Surfaces can be probed with a variant of secondary ion mass spectrometry (SIMS) where the bombardment is with a sequence of single keV projectiles, each resolved in time and space, coupled with the separate record of the secondary ions (SIs) ejected from each projectile impact. The goal of this study was to demonstrate an efficient mode of SIMS where one obtains valid analytical information with a minimum of projectiles and hence a minimum of sample consumption. An inspection of the ejected SIs from individual bombardment events will reveal ??super efficient?? collision cascades i.e., events, where two or more secondary ions were emitted simultaneously. It has been shown that these coincidental emissions can provide information about the chemical composition of nano-domains. Previous studies using coincidence counting mass spectrometry (CCMS) indicated an enhancement of identifying correlations between SIs which share a common origin. This variant of SIMS requires an individual projectile impact thus causing SI emission from a surface area of ~5 nm in radius. Thus, in an event where two or moreSIs are ejected from a single projectile impact, they must originate from atoms and molecules co-located within the same nano-domain. Au nanorods covered by a 16-mercaptohexadecanoic acid (MHDA) monolayer were analyzed using this methodology. A coincidence ion mass spectrum was obtained for the MHDA monolayer covered Au nanorods which yielded a peak for a Au adduct. Similar results were obtained for a sample with a MHDA monolayer on a Au coated Si wafer. A series of samples consisting of Cu aggregates and AuCu alloys were investigated by SIMS to demonstrate that this technique is appropriate for characterizing nanoparticles. The mass spectra of these samples indicated that Au200 4+ is an effective projectile to investigate the surface of the target because it was able to penetrate through the poly(vinylpyrrolidone) (PVP) stabilizer that coated the surface of these nanoparticles. Coincidence mass spectra of the Cu aggregates yielded molecules colocated within the same nano-domain. Finally, this methodology was used to investigate surface structural effects on the occurrence of ??super-efficient?? events. The results indicated that it is possible to distinguish between two phases of ??-ZrP compounds although the stoichiometry remains the same.

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Graduation date: 1993

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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.

Impacts of high kinetic energy massive gold clusters (~ 500 keV Au400+4) exhibit significantly enhanced secondary ion yields relative to traditional atomic or polyatomic primary ions (e.g. Au3 and C60). The one-of-a-kind instrument used to generate these hypervelocity nanoparticles (~2 nm diameter, ~30 km/s) and monitor emissions from their impacts (SIMS) is described in detail for the first time. The projectile range of 520 keV Au400+4 is measured to be ~20 nm in amorphous carbon and projectile disintegration is observed at the exit of carbon foils as thin as 5 nm. These experiments were performed by monitoring carbon cluster ions emitted from both sides of a foil impacted by the projectile. Surprisingly, clusters emitted in the forward direction are larger than those emitted backward. The composition of the mass spectra is shown to depend on both the thickness of the foil and the size of the projectile. Secondary ion yields for a variety of materials including peptides, lipids, drugs, polymers, inorganic salts, and various small molecules have been measured and molecular ion yields for many of these species exceed unity. Multiplicity measurements show that up to seven molecular ions of leucine-enkephalin (YGGFL) can be detected from the impact of a single projectile. SI yields measured with ~500 keV Au400+4 are generally one to two orders of magnitude greater than those obtained with 130 keV Au3+ and 50 keV C60+ projectiles. The high molecular ion yields observed suggest the internal energies of ions emitted from massive cluster impacts are relatively low. In order to address this hypothesis, a novel method for measuring secondary ion internal energies was developed using a series of benzylpyridinium salts. Using this method, the internal energies were measured to be ~0.19 eV/atom, which is a factor of five less than that seen in atomic-SIMS. Sample metallization is shown to be ineffective for further increasing secondary ion yields with Au400, despite observations from previous molecular dynamic simulations. Coincidence mass spectrometry is applied to nanometric chemical segregations found on samples coated with thin layers of gold and silver. It is possible to measure the surface coverages of the metallic and underlying organic layers using mass spectrometry in a non-imaging mode.

The chemical characterization of individual nanoparticles (NPs) </= 100 nm in diameter is one of the current frontiers in analytical chemistry. We present here, a methodology for the characterization of individual NPs by obtaining molecular information from single massive cluster impacts. The clusters used in this secondary ion mass spectrometry (SIMS) technique are Au4004+ and C60+. The ionized ejecta from each impact are recorded individually which allows to identify ions emitted from a surface volume of ~10 nm in diameter and 5-10 nm in depth. The mode of analyzing ejecta individually from each single cluster impact gives insight into surface homogeneity, in our case NPs and their immediate surroundings. We show that when the NPs (50 nm Al) are larger than the size of the volume perturbed by the projectile, the secondary ion emission (SI) resembles that of a bulk surface. However, when the NP (5 nm Ag) is of the size range of the volume perturbed by projectile the SI emission is different from that of a bulk surface. As part of this sub-assay volume study, the influence of neighboring NP on the SI emission was examined by using a mixture of different types of NPs (5 nm Au and 5 nm Ag). The methodology of using cluster SIMS via a sequence of stochastic single impacts yield information on the surface coverage of the NPs, as well as the influence of the chemical environment on the type of SI emission. We also present a case of soft landing NPs for laser desorption ionization mass spectrometry. NPs enhance the SI emission in a manner that maintains the integrity of the spatial distribution of molecular species. The results indicate that the application can be extended to imaging mass spectrometry.

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.

Combining cesium (Cs) bombardment with positive secondary molecular ion detection (MCs+) can extend the analysis capability of Secondary Ion Mass Spectrometry (SIMS) from the dilute limit (<1%) to matrix elements. The MCs+ technique has had great success in quantifying the sample composition of III-V semiconductors as well as dopants and/or impurities; however, it has been less effective at reducing the matrix effect for IV compounds, particularly Si-containing compounds, due to Cs overloading at the surface during the analysis from the Cs primary ion beam. The Cs overloading issue is attributable to the mobility and relocation of the implanted Cs to the surface; this effect happens almost instantaneously. Once the surface is overloaded with Cs, the excess Cs begins to reneutralize the ionization Cs and, as a result, the MCs+ technique is ineffective at reducing the matrix effect. This research provides new insights for improving the MCs+ technique and elucidating the Cs mobility. A combination of multiple experimental techniques and theoretical modeling was implemented to assess the Cs retention, up-take, and distribution differences between group III-V and IV materials. Early experiments revealed a temperature-dependent component of the Cs mobility, prompting an investigation of this phenomenon. Therefore, we designed, built, and installed a variable temperature stage for our SIMS with temperatures ranging from -150 to 300 C. This enabled us to study the temperature-dependent component of the Cs mobility and the effect it has on the secondary ion emission processes. Additionally, a method was devised to quantify the amount of neutralization and ionization due to the relocated Cs. The results allow for a more thorough understanding of the material dependence on the Cs+-sample interaction and the temperature component of the Cs mobility. / Ph. D.

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