Secondary ion mass spectrometry (SIMS) is a surface analysis technique capable of providing isotopic and molecular information. SIMS uses keV projectiles to impinge upon a sample resulting in secondary ion emission from nanometric dimensions. It is well documented that secondary ion emission is enhanced using cluster projectiles compared to atomic projectiles. Previous studies of enhanced secondary ion yields with cluster projectiles have led to the present study dealing with the scope of C60 as a projectile for SIMS. The secondary ion yields (i.e., the number of secondary ions detected per projectile impact) from impacts of 10-26 keV C24H12+, C60+, gramicidin S+ and C60F40+ projectiles were examined to compare the effectiveness of the projectiles. The [M-H]- secondary ion yields from several organic samples varied inversely with the molecular weight. Multiple ion emission decreases monotonically as a function of the number of secondary ions emitted per impact and varies with impact energy such that higher energies produce more multiple ion emission. The emission of CN- from biological samples as a function of carbon-based projectile characteristics was examined to explore the possibility of using CN- as a molecular identifier. CN- emission was found to be the product of both direct and recombination/rearrangement emission. Re-emitted projectile atoms in the form F- were found under C60F40+ bombardment. Two forms of re-emitted F- were found: One form in which F atoms retained a portion of the initial kinetic energy, and a second in which the F atoms deposited most of the initial kinetic energy into the surface before being ejected. The [M-H]- secondary ion yield of gramicidin S was increased ~ 15 times by embedding the analyte in a matrix of sinapic acid. These results show the optimum carbon based projectile for a given sample is dependent upon the signal to be monitored from the surface. The results also show CN- has potential as a molecular identifier. Additionally, the detection of re-emitted F- confirms prior predictions of re-emitted projectile atoms.

Secondary ion mass spectrometry (SIMS) is a surface analysis technique capable of providing isotopic and molecular information. SIMS uses keV projectiles to impinge upon a sample resulting in secondary ion emission from nanometric dimensions. It is well documented that secondary ion emission is enhanced using cluster projectiles compared to atomic projectiles. Previous studies of enhanced secondary ion yields with cluster projectiles have led to the present study dealing with the scope of C60 as a projectile for SIMS. The secondary ion yields (i.e., the number of secondary ions detected per projectile impact) from impacts of 10-26 keV C24H12+, C60+, gramicidin S+ and C60F40+ projectiles were examined to compare the effectiveness of the projectiles. The [M-H]- secondary ion yields from several organic samples varied inversely with the molecular weight. Multiple ion emission decreases monotonically as a function of the number of secondary ions emitted per impact and varies with impact energy such that higher energies produce more multiple ion emission. The emission of CN- from biological samples as a function of carbon-based projectile characteristics was examined to explore the possibility of using CN- as a molecular identifier. CN- emission was found to be the product of both direct and recombination/rearrangement emission. Re-emitted projectile atoms in the form F- were found under C60F40+ bombardment. Two forms of re-emitted F- were found: One form in which F atoms retained a portion of the initial kinetic energy, and a second in which the F atoms deposited most of the initial kinetic energy into the surface before being ejected. The [M-H]- secondary ion yield of gramicidin S was increased ~ 15 times by embedding the analyte in a matrix of sinapic acid. These results show the optimum carbon based projectile for a given sample is dependent upon the signal to be monitored from the surface. The results also show CN- has potential as a molecular identifier. Additionally, the detection of re-emitted F- confirms prior predictions of re-emitted projectile atoms.

Some collision cascades, induced by keV polyatomic projectiles, result in the emission of multiple secondary ions. Such co-emissions imply that the ejecta originate from molecules co-located within the nano-volume perturbed by a single projectile impact. The relevance for the chemical analysis of nano-domains depends on the effectiveness of the projectile to cause co-emission of two or more secondary ions. This research examines how projectile characteristics, i.e. the energy and number of constituent atoms in the projectile, influence multiple secondary ion emission, or "superefficient" events. In addition we examine the relevance of this technique for nanostructure investigation. Yields have been measured for multi-ion emission events as a function of projectile characteristics. The data show that some collision cascades are "superefficient". For example, in a four-ion emission event, the yield for the phenylalanine quasi-molecular ion is two orders of magnitude larger from Au4+ impacts than from equal velocity Au+ projectiles. Yields for the co-emission of two phenylalanine quasi-molecular ions from "super-efficient" events have been measured. This case is particularly productive in that the detection of two analytically significant ions is recorded from a single event. Large increases (one to two orders of magnitude) in co-emitted ion yields were observed with increasing projectile energy and complexity. Correlation coefficients were calculated for the co-emission of two Ph ions, their behavior suggests differences in emission pathways for bombardment by atomic and polyatomic projectiles. Finally, we use this methodology to investigate surface structural effects on the occurrence of "super-efficient" events. The results indicate that it is possible to distinguish between two phases of a chemical compound although the stoichiometry remains the same. These results confirm previous predictions concerning the chemical nature of these "super-efficient" events. Also shown is that they are sensitive to the surface nanoenvironment. This approach extends the technology of Secondary Ion Mass Spectrometry by providing a methodology for probing surface nano-domains at the sub100 nm level.

Some collision cascades, induced by keV polyatomic projectiles, result in the emission of multiple secondary ions. Such co-emissions imply that the ejecta originate from molecules co-located within the nano-volume perturbed by a single projectile impact. The relevance for the chemical analysis of nano-domains depends on the effectiveness of the projectile to cause co-emission of two or more secondary ions. This research examines how projectile characteristics, i.e. the energy and number of constituent atoms in the projectile, influence multiple secondary ion emission, or "superefficient" events. In addition we examine the relevance of this technique for nanostructure investigation. Yields have been measured for multi-ion emission events as a function of projectile characteristics. The data show that some collision cascades are "superefficient". For example, in a four-ion emission event, the yield for the phenylalanine quasi-molecular ion is two orders of magnitude larger from Au4+ impacts than from equal velocity Au+ projectiles. Yields for the co-emission of two phenylalanine quasi-molecular ions from "super-efficient" events have been measured. This case is particularly productive in that the detection of two analytically significant ions is recorded from a single event. Large increases (one to two orders of magnitude) in co-emitted ion yields were observed with increasing projectile energy and complexity. Correlation coefficients were calculated for the co-emission of two Ph ions, their behavior suggests differences in emission pathways for bombardment by atomic and polyatomic projectiles. Finally, we use this methodology to investigate surface structural effects on the occurrence of "super-efficient" events. The results indicate that it is possible to distinguish between two phases of a chemical compound although the stoichiometry remains the same. These results confirm previous predictions concerning the chemical nature of these "super-efficient" events. Also shown is that they are sensitive to the surface nanoenvironment. This approach extends the technology of Secondary Ion Mass Spectrometry by providing a methodology for probing surface nano-domains at the sub100 nm level.