MCs+ secondary ion and sputtering yields of oxygen-exposed semiconductors and glasses

The emission of MCs⁺ molecular ions sputtered by Cs⁺ ion impact from a variety of elemental (Si and Ge) and compound (GaAs, InP, InSb, ZnSe, CdS, CdSe, CdTe and CdZnTe) semiconductors and a selection of glass samples of different composition has been investigated. For the glass samples a set of relative sensitivity factors has been determined which are largely composition-independent and provide the possibility of a reliable quantification of glasses by MCs⁺ SIMS. For the semiconductors fractional ion yields (i.e. the number of detected MCs⁺ ions per sputtered M atom) range from 10^–6 to some 10^–4 and exhibit little variation with the oxygen surface coverage of the specimen. Depending on M, the emission of MOCs⁺ molecular species becomes prominent (or even dominating) at high oxygen concentrations. Furthermore, total sputtering yields for 5.5 keV Cs⁺ impact and different oxygen partial pressures have been determined from sputtered craters.     

On the generation of MCs+ ions in SIMS with Cs+ primary beams

The formation of MCs⁺ secondary ions in SIMS operated with Cs⁺ ion beams is discussed on the basis of a well-confirmed quadratic dependence of MCs⁺ yields on the atomic polarizabilities of elements M contained in semiconductor samples. This behavior is understood by the generation of a dipole induced in M by the positive charge of a neighboring Cs⁺ projectile and the mutual induction of a dipole in Cs⁺, both dipoles depending on the atomic polarizability of M. An evaluation of the dipole–dipole interaction energy indicates that MCs⁺ ions generated at the target are emitted according to the direct emission model (DEM). This mechanism is in contrast with an association model where constituents of MCs⁺ are assumed to combine after their independent sputter emission.     

SIMS depth profile analysis using MCs+ molecular ions

Summary The use of Cs⁺ primary ions in conjunction with the detection of MCs⁺ molecular ions (where M is the element to be monitored) in SIMS depth profiling is shown to be an efficient method of minimizing the variations of ion yields with sample composition, e.g., at the interface of multilayer structures. Depth profiles of several such samples demonstrate that MCs⁺ intensities follow closely the concentrations of the respective elements, providing the possibility of a (semi)quantitative analysis of major components by means of secondary ion mass spectrometry. As indicated by the similarity of their energy distribution data, the formation and emission process of MCs⁺ molecules seems coupled to that of Cs⁺ ions.     

Comparative studies of MCs+-SIMS and e?-beam SNMS for quantitative analysis of bulk materials and layered structures

For the quantification of heterostructure depth profiles the knowledge of relative sensitivity factors (RSF) and the influence of matrix effects on the measured profiles is necessary. Matrix dependencies of the measured ion intensities have been investigated for sputtered neutral mass spectrometry (SNMS) and MCs⁺-SIMS. The use of Cs as primary ions for SNMS is advantageous compared to Ar because the depth resolution is improved without changing RSFs determined under Ar bombardment. No significant amount of molecules has been found in the SNMS spectra under Cs bombardment. Using MCs⁺-SIMS the RSFs are matrix dependent. An improvement of depth resolution can be achieved by biasing the sample against the primary ion beam for SNMS due to a reduction of the net energy of the primary ions and a resulting more gracing impact angle.     

Quantification of SIMS depth profiles of ODS-superalloys by using cluster ion formation from reactive primary ions

Cluster ion formation, with both oxygen and caesium as reactive elements, (MO^– and MCs⁺ ions) has been studied using secondary ion mass spectrometry. A comparison of various primary ion beam conditions is given. The investigations were carried out on aluminium oxide films and required a special charge compensation method. An improvement in the quantification concentration by use of cluster ions can only be expected from MCs⁺ measurements; however the total ionization probabilities still depend on matrix composition.     

SIMS sputtering rates in biogenic aragonite: implications for culture calibration studies for palaeoenvironmental reconstruction

We used scanning white light interferometry to view the craters produced during secondary ion mass spectrometry (SIMS) analysis of the CaCO₃ skeleton of an aragonitic coral. The dimensions and volumes of craters sputtered during trace element, δ¹⁸O, δ¹³C and δ¹¹B analyses were determined. Sputtering rates were ~6 µm³ nA^?1 min^?1 for a ¹⁶O^? primary beam and ranged from ~12 µm³ nA^?1 min^?1 (for δ¹⁸O analyses) to ~19 µm³ nA^?1 (for δ¹³C analyses) using a Cs⁺ primary beam. Sputter yields (atoms sputtered/impinging primary ions) ranged from 1.3 to 1.4 for a ¹⁶O^? primary beam and from 2.5 to 4.5 using a Cs⁺ primary beam. Useful ion yields (ions detected/atoms sputtered), using instrument conditions typically used in geoscience applications, were of the order of 10^?4 for B, Mg, Ca, Sr, Ba and C and 10^?2 for O. The maximum lengths of the SIMS craters, at the sample surface, range from ~17 µm (δ¹³C analyses) to ~36 µm (δ¹¹B analyses) and crater depths range from ≤3 µm (δ¹⁸O analyses) to >20 µm (δ¹¹B analyses). These dimensions are significant in relation to accretion rates in a range of biogenic carbonates and SIMS analyses typically sample carbonate deposited over time periods of days to months depending on the organism and structure analysed. In culture calibration studies, accurate determination of the temporal resolution of the analysed volume is crucial to ensure that the entire volume reflects the culture conditions and does not include carbonate deposited prior to introduction of the organism to the culture system. Copyright © 2013 John Wiley & Sons, Ltd.     

EPMA and Quantitative MCs+-SIMS of Metal-DLC Coating Materials

 Compositional characterization of metal-DLC (metal-containing diamond-like carbon) hard coatings is carried out by (WDS)-EPMA and MCs⁺-SIMS. EPMA enables accurate (± 5% relative) quantitative analysis including minor concentrations (0.1–10 at%) of N, O and Ar. Under conditions of “near-surface” EPMA (E₀ < 10 keV) the influence of surface oxide films on “pure” metal standards may be a limiting factor in respect of accuracy. Depth profiling of sufficiently “thick” layered structures (film thickness ≥ 2 μm) is carried out by EPMA-line scans along mechanically prepared bevels. The depth resolution is about 0.2 μm. SIMS in the MCs⁺-mode enables high resolution (< 20 nm) depth profiling of metal-DLC layered structures including the determination of H (1–20 at%). MCs⁺-SIMS, i.e. employing Cs⁺ primary ions and monitoring MCs⁺ molecular secondary ions (M is the element of interest) is presented as a promising route towards sufficiently accurate (10–20%) SIMS-quantification. Matrix-independent relative sensitivity factors for MCs⁺-SIMS are derived from homogeneous coating materials defined by EPMA. EPMA proves to be also useful to detect problems related to SIMS of Ar in metal-DLC materials. The combination EPMA-SIMS is demonstrated as an effective analytical strategy for quality control in industrial production and to support the development of metal DLC layered structures with optimum tribological properties.     

3D analysis of solids using sputtered MCs+ ions

The 3-dimensional characterization of solids by means of secondary-ion mass spectrometry is investigated. Monitoring MCs⁺ molecular ions emitted from surfaces upon Cs⁺ bombardment, laterally-resolved ion images were recorded with acquisition times of typically a few seconds which exhibit a dynamic sensitivity range in excess of 10² and a lateral resolution of about 2–3 μm. A quantitative data evaluation via relative sensitivity factors (RSFs) transforms them into elemental distribution maps. From the applied RSFs, local (i.e. erosion-time dependent) sputtering yields can be derived; together with atomic densities (which might be interpolated from pure-element values) a local depth scale (relative to some reference level) is assigned to each pixel of the 3D data volume recorded during the analysis. In conjunction with the elemental concentration values, this provides the possibility of a complete reconstruction of the 3D sample volume removed by sputtering. This approach is exemplified by means of a laterally inhomogeneous semiconductor test specimen.     

Assessment of Potassium Zinc Ferrocyanide as an Alkali-Metal Ion-Exchanger in Ion-Selective Electrodes

Abstract

Silicone rubber membranes containing potassium zinc ferrocyanide have been assessed as ion-selective electrode sensors for the determination of alkali metal ions. The slope of the calibration graph for potassium ion is 59 mV per decade change in concentration within the concentration range 5 × 10^?4 to 10^?1 M at 25°C. Selectivity constants (K_K + _/M+)are 9. 5, Cs⁺; 3. 3, Rb⁺; 0. 025, Na⁺; 0. 003, Li⁺; and 1.8, NH₄ ⁺, calculated from potential data obtained at 10^?1 M concentrations of each ion separately. Similar membranes prepared from PVC responded similarly with a slight improvement in selectivity.     

Lithium,rubidium and cesium ion removal using potassium iron(III) hexacyanoferrate(II) supported on polymethylmethacrylate

Potassium iron(III) hexacyanoferrate(II) supported on poly methyl methacrylate, has been developed and investigated for the removal of lithium, rubidium and cesium ions. The material is capable of sorbing maximum quantities of these ions from 5.0, 2.5 and 4.5 M HNO₃ solutions respectively. Sorption studies, conducted individually for each metal ion, under optimized conditions, demonstrated that it was predominantly physisorption in the case of lithium ion while shifting to chemisorption with increasing ionic size. Distribution coefficient (K _d) values followed the order Cs⁺ > Rb⁺ > Li⁺ at low concentrations of metal ions. Following these findings Cs⁺ can preferably be removed from 1.5 to 5 M HNO₃ nuclear waste solutions.     

Calix[4]pyrrole‐Based Heteroditopic Ion‐Pair Receptor That Displays Anion‐Modulated,Cation‐Binding Behavior

A new ditopic ion‐pair receptor 1 was designed, synthesized, and characterized. Detailed binding studies served to confirm that this receptor binds fluoride and chloride ions (studied as their tetraalkylammonium salts) and forms stable 1:1 complexes in CDCl₃. Treatment of the halide‐ion complexes of 1 with Group I and II metal ions (Li⁺, Na⁺, K⁺, Cs⁺, Mg²⁺, and Ca²⁺; studied as their perchlorate salts in CD₃CN) revealed unique interactions that were found to depend on both the choice of the added cation and the precomplexed anion. In the case of the fluoride complex [ 1? F]^? (preformed as the tetrabutylammonium (TBA⁺) complex), little evidence of interaction with the K⁺ ion was seen. In contrast, when this same complex (i.e., [ 1? F]^? as the TBA⁺ salt) was treated with the Li⁺ or Na⁺ ions, complete decomplexation of the receptor‐bound fluoride ion was observed. In sharp contrast to what was seen with Li⁺, Na⁺, and K⁺, treating complex [ 1? F]^? with the Cs⁺ ion gave rise to a stable, receptor‐bound ion‐pair complex [Cs ?1? F] that contains the Cs⁺ ion complexed within the cup‐like cavity of the calix[4]pyrrole, which in turn was stabilized in its cone conformation. Different complexation behavior was observed in the case of the chloride complex [ 1? Cl]^?. In this case, no appreciable interaction was observed with Na⁺ or K⁺. In addition, treating [ 1? Cl]^? with Li⁺ produces a tightly hydrated dimeric ion‐pair complex [ 1? LiCl(H₂O)]₂ in which two Li⁺ ions are bound to the crown moiety of the two receptors. In analogy to what was seen in the case of [ 1? F]^?, exposure of [ 1? Cl]^? to the Cs⁺ ion gives rise to an ion‐pair complex [Cs ?1? Cl] in which the cation is bound within the cup of the calix[4]pyrrole. Different complexation modes were also observed when the binding of the fluoride ion was studied by using the tetramethylammonium and tetraethylammonium salts.     

Oligoether‐Strapped Calix[4]pyrrole: An Ion‐Pair Receptor Displaying Cation‐Dependent Chloride Anion Transport

A ditopic ion‐pair receptor ( 1 ), which has tunable cation‐ and anion‐binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([ 1? F]^? and [ 1? Cl]^?) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li⁺, Na⁺, K⁺, Cs⁺, as their perchlorate salts), ion‐dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [ 1? F]^?, no appreciable interaction with the K⁺ ion was seen. On the other hand, when this complex was treated with Li⁺ or Na⁺ ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li⁺, Na⁺, K⁺, treating [ 1?F ]^? with Cs⁺ ions gave rise to a stable, host‐separated ion‐pair complex, [F ?1? Cs], which contains the Cs⁺ ion bound in the cup‐like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [ 1? Cl]^?. Here, no appreciable interaction was observed with Na⁺ or K⁺. In contrast, treating with Li⁺ produces a tight ion‐pair complex, [ 1? Li ? Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [ 1? F]^?, treatment of [ 1? Cl]^? with Cs⁺ ions gives rise to a host‐separated ion‐pair complex, [Cl ?1? Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co‐transport) and antiport (nitrate‐for‐chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate‐for‐chloride anion exchange mechanism.     

A fast atom bombardment and field ionization/field desorption study of some isomeric unsaturated dicarboxylic acids

Geometrically isomeric dicarboxylic acids, such as maleic and fumaric acid and their methyl homologues, and the isomeric phthalic acids, have been investigated using fast atom bombardment, field ionization and field desorption mass spectrometry. The most intense peak in the positive ion fast atom bombardment spectra corresponds with the [M + H]⁺ ion. This ion, when derived from the E -acids, tragments either by successive loss of water and carbon monoxide or by elimination of carbon dioxide. In the case of the Z -acids only elimination of water from the [M + H]⁺ ions is observed to occur to a significant extent. The same is true for the [M + H]⁺ ions of the isomeric phthalic acids, that is the [M + H] ions derived from iso- and terephthalic acid exhibit more fragmentation than those of phthalic acid. All these acids undergo much less fragmentation upon field ionization, where not only abundant [M + H]⁺ ions, but also abundant [M]^+· ions, are observed. Upon field desorption only the [M + H]⁺ and [M + Na]⁺ ions are observed under the measuring conditions. Negative ion fast atom bombardment spectra of the acids mentioned have also been recorded. In addition to the most abundant [M? H]^? ions relatively intense peaks are observed, which correspond with the [M]^?˙ ions. The fragmentations observed for these ions appear to be quite different from those reported in an earlier electron impact study and in a recent atmospheric pressure ionization investigation.     

Synthesis and binding studies of novel thiacalixpodands and bisthiacalixarenes having O,O″-dialkylated thiacalix[4]arene unit(s) of 1,3-alternate conformation

A series of thiacalixpodands and bisthiacalixarenes with imine units have been prepared by condensation of O,O″-bis(2-aminoethyl)-O′,O?-dipropyl-p-tert-butylthiacalix[4]arene of 1,3-alternate conformation with different aromatic (di)aldehydes. The molecules derived from pyridine-2-carbaldehyde and -2,6-dicarbaldehyde quantitatively extract silver ion from aqueous into organic phase with complete selectivity over other metal ions (Na⁺, K⁺ and Cs⁺) under neutral conditions. The former compound forms a 1:2 (L:M) complex with silver ion as proved by NMR spectroscopy, Job’s plot and X-ray crystallography.     

Effect of Cs+ ions on the electrochemical nanogravimetric response of platinum electrode in acid media

Platinum electrodes have been investigated in sulfuric acid solutions in the presence and absence of Cs⁺ ions by electrochemical quartz crystal nanobalance (EQCN). An unusual potential dependence of the quartz crystal frequency response has been observed in the presence of Cs⁺ ions. The frequency decrease is more pronounced in the region of the underpotential deposition of hydrogen, and the frequency decrease in the double layer region diminishes as the concentration ratio of Cs⁺ and H⁺ ions increases. After immersion in Cs₂SO₄ solutions the frequency change was higher than that expected taking into account the density and viscosity. The effects observed can be explained by the specific adsorption of Cs⁺ ions on the Pt surface, which competes with the hydrogen adsorption. At more positive potentials than the potential of zero charge (pzc) a desorption of the Cs⁺ ions starts. In this potential region both Cs⁺ and HSO₄^? ions are adsorbed at the platinum surface. In the double layer region the mass change caused by the desorption of Cs⁺ ions and the starting adsorption of sulfate ions compensates each other.     

Characteristic Fragmentation of Polysiloxane Monolayer Films by Bombardment with Monatomic and Polyatomic Primary Ions in TOF-SIMS

This study reports the characteristic fragmentation patterns from two polysiloxane polymers that form ordered overlayer on silver substrates. Results are compared for the bombardment of various monatomic and polyatomic projectiles of Cs⁺, C₆₀⁺ (10 keV), Bi₁⁺, and Bi₃⁺ (25 keV) in the high mass range time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra. Results are reported from sub-monolayer (solution cast) coverages of poly(dimethylsiloxane)s with the number average molecular weights (M_n) of 2200 and 6140 Da, respectively, and Langmuir-Blodgett monolayers of poly(methylphenylsiloxane) with molecular weights (MW) from 600 and 1000 Da. For each film, Bi projectiles resulted in the emission of positive silver cluster ions from the substrate under the polymer overlayer and peaks corresponding to silver cluster ions with larger mass were observed by impact of polyatomic 25 keV Bi₃⁺ projectiles. In addition, depending on the change of energy of Bi₃⁺, a different pattern of fragments was observed. With Cs⁺ and C₆₀⁺ impact, however, the emission of silver cluster ions was not detected. In the case of C₆₀⁺ impact for PDMS-6140, peaks corresponding to silver-cationized intact oligomers were not observed. In this paper, these results are explained by the possible bombardment mechanism for each projectile, based on its mass, energy, and split trajectories of the component atoms under the polyatomic impact.     

Electron impact,chemical ionization and negative chemical ionization mass spectra,and mass-analysed ion kinetic energy spectrometry–collision-induced dissociation fragmentation pathways of some deuterated 2,4,6-trinitrotoluene (TNT) derivatives

Mass-analysed ion kinetic energy spectrometry (MIKES) with collision-induced dissociation (CID) has been used to study the fragmentation processes of a series of deuterated 2,4,6-trinitrotoluene (TNT) and deuterated 2,4,6-trinitrobenzylchloride (TNTCI) derivatives. Typical fragment ions observed in both groups were due to loss of OR′ (R′ = H or D) and NO. In TNT, additional fragment ibns are due to the loss of R₂′O and 3NO₂, whilst in TNTCI fragment ions are formed by the loss of OCI and R₂′OCI. The TNTCI derivatives did not produce molecular ions. In chemical ionization (Cl) of both groups. MH⁺ ions were observed, with [M – OR′]⁺ fragments in TNT and [M – OCI]⁺ fragments in TNTCI. In negative chemical ionization (NCI) TNT derivatives produced M^?′, [M–R′]^?, [M–OR′]^? and [M–NO]^? ions, while TNTCI derivatives produced [M–R]^?, [M–Cl]^? and [M – NO₂]^? fragment ions without a molecular ion.     

Charge reversal of the conjugate base of formamide

Charge reversal collisional activation mass spectremetry of negative ions has been used in conjunction with positive ion collisional activation to investigate several isomeric [H₂, C, N, O]⁺ ions. Generation of m/z 44 ions from formamide, acetamide, JV-methylformamide, acetaldoxime and by charge reversal of the [M–1]^? ion formed from formamide yields several different isomeric structures. Charge reversal of the conjugate base of formamide appears to yield a mixture of singlet and triplet H₂NC?O⁺ ions; experiments with deuterium-labeled compounds have been used to support this. Ab initio molecular orbital calculations indicate that the triplet ion is a stable structure, existing in a potential minimum 390.6 kJ mol^?1 above the ground state singlet.     

Polymeric membrane coated graphite cesium selective electrode based on 4′,4″(5′) di–tert-butyl di-benzo-18-crown-6

A new PVC membrane coated graphite electrode for cesium ion based on 4′,4″(5′)di–tert-butyl di-benzo-18-crown-6 (DTBDB18C6) as ionophore was prepared. The electrode shows a near Nernstian response of 57.0 ± 1.8 mV decade^?1 over a wide activity range of 6.0 × 10^?6–1.0 × 10^?1 mol L^?1 with a limit of detection 4.0 × 10^?6 mol L^?1. The proposed electrode is suitable for use in aqueous solution in the pH range of 3.0–9.5. It has a fast response time of 10 s and can be used for at least 1 month without any considerable divergence in potential. The selectivity coefficients for Cs⁺ ion with respect to ammonium, alkali, alkaline earth and some selected transition metal ions were determined and showed a superior selectivity over Li⁺, Na⁺ and alkaline earth metal ions. The new electrode was applied for determination of Cs⁺ in spiked tap water. The electrode was also used as indicator electrode in potentiometric titration of Cs⁺ with sodium tetraphenyl borate.     

Vibrational spectroscopy of Cs+ solvated by methylamine

We report the vibrational spectra of the cluster ions Cs⁺(CH₃NH₂)_N, N=3–22. Bands in the 1015–1050 cm^?1 region of the infrared are due to the v8 mode (CN stretch) of methylamine molecules displaying different degrees of interaction with the central ion. Monte Carlo simulations of the solvated Cs⁺ ion indicate that nine methylamine molecules fill the first solvation shell of Cs⁺ and that possible rearrangements in cluster structure occur at N=14?15. No absorptions due to bulklike methylamine molecules are observed through N=22.