Low energy sputtering of neutral Cu2 molecules

The ratios of relative yields of neutral sputtered Cu₂ molecules to neutral sputtered Cu atoms were found to be linearly proportional to the sputtering yield of Cu, from a Cu target under bombardment by Ar⁺ ions (energy 50–90 eV), as determined by secondary neutral mass spectrometry.     

Femtosecond laser-induced fragmentation and cluster formation studies of solid phase trinitrotoluene using time-of-flight mass spectrometry

We use surface-femtosecond laser mass spectrometry to study the fragments/products formed when trinitrotoluene (TNT) is subjected to femtosecond laser pulse irradiation and to study the conditions under which TNT is removed from a solid surface. In surface-femtosecond laser mass spectrometry a compound is deposited on a solid substrate and is desorbed into vacuum by femtosecond irradiation forming a plume of ionized and neutral species. The positive or negative ions are then accelerated by an electric potential and allowed to drift in the field-free region of a time-of-flight mass spectrometer. The mass-to-charge ratio of each ion is obtained using the value of the accelerating field and the ion flight time. In this paper we report femtosecond laser mass spectra for the positive ions formed by desorbing TNT with 130 fs pulses centered at 800 nm for fluences ranging from 7 to 1.4 × 10⁵ J/m². The conditions under which TNT removal and ionization occur are also discussed.     

Depth distribution of SiD and SiD2 complexes in silicon bombarded by 10 keV D+ 2 ion

Abstract

A secondary ion mass spectrometry (SIMS) and a neutral molecule mass spectrometry (NMMS) study of deuterium trapping in a single crystalline silicon as a result of ion irradiation at fluences 10^16--10¹⁸ cm-² are presented. An attempt has been made to observe the formation and evolution of defect profiles containing one or two deuterium atoms (SiD- and SiD₂-complexes). The proposed model of radiation-induced sequential reactions describes satisfactorily the accumulation of SiD- and SiD₂-complexes and the reemission of D₂-molecules.     

Praseodymium-doped Ti:LiNbO3 waveguides

3 by diffusion doping is investigated by means of secondary neutral mass spectrometry and secondary ion mass spectrometry. The diffusion of praseodymium in LiNbO₃ can be described by Fick’s laws of diffusion with a concentration-independent diffusion coefficient and a limited solubility of praseodymium in LiNbO₃ increasing exponentially with rising temperature. The diffusion depends on the Li₂O content of the LiNbO₃ crystal. For LiNbO₃ crystals with a nominal slight difference in the congruent composition, the diffusion constants and activation energies for Z-cut LiNbO₃ are 3.28×10^-5 cm²/s and 2.27 eV, and 1.39×10^-5 cm²/s and 2.24 eV, respectively. Titanium-doped waveguides are formed in Pr:LiNbO₃ and characterised in relation to waveguide loss and absorption in the visible and near infrared. Received: 17 September 1998 / Accepted: 11 November 1998     

Pressing to the extremes

In the last decade the study of ion-neutral reactions has been dramatically advanced by the development and energetic exploitation of the steady-state flowing afterglow method by Eldon Ferguson and his colleagues at the National Oceanic and Atmospheric Administration (NOAA), Boulder, Colorado. This new technique has provided a very large number of ion–molecule rate coefficients for reactions at thermal energy.

In this method a fast flow of carrier gas (usually helium) is established in a long flow tube, the reactant ions (A⁺) are generated near the gas input end of the tube (the excitation region) and these ions are carried along the tube in the carrier gas flow. The neutral reactant (B) is introduced into the flowing gas stream near the mid-point of the flow tube so that the reaction A⁺+ B →products, takes place along the remainder of the tube length (the reaction region). The reactant ion A⁺ and any ions produced in the reaction are monitored by a mass spectrometer located at the gas exit end of the tube. The variation of the A⁺ mass spectrometer signal as a function of neutral reactant injection rate B yields the rate coefficient k for the reaction if gas flow rates and tube dimensions are known.

The great advantage and versatility of the steady-state flowing afterglow system lies primarily in the separate control that can be exercised over the ions and the neutrals prior to the reaction and also to the fact that the atomic processes occurring in the afterglow are susceptible to many diverse forms of investigation such as emission and absorption spectroscopy, laser spectroscopy, microwave interferometry and Langmuir probes, as well as mass spectrometry. Furthermore, chemically unstable neutral particles can be readily studied in these systems.     

Experiments on clusters

In this contribution we discuss four different types of experiments that have been conducted at molecular beams of neutral clusters. The size of particularly stable sodium chloride clusters and their corresponding geometrical structure is inferred from intensity anomalies in mass spectra. This information is obtained either for charged or for neutral clusters depending on whether the clusters are ionized by electron impact or by multiphoton absorption. The important role of fragmentation in mass spectrometry of xenon clusters is revealed by multiphoton ionization; dissociative reactions occurring on the time scale of 10⁻⁷ s with respect to the ionizing event can be analyzed. The solvation energy of negatively charged carbon dioxide clusters as a function of cluster size is obtained from electron attachment spectra. A resonance in the ion yield close to zero eV electron energy signifies that all clusters except for the monomer feature a positive electron affinity. An analysis of the kinetic energy of fragment ions, originating from delayed dissociation of triply charged carbon dioxide clusters, reveals that the size distribution of their fission fragments is extremely symmetric.     

High-temperature thermal evolution of SiAs precipitates in silicon

The thermal evolution of monoclinic SiAs precipitates at 1050° C in silicon samples implanted with 1 and 1.5×10¹⁷ As/cm² was followed by transmission electron microscopy (TEM) and secondary neutral mass spectrometry (SNMS). These experiments show, for the first time, the coexistence of two different states of As in silicon, i.e., the electrically active and the inactive mobile dopant, in equilibrium with monoclinic SiAs precipitates. Moreover, they provide, for the saturation concentration of As in silicon, which includes both these states, a value of 3×10²¹ cm^–3 at 1050° C.     

Experiments on the sputtering of neutral Cu2 dimers from Cu by Ar+ ions (60–300 eV)

A planar polycrystalline copper target was bombarded normally by Ar⁺ ions with energies ranging from 60 to 300 eV. in the source of a mass spectrometer. The neutral particles sputtered normally from the target were post-ionized and analyzed in the mass spectrometer. A thermionically sustained, magnetically confined low pressure arc plasma was used to supply the bombarding ions, and for post-ionization of the neutral sputtered species. It was found that the relative yields of the sputtered neutral post-ionized Cu₂ dimers are linearly proportional to S², where S is the total sputtering yield for Ar⁺ -Cu. The results support the recombination model for the formation of neutral dimers in sputtering.     

Application of the surface ionization for the detection of secondary particles in the secondary-ion mass spectrometry (SIMS)

A method for postionization in the course of ion sputtering that is based on surface ionization of the sputtered particles is developed. The estimations show that the method allows a significant increase in the sensitivity of the secondary-ion mass spectrometry for several elements. Nonadditive increase in the sputtering coefficient of indium is experimentally studied using the surface-ionization method of postionization when the number of atoms in projectile clusters Bi _m ⁺ (m = 1–7) increases at energies 2–10 keV. Such a scheme for the detection of neutral particles can be used in alternative methods for the surface analysis, in particular, laser evaporation of surface and electron-stimulated desorption.     

Observation of the matrix effect due to the electron transfer in laser ablation plasma

We investigate the so-called “matrix effect” on the relative intensities of ions in mixed solutions of alkali salts by using femtosecond laser ablation time-of-flight mass spectrometry (fsLA-TOFMS). For the 1:1 mixed solution of sodium and potassium salts, the intensity ratio of cations (Na⁺/K⁺) decreases as the total concentration increases. From the measurement for the mixed solution of lithium, sodium, potassium, rubidium, and cesium solutions, we find out significant dependence of each ion intensity on the total concentration. The results suggest that the electron transfer from neutral atoms to cations coexistent in the ablation plasma affects the relative ion intensities observed with TOFMS when the total ion concentration is high.     

Supersymmetric relics from the big bang

We consider the cosmological constraints on supersymmetric theories with a new, stable particle. Circumstantial evidence points to a neutral gauge/Higgs fermion as the best candidate for this particle, and we derive bounds on the parameters in the lagrangian which govern its mass and couplings. One favored possibility is that the lightest neutral supersymmetric particle is predominantly a photino $\text{～}\text{γ}$ with mass above $\text{1}\text{2}$ GeV, while another is that the lightest neutral supersymmetric particle is a Higgs fermion with mass above 5 GeV or less than O(100) eV. We also point out that a gravitino mass of 10 to 100 GeV implies that the temperature after completion of an inflationary phase cannot be above 10¹⁴ GeV, and probably not above 3 × 10¹² GeV. This imposes constraints on mechanisms for generating the baryon number of the universe.     

Unimolecular dissociation of singly- and multiply-charged fullerene ions

The formation of fragment ions from C₆₀ due to electron impact ionization leading to a bimodal fragmentation pattern with a minimum around the cluster size of 30 is investigated with help of mass spectrometric techniques. Based on a detailed analysis of the energetics and kinetics of the singly- and multiply-charged fragment ions by two-sector field mass spectrometry (MIKE-scans) we can conclude that on the one hand some of the dissociation reactions proceed via evaporation of an intact C₆ ⁺ or C₄ ⁺ unit (and not via the sequential loss of smaller molecular carbon units). On the other hand, measured appearance energies and the direct observation of sequential C₂-loss reactions confirm that the sequential loss of neutral C₂ units is the dominant production mechanism for C_n ^z+ fragment ions with sizes 40 < n < 60. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phosphorus cluster production by laser ablation

Neutral and charged phosphorus clusters of a wide size range have been produced by pulsed laser ablation (PLA) in vacuum at 532, 337, and 193 nm ablating wavelengths and investigated by time-of-flight mass spectrometry. The neutral P_n clusters are even-numbered with local abundance maxima at n=10 and 14, while the cationic and anionic clusters are preferentially odd-numbered with P₇⁺, P₂₁⁺, and P₁₇^- being the most abundant ions. The dominance of the magic clusters is more pronounced at 337-nm ablation that is explained by efficient direct ejection of their building blocks under these conditions. Nanocrystalline phosphorus films have been produced by PLA in ambient helium gas. PACS 52.38.MF; 61.46.+w; 79.20.Ds; 81.07.B; 81.16.Mk     

Mass spectrometry of molecular neutrals sputtered from amino acid overlayers on Au and Ni

Mass spectrometry of electron post-ionized sputtered neutrals (e-beam SNMS) is a useful new surface mass spectrometry, complementary to secondary ion (SIMS) and thermal desorption (TDMS) mass spectrometry. This is demonstrated by applying these three techniques to identical mono- and multimolecular overlayers of glycine on the metal (Me) substrates Ni and Au. In particular the molecular neutrals M⁰ and (M + Me)^o supply new information about the sputtering process, and show the analytical potential of e-beam SNMS for quantitative molecular surface analysis.     

Capture of an electron by ions in methionine and norleucine molecules

The relative cross sections of processes taking place when H⁺ and He²⁺ ions with an energy of 6z keV (z is the ionic charge) capture an electron from molecules of C₅H₁₁NO₂S methionine (proteogenic amino acid) and C₆H₁₃NO₂ norleucine (nonproteogenic amino acid) are measured by time-of-flight mass spectrometry (a methionine molecule transforms into a norleucine molecule by substituting the CH₂ group for the S heteroatom). The fragmentation pattern of resulting molecular ions is established from correlation analysis of the detection times of all fragment ions. The results are compared with experimental data for fragmentation of the same molecules ionized by electrons and photons. In these amino acids, the pattern of molecular ion fragmentation is found to depend on the type of molecule ionization. However, the detachment cross section of the COOH neutral group or residue (neutral or charged) R of a side chain of the amino acid is invariably among the largest. The relative cross sections of capture with single and double ionization of molecules are measured.     

XeCl-laser-generated ablation products from a nitrogen-rich polymer studied by laser-ionization mass spectrometry

Laser-ionization time-of-flight mass spectrometry has been used to probe laser-ablation products from a nitrogen-rich polymer at a wavelength of 308 nm. The ablation products at a laser fluence of 150 mJ/cm² showed, similar to 532 nm ablation studied previously [18], two strong peaks due to neutral species that were assigned to C⁺ and CN⁺, as well as several weak peaks that were assigned to CH⁺, HCN⁺, HCNH⁺, H_nN–CN⁺ (n=1–3), and H₂N–C=N–CN⁺ or H₂N–C=N–CN⁺. The ablation products at 870 mJ/cm² revealed, in addition to a broad signal due to ionic products generated directly by the ablation laser, several peaks due to neutral products that were assigned to C⁺, C ₂ ⁺ , C ₃ ⁺ , CN⁺, HCN⁺, HCNH⁺, and NCCN⁺. The most probable flight velocities for major neutral products are 5.7×10⁴ cm/s at 150 mJ/cm² and 2.3–2.7×10⁴ cm/s at 870 mJ/cm². The results at a laser fluence of 150 mJ/cm² support the finding that the translational energy of the tragments has importance for the collision-induced product generation in the laser plume, as suggested earlier [18]. Furthermore, the product generation at 870 mJ/cm² is interpreted by the ejection of small neutral and ionic fragments, and subsequent reactions among the fragments.     

FTICR/MS studies of gas-phase actinide ion reactions: fundamental chemical and physical properties of atomic and molecular actinide ions and neutrals

Fundamental aspects of the chemical and physical properties of atomic and molecular actinide ions and neutrals are being examined by Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS). To date, gas-phase reactivity studies of bare and ligated An⁺ and An²⁺ ions, where An = Th, Pa, U, Np, Pu, Am, and Cm, with oxidants and with hydrocarbons have been performed. Among the information that has been deduced from these studies are thermodynamic properties of neutral and ionic actinide oxide molecules and the role of the 5f electrons in actinide chemistry. Parallel theoretical studies of selected actinide molecular ions have also been carried out to substantiate the interpretation of the experimental observations.     

The Composition of Saturated Vapor over 1-Butyl-3-methylimidazolium Tetrafluoroborate Ionic Liquid: A Multi-Technique Study of the Vaporization Process

A multi-technique approach based on Knudsen effusion mass spectrometry, gas phase chromatography, mass spectrometry, NMR and IR spectroscopy, thermal analysis, and quantum-chemical calculations was used to study the evaporation of 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF₄). The saturated vapor over BMImBF₄ was shown to have a complex composition which consisted of the neutral ion pairs (NIPs) [BMIm⁺][BF₄⁻], imidazole-2-ylidene C₈N₂H₁₄BF₃, 1-methylimidazole C₄N₂H₆, 1-butene C₄H₈, hydrogen fluoride HF, and boron trifluoride BF₃. The vapor composition strongly depends on the evaporation conditions, shifting from congruent evaporation in the form of NIP under Langmuir conditions (open surface) to primary evaporation in the form of decomposition products under equilibrium conditions (Knudsen cell). Decomposition into imidazole-2-ylidene and HF is preferred. The vapor composition of BMImBF₄ is temperature-depended as well: the fraction ratio of [BMIm⁺][BF₄⁻] NIPs to decomposition products decreased by about a factor of three in the temperature range from 450 K to 510 K.     

Kinetic energy distributions of neutral In and In2 sputtered by polyatomic ion bombardment

Kinetic energy distributions of neutral In monomers and In₂ dimers sputtered from a polycrystalline indium surface under bombardment with 5 keV/atom Au₁⁻ and Au₂⁻ projectiles have been investigated by means of laser postionization time-of-flight mass spectrometry. Results show that 5 keV Au₁ bombardment leads to results in full compliance with linear cascade sputtering theory. For polyatomic ion bombardment, we find a clear transition to a collisional spike dominated emission process. The spike contribution appears as a low-energy part in the sputtered flux which increases with increasing projectile nuclearity and energy. We show that, the velocity spectrum associated with the low-energy contribution is virtually identical for sputtered monomers and dimers. This finding has important implications with respect to the particle emission mechanism under polyatomic projectile bombardment.     

Carbon Isotope Analysis in Urea at High 13C-Abundances Using the 13/12CO2-Breath Test Device Fanci2

Abstract

The increasing application of ¹³C-labelled urea in medicine requires simple and reasonable methods for measuring highly enriched ¹³C in urea. The combination: ultimate organic analysis—mass spectrometry so far prescribed is complicated and expensive. For medical diagnosis, however, isotope selective nondispersive infrared spectrometers (NDIRS) have been available for many years. One of these tools is FANci2 which is very reasonable and easily to be operated. By means of such devices also urea highly enriched in ¹³C can be analysed, provided that the samples are first diluted with a defined amount of urea of natural isotopic composition and then transformed into carbon dioxide by means of urease. The relative abundance of ¹³C in this carbon dioxide, measured by nondispersive infrared spectrometry, is then a measure of the ¹³C abundance in the initial urea sample. Comparison of results of such measurements with those attained by mass spectrometry proves that this procedure is feasible and yields precise results.