SIMS of organic anions adsorbed onto an aminoethanethiol self-assembled monolayer: an approach for enhanced secondary ion emission

Secondary ion mass spectrometry (SIMS) was used to monitor the uptake of organic anions from solution by aminoethanethiol (AET) monolayers on Au substrates, as a test of the applicability of this monolayer as a substrate for organic SIMS analysis. Event-by-event bombardment and detection mode coupled with coincidence counting allowed the atomic and polyatomic projectile impacts on a particular sample surface to be compared simultaneously and under the same experimental conditions. The mass spectra produced from the monolayer surface and those from Au and Si blanks demonstrate that the AET monolayer is important to the uptake of the organic anion. The exchanged monolayer surfaces were used to measure secondary ion yields, defined as the number of secondary ions detected per incident primary ion, produced from ultrathin films by (CsI)nCs+ (n = 0-2) projectiles at the limit of single-ion impacts. The yield of a tetradecyl sulfate (IDS) anion was improved by a factor of 200 using the AET substrate instead of the thick salt target. The intact ion and fragment ion yield trends produced from the AET surface were measured as a function of number of atoms in the primary projectile and energy. We observed a yield increase for both the intact ion and the fragment ion with the projectile complexity and energy. The increase in yield per projectile atom was linear for the emission of intact TDS and intact dodecyl sulfate from the AET surfaces. A supralinear yield enhancement, however, was observed for the fragment ion SO3- when the three-atom (CsI)Cs+ cluster was used. The experiments demonstrate that the various organosulfate and suffonates are weakly bound to the AET surface and their adsorption to the AET monolayer is reversible. The utility of the AET monolayer on Au was also tested as a general substrate for the characterization of derivatized organic molecules with biological and industrial importance by TOF-SIMS.     

Projectile density, impact angle and energy effects on hypervelocity impact damage to carbon fibre/peek composites

This paper explores the effects of projectile density, impact angle and energy on the damage produced by hypervelocity impacts on carbon fibre/PEEK composites. Tests were performed using the light gas gun facilities at the University of Kent at Canterbury, UK, and the NASA Johnson Space Center two-stage light gas gun facilities at Rice University in Houston, Texas. Various density spherical projectiles impacted AS4/PEEK composite laminates at velocities ranging from 2.71 to 7.14 km/s. In addition, a series of tests with constant size aluminum projectiles (1.5 mm in diameter) impacting composite targets at velocities of 3, 4, 5 and 6 km/s was undertaken at incident angles of 0, 30 and 45 degrees. Similar tests were also performed with 2 mm aluminum projectiles impacting at a velocity of approximately 6 km/s. The damage to the composite was shown to be independent of projectile density; however, debris cloud damage patterns varied with particle density. It was also found that the entry crater diameters were more dependent upon the impact velocity and the projectile diameter than the impact angle. The extent of the primary damage on the witness plates for the normal incidence impacts was shown to increase with impact velocity, hence energy. A series of tests exploring the shielding effect on the witness plate showed that a stand-off layer of Nextel fabric was very effective at breaking up the impacting debris cloud, with the level of protection increasing with a non-zero stand-off distance.     

Effects of metal nanoparticles on the secondary ion yields of a model alkane molecule upon atomic and polyatomic projectiles in secondary ion mass spectrometry

A model alkane molecule, triacontane, is used to assess the effects of condensed gold and silver nanoparticles on the molecular ion yields upon atomic (Ga(+) and In(+)) and polyatomic (C60(+) and Bi3(+)) ion bombardment in metal-assisted secondary ion mass spectrometry (MetA-SIMS). Molecular films spin-coated on silicon were metallized using a sputter-coater system, in order to deposit controlled quantities of gold and silver on the surface (from 0 to 15 nm equivalent thickness). The effects of gold and silver islets condensed on triacontane are also compared to the situation of thin triacontane overlayers on metallic substrates (gold and silver). The results focus primarily on the measured yields of quasi-molecular ions, such as (M - H)(+) and (2M - 2H)(+), and metal-cationized molecules, such as (M + Au)(+) and (M + Ag)(+), as a function of the quantity of metal on the surface. They confirm the absence of a simple rule to explain the secondary ion yield improvement in MetA-SIMS. The behavior is strongly dependent on the specific projectile/metal couple used for the experiment. Under atomic bombardment (Ga(+), In(+)), the characteristic ion yields an increase with the gold dose up to approximately 6 nm equivalent thickness. The yield enhancement factor between gold-metallized and pristine samples can be as large as approximately 70 (for (M - H)(+) under Ga(+) bombardment; 10 nm of Au). In contrast, with cluster projectiles such as Bi3(+) and C60(+), the presence of gold and silver leads to a dramatic molecular ion yield decrease. Cluster projectiles prove to be beneficial for triacontane overlayers spin-coated on silicon or metal substrates (Au, Ag) but not in the situation of MetA-SIMS. The fundamental difference of behavior between atomic and cluster primary ions is tentatively explained by arguments involving the different energy deposition mechanisms of these projectiles. Our results also show that Au and Ag nanoparticles do not induce the same behavior in MetA-SIMS of triacontane. The microstructures of the metallized layers are also different. While metallic substrates provide higher yields than metal islet overlayers in the case of silver, whatever the projectile used, the situation is reversed with gold.     

Metal-assisted secondary ion mass spectrometry using atomic (Ga+, In+) and fullerene projectiles

The advantages and drawbacks of using either monatomic or buckminsterfullerene primary ions for metal-assisted secondary ion mass spectrometry (MetA-SIMS) are investigated using a series of organic samples including additive molecules, polyolefins, and small peptides. Gold deposition is mostly performed by sputter-coating, and in some cases, the results are compared to those of thermal evaporation (already used in a previous article: Delcorte, A.; Médard, N.; Bertrand, P. Anal. Chem. 2002, 74, 4955). The microstructure of the gold-covered sample surfaces is assessed by scanning and transmission electron microscopies. The merits of the different sets of experimental conditions are established via the analysis of fragment and parent-like ion yields. For most of the analyzed samples, the highest yields of fragment and parent-like ions are already reached with the sole use of C60+ projectiles. Metallization of the sample does not lead to a significant additional enhancement. For polyethylene and polypropylene, however, gold metallization associated with Ga+/In+ projectiles appears to be the only way to observe large cationized, sample-specific chain segments (m/z approximately 1000-2000). A detailed study of the polypropylene mass spectra as a function of gold coverage shows that the dynamics of yield enhancement by metal nanoparticles is strongly dependent on the choice of the projectile, e.g., a pronounced increase with Ga+ and a slow decay with C60+. The cases of Irganox 1010, a polymer antioxidant, and leucine enkephalin, a small peptide, allow us to investigate the specific influence of the experimental conditions on the emission of parent(like) ions such as M+, (M + Na)+, and (M + Au)+. The results show a dependence on both the type of sample and the considered secondary ion. Using theoretical and experimental arguments, the discussion identifies some of the mechanisms underlying the general trends observed in the results. Guidelines concerning the choice of the experimental conditions for MetA-SIMS are provided.     

Structural analysis of ionic organotin(IV) compounds using electrospray tandem mass spectrometry

A novel electrospray ionization (ESI) mass spectrometric approach for the structure elucidation of ionic organotin(IV) compounds or complexes with weakly bonded ligands as for example monodentate carboxylates or sulfonates is proposed using both positive-ion and negative-ion ESI tandem mass spectra. The ionization mechanism of organotin(IV) compounds involves the cleavage of the most labile bond with an ionic character yielding two complementary ions, [Cat]+ and [An]-. Positively charged species containing tin atom, [Cat]+, are analyzed in the positive-ion mode and negatively charged species without the tin atom, [An]-, in the negative-ion mode. Fragmentation patterns of [C24H29N2Sn]+, [C21H22NSn]+, and [C17H30NSn]+ ions are proposed based on the detailed interpretation of MSn spectra, which is simplified by an easy recognition of characteristic tin isotopic clusters in particular fragment ions. Proposed fragmentation mechanisms are supported by comparison with MSn spectra of deuterium-labeled analogues. The applicability of this method is illustrated on two sets of organotin(IV) compounds, including seven [2,6-bis(dimethylaminomethyl)phenyl]diphenyltin(IV) derivatives with small inorganic counteranions X (Br, NO3, SCN, BF4, SeCN, CN, PF6), six organotin(IV) complexes containing two C,N-chelating ligands with azo dyes, and the identification of unknown hydrolysis products.     

Neutron energy spectra produced from thick targets by light-mass heavy ions

The measured neutron energy spectra produced from thick targets by light-mass heavy ion beams were analyzed with the phenomenological hybrid model of equilibrium and pre-equilibrium emissions. The neutron energy spectra are fitted to two (in the energy region of incident projectile energy lower than 100 MeV) and three (in the energy region of incident projectile energy higher than 100 MeV) Maxwellian-type components. The lowest energy component corresponds to the evaporation neutrons from a compound nucleus having a nuclear temperature independent of the neutron emission angle and the higher two components to the pre-equilibrium neutron emission having a nuclear temperature depending on the angle.     

In-source and postsource decay in negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of neutral oligosaccharides

Cross-ring cleavage ions produced by in-source decay (ISD), as well as deprotonated molecular ions [M - H]-, are invariably observed in negative-ion linear-mode matrix-assisted laser desorption/ionization time-of-flight mass spectrometry spectra of neutral oligosaccharides with 9H-pyrido[3,4-b]indole (norharman) as a matrix. The patterns of ISD ions depend on the oligosaccharide linkage type; thus, these ions are potentially useful in linkage analysis. In postsource decay (PSD) spectra from chlorinated molecular ions [M + Cl]-, all PSD ions are observed in the deprotonated form, although no deprotonated molecular ions are detected. In oligosaccharides having an alditol at the reducing end, deprotonated molecular ions [M - H]- are clearly seen in linear-mode mass spectra and survive in the PSD measurements. These results indicate that the deprotonation process drives ISD and PSD of oligosaccharides and that keto-enol tautomerization at the reducing terminal promotes ISD and PSD processes.     

用Bessel-Box型能量分析器的离子规和四极质谱计的性能

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Chemical sputtering and surface damage of graphite by low-energy atomic and molecular hydrogen and deuterium projectiles

We present experimental methane production yields for H⁺, ions incident on ATJ graphite in the energy range 10–250 eV/H. Below about 60 eV/H, the molecular H species give higher methane yields/H when compared with isovelocity H⁺, similar to our earlier measurements for incident deuterium atomic and molecular ions. For both D and H atomic and molecular projectiles, the yields/atom coalesce onto a single curve below projectile energies of 60 eV/atom, when plotted as a function of maximum energy transfer, under the assumption that, below this energy, the incident molecular species are largely undissociated when undergoing C–C bond breaking collisions during their collision cascade and thus produce more damage. Raman spectroscopy of a graphite sample exposed to high fluences of D⁺ and beams at high and low energies qualitatively confirmed the assumption that more surface damage is produced by the low-energy incident molecular species than by isovelocity atomic ions. While the two high-energy beam-exposed spots showed similar damage, the low-energy molecular-beam-exposed spot showed slightly more damage than the corresponding D⁺-beam-exposed spot.     

Systematic analysis of neutron yields from thick targets bombarded by heavy ions and protons with moving source model

A simple phenomenological analysis using the moving source model has been performed on the neutron energy spectra produced by bombarding thick targets with high energy heavy ions which have been systematically measured at the Heavy-Ion Medical Accelerator (HIMAC) facility (located in Chiba, Japan) of the National Institute of Radiological Sciences (NIRS). For the bombardment of both heavy ions and protons in the energy region of 100–500 MeV per nucleon, the moving source model incorporating the knock-on process could be generally successful in reproducing the measured neutron spectra within a factor of two margin of accuracy. This phenomenological analytical equation is expressed having several parameters as functions of atomic number Z_p, mass number A_p, energy per nucleon E_p for projectile, and atomic number Z_T, mass number A_T for target. By inputting these basic data for projectile and target into this equation we can easily estimate the secondary neutron energy spectra at an emission angle of 0–90° for bombardment with heavy ions and protons in the aforementioned energy region. This method will be quite useful to estimate the neutron source term in the neutron shielding design of high energy proton and heavy ion accelerators.     

Calcium Phosphate Phase Identification Using XPS and Time-of-Flight Cluster SIMS

Reproducible time-of-flight cluster static secondary ion mass spectra (ToF-SSIMS) were obtained for various standard calcium phosphate (CP) powders, which allowed for phase identification. X-ray diffraction was not able to detect signals from microscopic amounts of CP (～15 mmol m(-)(2)). The phases studied were α-tricalcium phosphate [α-Ca(3)(PO(4))(2)], β-tricalcium phosphate [β-Ca(3)(PO(4))(2)], amorphous calcium phosphate [Ca(3)(PO(4))(2)·xH(2)O], octacalcium phosphate [Ca(8)H(2)(PO(4))(6)·H(2)O], brushite (CaHPO(4)·2H(2)O), and hydroxyapatite [Ca(10)(PO(4))(6)(OH)(2)]. The SIMS spectra were obtained via bombardment with (CsI)Cs(+) projectiles. X-ray photoelectron spectroscopy (XPS) core levels of the P 2p, Ca 2p, and O 1s orbitals and the relative O 1s loss intensity were examined. The PO(3)(-)/PO(2)(-) ratios from ToF-SSIMS spectra in conjunction with XPS of the CP powders showed much promise in differentiating between these phases at microscopic CP coverages on the metal oxide surface.     

Desorption of organic overlayers by Ga and C60 bombardment

This paper reviews our recent work on computer simulations of Ga and C₆₀ bombardment of thin organic overlayers deposited on metal substrate. A multilayer of benzene, a monolayer of PS4 on Ag{1 1 1} and a self-assembled monolayer of octanethiol molecules on Au{1 1 1} were irradiated with 15 keV monoatomic (Ga) and polyatomic (C₆₀) projectiles that are recognized as valuable sources for desorption of high mass particles in secondary ion and neutral mass spectrometry (SIMS/SNMS) experiments. The results indicate that the sputtering yield decreases with the increase of the binding energy and the average kinetic energy of parent molecules is shifted toward higher kinetic energy. Although the total sputtering yield of organic material is larger for 15 keV C₆₀, the impact of this projectile leads to a significant fragmentation of ejected species. As a result, the yield of the intact molecules is comparable for C₆₀ and Ga projectiles. Our results indicate that the chemical analysis of thin organic films performed by detection of sputtered neutrals will not benefit from the use of C₆₀ projectiles.     

ACOLISSA: a powerful set-up for ion beam analysis of surfaces and multilayer structures

The experimental set-up for analysis of the charge of light ions scattered from surface atoms (ACOLISSA) is described in the following paper. ACOLISSA is used for determination of flight times of low-energy ions. It permits time-of-flight low energy ion scattering spectra of all scattered projectiles (TOF-LEIS-AP) as well as charge separated (TOF-LEIS-CS) spectra to be recorded. The evaluation of TOF-LEIS-AP spectra allows subsurface layers of the target to be studied. The analysis of TOF-LEIS-CS spectra together with ions only spectra (TOF-LEIS-IO) is used for investigation of the neutralization behaviour of projectiles at the outermost atomic layer. The performance of the set-up is described and, as an example, spectra are shown for a polycrystalline Cu target and a 7 Å Cu layer deposited on top of an alumina substrate.     

Secondary ion mass spectrometry of zeolite materials: observation of abundant aluminosilicate oligomers using an ion trap

Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)(-)(m+n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (approximately 5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.     

Deformation and fracture of a long-rod projectile induced by an oblique moving plate: Experimental tests

The influence of projectile length to diameter ratio (15, 30 and 45), plate thickness (0.5, 1 and 2 projectile diameters), projectile velocity (1500, 2000 and 2500 m/s) and plate velocity (−300 to 300 m/s) on the interaction between long-rod tungsten projectiles and oblique steel plates (obliquity 60°) was studied experimentally in small-scale reverse impact tests. The residual projectiles and their motions were characterised in terms of changes in length, velocity, angular momentum, linear momentum and kinetic energy. The parameters found to have the largest influence on the disturbance of the projectile were the plate velocity, in particular its direction, and the thickness of the plate. In the ranges studied, the influence of length to diameter ratio and of projectile velocity were found to be less important.     

Exploratory investigations of hypervelocity intact capture spectroscopy

The ability to capture hypervelocity projectiles intact opens a new technique available for hypervelocity research. A determination of the reactions taking place between the projectile and the capture medium during the process of intact capture is extremely important to an understanding of the intact capture phenomenon, to improving the capture technique, and to developing a theory describing the phenomenon. The intact capture of hypervelocity projectiles by underdense media generates spectra, characteristic of the material species of projectile and capture medium involved. Initial exploratory results into real-time characterization of hypervelocity intact capture techniques by spectroscopy include ultra-violet and visible spectra obtained by use of reflecting gratings, transmitting gratings, and prisms, and recorded by photographic and electronic means. Spectrometry proved to be a valuable real-time diagnostic tool for hypervelocity intact capture events, offering understanding of the interactions of the projectile and the capture medium during the initial period and providing information not obtainable by other characterizations. Preliminary results and analyses of spectra produced by the intact capture of hypervelocity aluminum spheres in polyethylene (PE), polystyrene (PS), and polyurethane (PU) foams are presented. Included are tentative emission species identifications, as well as gray body temperatures produced in the intact capture process.     

Europium emission centers in CsI:Eu crystal

Absorption, excitation and luminescence spectra of pure and Eu doped CsI crystals were studied depending on the activator content, excitation energy, heat treatment and X-ray irradiation. Several types of Eu²⁺ related centers were found. It is shown that complex centers are stable at room temperature but their structure and concentration changes at heat treatment and under irradiation. The increased content of oxygen-containing radicals was determined by IR spectroscopy in Eu-containing crystals as opposed to pure one. It is supposed that some of emission centers in CsI:Eu are caused by the presence of intrinsic (vacancy type) and extrinsic (oxygen or hydroxyl ions) defects located in the nearest environment of Eu²⁺ ions.     

Experimental and theoretical study of the neutron dose produced by carbon ion therapy beams

High-energy (12)C ions offer favourable conditions for the treatment of deep-seated local tumours. Several facilities for the heavy ion therapy are planned or under construction, for example the new clinical ion-therapy unit HIT at the Radiological University Clinics in Heidelberg. In order to improve existing treatment planning models, it is essential to evaluate the secondary fragment production and to include these contributions to the therapy dose with higher accuracy. Secondary neutrons are most abundantly produced in the reactions between (12)C beams and tissues. The dose contribution to tissues by a neutron is fairly small compared with the projectile and the other charged fragments due to no ionisation and the small reaction cross-sections; however, it distributes in a considerably wider region beyond the bragg-peak because of the strong penetrability. Systematic data on energy spectra and doses of secondary neutrons produced by (12)C beams using water targets of different thicknesses for various detection angles have therefore been measured in this study at GSI Darmstadt.     

Effect of thin oblique moving plates on long rod projectiles: A reverse impact study

The geometry and motion of long rod projectiles after penetrating thin obliquely oriented and moving armour plates were studied. Plates moving in their normal directions towards as well as away from the projectile (scalar product of velocities negative and positive, respectively) were considered. The influences of plate velocity and obliquity (angle between the normal of the plate and the axis of the projectile) were investigated through small-scale reverse impact tests with tungsten projectiles of length 30 mm and diameter 2 mm, and with 2 mm-thick steel plates. The obliquity (30°, 60° and 70°) and the plate velocity (300 to −300 m/s) were varied systematically for a projectile velocity of 2000 m/s. The disturbing effect of the plate on the projectile was characterised in terms of changes in length, velocity, angular momentum, linear momentum and kinetic energy. Plates with obliquity 60–70° moving away from the projectiles with velocity 200–300 m/s were found to cause extensive fragmentation of the projectile and to have large disturbing effects in terms of all measures used.