Comparative study of organic dyes with time-of-flight static secondary ion mass spectrometry and related techniques.

A series of cationic, zwitterionic and anionic fluorinated carbocyanine dyes, spin-coated on Si substrates, were measured with time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) under Ga(+) primary ion bombardment. Detailed fragmentation patterns were developed for all dyes measured. In the positive mode, the resulting spectra showed very intense signals for the precursor ions of the cationic dyes, whereas the protonated signals of the anionic dyes were hardly detected. Differences of three orders of magnitude were repeatedly observed for the secondary ion signal intensities of cationic and anionic dyes, respectively. All measured dyes yielded mass spectra containing several characteristic fragment ions. Although the secondary ion yields were still higher for the cationic than the anionic dye fragments, the difference was reduced to a factor of < or =10. This result and the fact that M(+), [M + H](+) or [M + 2H](+) are even-electron species make it very likely that the recorded fragments were not formed directly out of the (protonated) parent ions M(+), [M + H](+) or [M + 2H](+). In the negative mode, none of the recorded spectra contained molecular information. Only signals originating from some characteristic elements of the molecules (F, Cl), the anionic counter ion signal and some low-mass organic ions were detected. A comparative study was made between TOF-S-SIMS, using Ga(+) primary ions, and other mass spectrometric techniques, namely fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). The measurements showed that MALDI, ESI and FAB all give rise to spectra containing molecular ion signals. ESI and FAB produced M(+) and [M + H](+) signals, originating from the cationic and zwitterionic dyes, in the positive mode and M(-) and [M - H](-) signals of the anionic and zwitterionic dyes in the negative mode. With MALDI, molecular ion signals were measured in both modes for all the dyes. Structural fragment ions were detected for FAB, ESI and MALDI in both the positive and negative modes. Compared with the other techniques, TOF-S-SIMS induced a higher degree of fragmentation.

Metal-assisted secondary ion mass spectrometry: influence of Ag and Au deposition on molecular ion yields.

A series of organic dyes and a pharmaceutical are used to study secondary ion yield enhancement by metal deposition. The molecules were dissolved in methanol and spin-casted on silicon substrates. Subsequently, silver or gold was evaporated onto the samples to produce a very thin coating. The coated samples, when measured with TOF-SIMS, showed a considerable increase in characteristic secondary ion intensity. Gold evaporated samples appeared to exhibit the highest signal enhancement. A major advantage of the metallization technique is that it can be used on real world samples. In particular, additive containing organic crystals could be studied; however, the observed signal increase does not occur at any given moment. The time between metal deposition on the sample surface and the measurement of the sample with TOf-SIMS appears to have an important influence on the enhancement of the secondary ion intensities. Therefore, the metal-coated samples were measured at different times after sample preparation. The results show that, depending on the sample and the metal deposited, the secondary ion signals reach their maximum at different times. Further study will be necessary to reveal the mechanism responsible for the observed enhancement effect.

Numerical investigation of ion-energy-distribution functions in single and dual frequency capacitively coupled plasma reactors.

Ion-energy-distribution functions (IEDFs) are numerically investigated in capacitively coupled (cc) radio frequency (rf) Ar/CF(4)/N(2) discharges by a one-dimensional particle-in-cell/Monte Carlo model. The simulation considers electron-neutral collisions, various kinds of collisions of ions (Ar+, CF+3, N+2, F-, and CF-3) with neutral, positive-negative ion, and electron-ion recombination. The influence of pressure, applied voltage amplitude, and applied frequency on the Ar+, CF+3, and N+2 IEDFs is presented. The dependence on the frequency regime is investigated by simulations of the Ar/CF(4)/N(2) mixture in single (13.56 MHz) and dual frequency (2+27 MHz or 1+27 MHz) cc reactors. A comparison of the simulation results with analytical calculations in a collisionless rf sheath is discussed. The results show that the IEDFs shift toward the low energies with increasing pressure or decreasing applied voltage amplitude. The Ar+ and N+2 IEDFs exhibit secondary maxima due to the charge transfer collisions. The CF+3 IEDF has a peak at high energies in consistency with the average sheath potential drop. The IEDFs in the dual frequency regime are broad and bimodal.

Electron anisotropic scattering in gases: a formula for Monte Carlo simulations.

The purpose of this Brief Report is to point out the mistake in a formula for anisotropic electron scattering, previously published in Phys. Rev. A 41, 1112 (1990), which is widely used in Monte Carlo models of gas discharges. Anisotropic electron scattering is investigated based on the screened Coulomb potential between electrons and neutral atoms. The approach is also applied for electron scattering by nonpolar neutral molecules. Differential cross sections for electron scattering by Ar, N2, and CH4 are constructed on the basis of momentum and integrated cross sections. The formula derived in this paper is useful for Monte Carlo simulations of gas discharges.

Local and fast relaxation phenomena after laser-induced photodetachment in a strongly electronegative rf discharge.

A one-dimensional self-consistent particle in cell/Monte Carlo method is used to study the local (at the laser impact region) and fast relaxation phenomena after laser-induced photodetachment in a strongly electronegative SiH(4)/H(2) rf discharge. The relaxation process of the local densities of the charged plasma species has been studied in association with the time evolution of the local electric field. The phenomena predicted theoretically about the relaxation processes, such as the potential well, the electrostatic oscillation, the long lasting potential structure, the distortion of the early potential perturbation on the measurement of negative ion temperature, and the depression in the positive ion density profile at the edges of the laser impact region, have been confirmed by our simulation results. Compared to the relaxation in weakly electronegative discharges, the local and even the global electric field in strongly electronegative discharges, has been weakened strongly after photodetachment. The relaxation of the local electric field lasts 100 rf cycles with the recovery of the local electron density and the local electron energy. The electrostatic oscillation exhibited as the deviation in quasineutrality, is very strong and continues over several rf cycles in our case. The large dip in the center of the positive ion density profile, observed in the experiment, is also reproduced by our model.

Modeling of the sputtering process of cubic silver halide microcrystals and its relevance in depth profiling by secondary-ion mass spectrometry (SIMS).

Secondary-ion mass spectrometry is frequently used for concentration-depth profiling of macroscopic samples, but it is certainly not a common analytical technique for the analysis of sub-micrometer-size particles. This is because of the additional ion-bombardment-induced artifacts which can occur when a three-dimensional microvolume is sputtered, instead of a flat surface. This paper presents a model of how small cubic photographic Ag(Cl,Br) crystals are eroded under primary-ion bombardment, and the extent to which secondary ions generated at different faces are extracted. The latter is studied by means of the program SIMION, which simulates ion trajectories in complex electrical field systems. It is shown that up to 90% of the secondary ions originating from the side face of a cubic crystal are unable to reach the detector, in contrast with most secondary ions originating from the top face. The angular dependence of the sputtering yield and the elemental ratio of Br/Cl sputtered particles have been calculated by using the well-known computer code TRIM (transport of ions in matter) under some limiting assumptions (possible preferential sputtering is disregarded and a steady-state sputtering process is assumed). The validity of the theoretical model and the calculated results were checked with experimental data. On the basis of the depth profiles presented it is explained why it is still possible to measure an interface inside a cubic volume, even though a group of several hundred crystals is sputtered simultaneously, and even though the orientations of the distinct faces of the cubes relative to the angle of incidence of the primary-ion beam are different.

Design and development of a new program for data processing of mass spectra acquired by means of a high-resolution double-focusing glow-discharge mass spectrometer.

An new program has been developed and implemented for data analysis of mass spectra obtained by use of the VG9000 glow-discharge mass spectrometer. The program, designed to run in a Windows 9X environment includes several tools for import and export of data, cluster generators, etc. An automated technique for the interpretation of mass spectra is also built into the program; this enables faster and operator-independent interpretation. When major interferences or not-well defined signals are involved, the automated technique might fail to find the correct result. Therefore, a manual, VG9000 software-like, bypass is at hand. A comparison of the different techniques and programs shows, in general, comparable results. An installable version of the software is available on the university FTP-server (ftp://PLASMA-FTP.uia.ac.be/ private/imsas/).

Kinetic modeling of relaxation phenomena after photodetachment in a rf electronegative SiH4 discharge.

The global relaxation process after pulsed laser induced photodetachment in a rf electronegative SiH4 discharge is studied by a self-consistent kinetic one-dimensional particle-in-cell-Monte Carlo model. Our results reveal a comprehensive physical picture of the relaxation process, including the main plasma variables, after a perturbation up to the full recovery of the steady state. A strong influence of the photodetachment on the discharge is found, which results from an increase of the electron density, leading to a weaker bulk field, and hence to a drop in the high energy tail of the electron energy distribution function (EEDF), a reduction of the reaction rates of electron impact attachment and ionization, and a subsequent decrease of the positive and negative ion densities. All the plasma quantities related to electrons recover synchronously. The recovery time of the ion densities is about 1-2 orders of magnitude longer than that of the electrons due to different recovery mechanisms. The modeled behavior of all the charged particles agrees very well with experimental results from the literature. In addition, our work clarifies some unclear processes assumed in the literature, such as the relaxation of the EEDF, the evolution of the electric field, and the recovery of negative ions.

Electron boltzmann kinetic equation averaged over fast electron bouncing and pitch-angle scattering for fast modeling of electron cyclotron resonance discharge

The electron distribution function (EDF) in an electron cyclotron resonance (ECR) discharge is far from Maxwellian. The self-consistent simulation of ECR discharges requires a calculation of the EDF on every magnetic line for various ion density profiles. The straightforward self-consistent simulation of ECR discharges using the Monte Carlo technique for the EDF calculation is very computer time expensive, since the electron and ion time scales are very different. An electron Boltzmann kinetic equation averaged over the fast electron bouncing and pitch-angle scattering was derived in order to develop an effective and operative tool for the fast modeling (FM) of low-pressure ECR discharges. An analytical solution for the EDF in a loss cone was derived. To check the validity of the FM, one-dimensional (in coordinate) and two-dimensional (in velocity) Monte Carlo simulation codes were developed. The validity of the fast modeling method is proved by comparison with the Monte Carlo simulations. The complete system of equations for FM is presented and ready for use in a comprehensive study of ECR discharges. The variations of plasma density and of wall and sheath potentials are analyzed by solving a self-consistent set of equations for the EDF.

Combined characterization of composite tabular silver halide microcrystals by cryo-EFTEM/EELS and cryo-STEM/EDX techniques.

The combination of cryo-energy filtering transmission electron microscopy (EFTEM)/electron spectroscopic diffraction (ESD)/electron energy-loss spectroscopy (EELS) and cryo-energy-dispersive X-ray (EDX) analysis in the scanning transmission (STEM) and scanning (SEM) modes was applied for the characterization of composite tabular Ag(Br,I) microcrystals. A low-loss fine structure in EEL spectra between 4 and 26 eV was attributed to excitons and plasmons possibly superimposed with interband transitions and many-electron effects. The contrast tuning under the energy-filtering in the low-loss region was used to image the crystal morphology, defect structure (random dislocations and ¿111¿ stacking faults) and bend and edge contours as well as electron excitations in the microcrystals. Sharp extra reflections at commensurate positions in between the main Bragg reflections and diffuse honeycomb contours in ESD patterns of the microcrystals taken near the [111] zone were assigned to the number of defects in the shell region parallel to the grain edges and polyhedral clusters of interstitial silver cations, respectively. The imaginary part of the energy-loss function, Im (-1/epsilon), and the real and imaginary parts, epsilon1 and epsilon2, of the dielectric permittivity were determined by means of a Kramers-Kronig analysis. An assignment of exciton peaks based on calculations of electronic band structure of silver bromide is proposed. Inner-shell excitation bands of silver halide were detected in line with EDX-analyses. The energy-loss near-edge structure (ELNES) of the AgM4,5-edge governed by spin-orbital splitting between the 3d3/2- and 3d5/2-states has been evaluated. Combined silver and halide distributions were obtained by a three-window method (EFTEM) and by EDX/STEM including area mapping and line profiling of iodide.

Microprobe speciation analysis of inorganic solids by fourier transform laser mass spectrometry.

Fourier transform (FT) laser microprobe mass spectrometry (LMMS) aims at the characterization of local constituents at the surface of solids. Signals from structural fragments specify the main building blocks of the analyte while adduct ions, consisting of one or two intact analyte molecules and a stable ion, allow specific identification of the molecule. A series of inorganic reference compounds including binary salts, oxides, and oxy salts was analyzed to assess the FT LMMS capabilities for the determination of the inorganic molecular composition. Compounds from different classes can be tentatively identified by deductive reasoning while those with the same elements in different stoichiometries require comparison with reference spectra.

Automated Particle Analysis of Populations of Silver Halide Microcrystals by Electron Probe Microanalysis under Cryogenic Conditions.

An automated particle analysis routine is implemented on an electron microprobe for analyzing the chemical composition and projective area of populations of individual silver halide microcrystals. An LN2 cryostage is used to prevent material degradation due to reaction with the impinging electron beam. The background in the EDX spectra is lowered by depositing the microcrystals on a carbon-coated copper grid, mounted in a transmission holder. The ILα/AgLα net X-ray intensity ratio, obtained from a spectrum-fitting algorithm, is used to determine the crystal composition by means of a standard-based calibration curve. The uncertainty on the concentration measurement of individual microcrystals is calculated using the uncertainties on the net X-ray counts and the uncertainties on the calibration curve. The area measurement is optimized by introducing a gray value histogram correction on each individual measurement. Overlapping microcrystals are scrapped from the analysis by defining a maximum shape factor, against which the shape factor of the microcrystal is tested. To minimize problems with drift of the cryostage, spectrum acquisition is carried out immediately after a single microcrystal has been located, based on the backscattered electron image. Several applications are discussed.

Laser microprobe mass spectrometry: principle and applications in biology and medicine.

Laser microprobe mass spectrometry (LMMS) is an interesting technique for micro- and surface analysis. It employs local ionization by a focused laser under high power density conditions and subsequent mass analysis of the generated ions. This paper surveys the main LMMS instruments and their operational principles. Sample preparation is discussed in the context of biological materials. The problem of quantification is addressed. Selected examples show the way that precise information on the molecular composition can be deduced from the detected signals. Both inorganic and organic substances can be identified, even without reference spectra, from in-situ analysis with a lateral resolution in the order of 1 to 5 micrograms.

Mathematical description of a direct current glow discharge in argon.

In order to achieve a better understanding of the glow discharge, different models have been developed for the different species present in the plasma. An overview of the models is given and some typical results are presented. These results include, among others, the densities and energy distributions of the plasma species, the electric field and potential distribution, the contribution of different ionization mechanisms to the ionization of argon and sputtered atoms, the relative contribution of different plasma species to the sputtering process, and the variation of the cathode dark space length and the electrical current as functions of voltage and pressure. The validity of the present models is supported by the good agreement of the calculated current-voltage curves with experiment.

Two-dimensional model of a direct current glow discharge: description of the argon metastable atoms, sputtered atoms, and ions.

A two-dimensional model is presented that describes the behavior of argon metastable atoms, copper atoms, and copper ions in an argon direct current glow discharge, in the standard cell of the VG9000 glow discharge mass spectrometer for analyzing flat samples. The model is combined with a previously developed model for the electrons, argon ions, and atoms in the same cell to obtain an overall picture of the glow discharge. The results of the present model comprise the number densities of the described plasma species, the relative contributions of different production and loss processes for the argon metastable atoms, the thermalization profile of the sputtered copper atoms, the relative importance of the different ionization mechanisms for the copper atoms, the ionization degree of copper, the copper ion-to-argon ion density ratio, and the relative roles of copper ions, argon ions, and atoms in the sputtering process. All these quantities are calculated for a range of voltages and pressures. Moreover, since the sticking coefficient of copper atoms on solid surfaces is not well-known in the literature, the influence of this parameter on the results is briefly discussed.

Laser microprobe mass spectrometry in biology and biomedicine.

An overview is given of laser microprobe mass spectrometry (LMMS) in biology and biomedicine (1989-1993). The present instrumentation and its analytical features are surveyed. Applications are presented with special attention on human and animal tissue samples, as well as plant material. The capabilities of LMMS to study the element distribution in histological sections, to identify the chemical composition of inorganic inclusions and to generate structural information from organic compounds are evidenced.

Laser microprobe mass spectrometry of quaternary phosphonium salts: Direct versus matrix-assisted laser desorption.

The use of laser microprobe mass spectrometry (LMMS) for the structural characterization of thermolabile quaternary phosphonium salts has been evaluated. A comparison has been made between LM mass spectra obtained by direct analysis of "neat" organic salts and the corresponding "matrix-assisted" LM mass spectra. Main limitations of LMMS for the direct analysis of neat organic salts (i.e., no matrix) result from (1) formation of artifact ions that originate from thermal degradation and surface recombination reactions and (2) poor shot-to-shot reproducibility of the spectra. Dilution of the organic salts in a suitable, UV-absorbing matrix (e.g., nicotinic acid) significantly enhances the quality of the LM mass spectra. Improvements are: (1) an increase of the ion yield of preformed cations, (2) reduction or elimination of thermal decomposition and other deleterious surface reactions, and (3) a much better shot-to-shot spectral reproducibility. An interesting analytical feature is that these LM mass spectra, which contain only a few matrix peaks, can be obtained for subnanogram amounts of sample.The results also show that triphenylphosphonium salts with polycyclic aromatic substituents can be used as "molecular thermometers" to probe both the temperatures experienced by the sample molecules during the laser-induced desorption ionization process and the internal energies of the desorbed ion species. In this way, quaternary phosphonium salts can be used for evaluating whether improvements have been achieved by applying different sample treatments. Comparison of four different matrices (i.e., nicotinic acid, ammonium chloride, glycerol, and 3-nitrobenzylalcohol) indicates that the effectiveness of a matrix to reduce thermal degradation and to decrease the internal energies of the ions depends on the UV-absorption characteristics and the volatilization/sublimation temperature of the matrix material.

Elemental analysis of high-purity solids by mass spectrometry.

The applications of mass spectrometry in the determination of trace elements in some of the high-purity solid materials used in modern technology are reviewed.

On the use of laser microprobe mass spectrometry for the analysis of organic biomolecules.

Laser microprobe mass spectrometry has been applied to a variety of organic polyfunctional molecules, covering a wide range of polarity and mass spectrometric behaviour. The technique apparently combines desorption under relatively soft conditions with extensive fragmentation and hence allows much structural information from intactly released thermolabiles to be obtained. The mass spectra appear unfamiliar in comparison to conventional techniques. Interpretation is attempted in a purely empirical way by means of the evidence from our database and tentative hypotheses to rationalize the desorption and ionization by laser microbeam irradiation of organic solids. Selected examples are presented to illustrate the potential and limitations of the method in the field of biomolecules, such as pyridoxine and pyridoxal phosphate, nucleosides, nucleotides and related analogues, drugs and the corresponding N-oxides.