Photoionization of gas-phase versus ion-beam-desorbed dopamine with femtosecond laser pulses.

We have investigated the photoionization of gas-phase and ion-beam desorbed dopamine using femtosecond laser pulses at wavelengths of 800, 400, 267, and 200 nm. Photoionization of gas-phase dopamine is found to produce the molecular ion, and three fragment ions at all four wavelengths, with the branching ratios strongly wavelength dependent. Photoionization at 400 and 267 nm yields the highest molecular ion signal, while that at 800 and 200 nm produces very little molecular ion signal. An excited-state lifetime of approximately 10 ps following 267-nm excitation has been measured for dopamine using time-resolved pump-probe techniques. The short-lived excited state suggests that internal conversion, intersystem crossing, and/or dissociation is a concern when ionizing at this wavelength using longer laser pulses. Photoionization of ion-beam-desorbed dopamine exhibits a large degree of fragmentation at all four wavelengths, though 267-nm photoionization produces the highest yield of dopamine fragment ions. Power dependence studies show a high degree of internal excitation. A direct comparison of ion yields obtained for photoionization of ion-beam-desorbed dopamine at 267 nm to that for SIMS shows a 20-fold increase in signal.

Vacuum ultraviolet single photon versus femtosecond multiphoton ionization of sputtered germanium clusters.

Neutral atoms and clusters desorbed from a solid germanium surface by ion bombardment are detected by laser postionization and time-of-flight mass spectrometry. Two different photoionization schemes are compared which are generally believed to be candidates for the 'soft' ionization of polyatomic species without significant photon induced fragmentation. First, a single photon ionization process is employed using an F2 laser as an intense VUV source with a photon energy in excess of all relevant ionization potentials. It is shown that the available laser pulse energy is sufficient to saturate the ionization of Ge atoms and all detected Ge(n) clusters. The resulting mass spectra are compared to those obtained with a non-resonant multiphoton ionization process using a high intensity laser delivering pulses of 250 femtoseconds duration at a wavelength of 267 nm. Also in this case, the ionization process can apparently be driven into saturation. The mass spectra measured under these conditions are found to be almost identical to those obtained using single photon ionization. We take this as an indication that the results obtained with both postionization techniques closely reflect the true cluster sputtering yields and, in particular, are not dominated by photon induced fragmentation.

Performance characteristics of a chemical imaging time-of-flight mass spectrometer.

A chemical imaging time-of-flight secondary ion mass spectrometer is described. It consists of a liquid metal ion gun, medium energy resolution reflectron mass analyzer, liquid nitrogen cooled sample stage, preparation chamber and dual stage entry port. Unique features include compatibility with laser postionization experiments, large field of view, cryogenic sample handling capability and high incident ion beam current. Instrument performance is illustrated by the characterization of scanning electron microscopy grids, silver and functionalized polystyrene beads and the postionization of an organic overlayer on a gold substrate.

Postionization of molecules desorbed from surfaces by keV Ion bombardment with femtosecond laser pulses.

We report the use of femtosecond laser photoionization of sputtered neutral molecules to enhance the sensitivity of detection and to improve the prospects for molecule-specific imaging experiments. Results are presented for patterned metal oxides, polycyclic aromatic hydrocarbons and several amino acids. In addition to increased signal levels, we find that is photoionization generally yields simpler mass spectra than the corresponding SIMS spectra, although considerable fragmentation is observed in both cases.