaller Pk+ cations (k > 2). The use of a time- and position-sensitive detector combined with numerical calculations provided information related to the molecule orientation, decay time, and kinetic energy release during dissociation phenomena. Results suggest that the dissociation processes are most likely due to the emission of Pk2+ cations in excited states and their subsequent decay in low field regions during their flight toward the detector. This study provides operative guidelines to obtain information on dissociation processes using a tomographic atom probe as a reaction microscope and indicates the current capabilities and limitations of such an approach.
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