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.     

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.     

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.     

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.     

A Novel Vanadosilicate with Hexadeca‐Coordinated Cs+ Ions as a Highly Effective Cs+ Remover

The effective removal of ¹³⁷Cs⁺ ions from contaminated groundwater and seawater and from radioactive nuclear waste solutions is crucial for public health and for the continuous operation of nuclear power plants. Various ¹³⁷Cs⁺ removers have been developed, but more effective ¹³⁷Cs⁺ removers are still needed. A novel microporous vanadosilicate with mixed‐valence vanadium (V⁴⁺ and V⁵⁺) ions is now reported, which shows an excellent ability for Cs⁺ capture and immobilization from groundwater, seawater, and nuclear waste solutions. This material is superior to other known materials in terms of selectivity, capacity, and kinetics, and at very low Cs⁺ concentrations, it was found to be the most effective material for the removal of radioactive Cs⁺ ions under the test conditions. This novel vanadosilicate also contains hexadeca‐coordinated Cs⁺ ions, which corresponds to the highest coordination number ever described.     

Crystal Structure,Electronic Structure,and Luminescence of Cs2KYF6:Pr3+

The crystal structure, electronic states and VUV spectroscopic behaviour of Cs₂KYF₆ doped with Pr³⁺ ions have been investigated both by experimental and theoretical methods. Cs₂KYF₆ ( , Z = 4, a = 945.5(3) pm, R1_all = 0.0297) crystallizes with the cubic elpasolite type of structure. The local relaxation of the activator ions in the host lattices has been calculated by the projector augmented wave method (computer code VASP). The electronic states have been calculated using a spin density functional procedure based on the atomic sphere approximation (computer code ASW). VUV spectroscopic measurements show fast 4f¹5d¹ → 4f² emission of nanosecond duration as well as slow 4f² → 4f² emission depending on the excitation energy which indicates the occupation of different sites in the host lattice. This assumption was verified by a recently developed quantum mechanical method. The combination of the experimental and the theoretical results show that the Pr³⁺ ions are occupying three different sites, namely the Y³⁺ and the Cs⁺ site as well as the K⁺ site.     

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.     

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.     

Examination of the role of ion size in determining double layer properties on the basis of a generalized mean spherical approximation

A new model for the diffuse double layer which accounts for the effects of ion size and solution permittivity is described. It is then used to estimate the potential drop across the diffuse layer at negative charge densities for the cases that Li⁺ and Cs⁺ are the electrolyte cations. The potential drop in the Li⁺ system is considerably smaller than that in the Cs⁺ system at 1 M, and both values are smaller than the value predicted by the Gouy–Chapman model. As the electrolyte concentration decreases these differences become smaller so that at 0.01 M, the present model predicts that the diffuse layer potential drop is approximately 90% of the Gouy–Chapman estimate. The results of the model are used to examine the differences in inner layer structure at mercury electrodes with Li⁺ and Cs⁺ ions at the outer Helmholtz plane, and to reconsider the question of the specific adsorption of Cs⁺ at negative-charge densities.     

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.     

Vibration-rotation transition probabilities in CH+ and CD+

Vibrational dipole matrix elements and radiative transition probabilities have been evaluated from electric dipole moment functions for the X¹Σ⁺ states of CH⁺ and CD⁺, which were calculated from highly correlated electronic wavefunctions. The dipole moments in ν = 0 amount to 1.679 D (CH⁺) and 1.313 D (CD⁺), respectively. In comparison to other molecular ions the infrared transition probabilities are found to be rather small. For instance, the Einstein coefficient of spontaneous emission A¹₀ amounts to 1.63 s⁻¹ (CH⁺) and 0.19 s⁻¹ (CD⁺). Dipole moment functions of the neutral CH species in the X²Π and a⁴ Σ⁻ states have also been calculated and are compared with previous theoretical functions.     

Competitive binding exchange between alkali metal ions (K+, Rb+, and Cs+) and Na+ ions bound to the dimeric quadruplex [d(G4T4G4)]2: a 23Na and 1H NMR study

A comparative study of the competitive cation exchange between the alkali metal ions K⁺, Rb⁺, and Cs⁺ and the Na⁺ ions bound to the dimeric quadruplex [d(G₄T₄G₄)]₂ was performed in aqueous solution by a combined use of the ²³Na and ¹H NMR spectroscopy. The titration data confirm the different binding affinities of these ions for the G‐quadruplex and, in particular, major differences in the behavior of Cs⁺ as compared to the other ions were found. Accordingly, Cs⁺ competes with Na⁺ only for the binding sites at the quadruplex surface (primarily phosphate groups), while K⁺ and Rb⁺ are also able to replace sodium ions located inside the quadruplex. Furthermore, the ¹H NMR results relative to the CsCl titration evidence a close approach of Cs⁺ ions to the phosphate groups in the narrow groove of [d(G₄T₄G₄)]₂. Based on a three‐site exchange model, the ²³Na NMR relaxation data lead to an estimate of the relative binding affinity of Cs⁺ versus Na⁺ for the quadruplex surface of 0.5 at 298 K. Comparing this value to those reported in the literature for the surface of the G‐quadruplex formed by 5′‐guanosinemonophosphate and for the surface of double‐helical DNA suggests that topology factors may have an important influence on the cation affinity for the phosphate groups on DNA. Copyright © 2009 John Wiley & Sons, Ltd.     

Competitive uptake of labelled Cs+, Ba2+ and Zn2+ ions by zeolite-3A

Competitive uptake of Cs⁺, Ba²⁺ and Zn²⁺ ions from aqueous medium by zeolite-3A is studied by the radiotracer technique. Suppression Cs⁺ uptake in presence of Ba²⁺ is the maximum amongst the competitive uptakes. The simultaneous uptakes of the individual cations are considered in the light of the zeolite pore size, hydration effects and mobilities of the competing cations.     

Depth profiling of Irganox‐3114 nanoscale delta layers in a matrix of Irganox‐1010 using conventional Cs+ and O2+ ion beams

Depth profiling of an organic reference sample consisting of Irganox 3114 layers of 3 nm thickness at depths of 51.5, 104.5, 207.6 and 310.7 nm inside a 412 nm thick Irganox 1010 matrix evaporated on a Si substrate has been studied using the conventional Cs⁺ and O₂⁺ as sputter ion beams and Bi⁺ as the primary ion for analysis in a dual beam time‐of‐flight secondary ion mass spectrometer. The work is an extension of the Versailles Project on Advanced Materials and Standards project on depth profiling of organic multilayer materials. Cs⁺ ions were used at energies of 500 eV, 1.0 keV and 2.0 keV and the O₂⁺ ions were used at energies of 500 eV and 1.0 keV. All four Irganox 3114 layers were identified clearly in the depth profile using low mass secondary ions. The depth profile data were fitted to the empirical expression of Dowsett function and these fits are reported along with the full width at half maxima to represent the useful resolution for all the four delta layers detected. The data show that, of the conditions used in these experiments, an energy of 500 eV for both Cs⁺ beam and O₂⁺ beam provides the most useful depth profiles. The sputter yield volume per ion calculated from the slope of depth versus ion dose matches well with earlier reported data. Copyright © 2013 John Wiley & Sons, Ltd.     

A new Na+ and K+ carrier from chemically modified monensin studied in human erythrocytes by 23Na nuclear magnetic resonance,K+ atomic absorption and H+ potentiometry

The transporting ability of a new monensin derivative 26-(1,2-diphenyl-1-ethoxy) monensin, highly active against Gram-positive bacteria, was explored with the human erythrocyte model using three technical approaches: ²³Na nuclear magnetic resonance (internal Na⁺), K⁺ atomic absorption (external K⁺) and H⁺ potentiometry (external H⁺) and compared with monensin 1 and 26-(4-chlorophenylurethane) monensin 3 of known transport selectivities for sodium and potassium respectively. Compound 2 proved to be a good carrier for both Na⁺ and K⁺ under our experimental conditions, thus constituting a new type of monensin derivative. The introduction of Li⁺, Rb⁺ or Cs⁺ in the external buffer as a replacement for Na⁺ led us to propose the transport sequence K⁺, Na⁺ ⪢ Rb⁺ > Li⁺ > Cs⁺ for 2.     

Enhancement of the positive secondary ion yield during low‐energy,dual‐beam depth profiling of polytetrafluoroethylene with 1‐keV Cs+

This work documents the behaviour of the positive secondary ion yield of bulk polytetrafluoroethylene (PTFE) under dual‐beam depth profiling conditions employing 1 keV Ar⁺, Cs⁺ and SF₅⁺. A unique chemical interaction is observed in the form of a dramatic enhancement of the positive secondary ion yield when PTFE is dual‐beam profiled with 1 keV Cs⁺. The distinct absence of such an enhancement is noted for comparison on two non‐fluorinated polymers, polyethylene terephthalate (PET) and polydimethylsiloxane (PDMS). The bulk PTFE was probed using 15‐keV, ⁶⁹Ga⁺ primary ions in dual beam mode under static conditions; 1‐keV Ar⁺ (a non‐reactive, light, noble element), Cs⁺ (a heavier metallic ion known to form clusters) and SF₅⁺ (a polyatomic species) served as the sputter ion species. The total accumulated primary ion dose was of the order of 10¹⁵ ions/cm², which is well beyond the static limit. The enhancement of the positive secondary yield obtained when profiling with 1‐keV Cs⁺ far exceeds that obtained when SF₅⁺ is employed. An explanation of this apparent reactive ion effect in PTFE is offered in terms of polarisation of C? F bonds by Cs⁺ in the vicinity of the implantation site thereby predisposing them to facile scission. The formation of peculiar, periodic Cs_xF_y⁺ (where y = x ? 1) and Cs_xC_yF_z⁺ clusters that can extend to masses approaching 2000 amu are also observed. Such species may serve as useful fingerprints for fluorocarbons that can be initiated via pre‐dosing a sample with low‐energy Cs⁺ prior to static 15‐keV Ga⁺ analysis. Copyright © 2005 John Wiley & Sons, Ltd.     

Investigation of polyelectrolytes by total reflection X-ray fluorescence spectrometry

Water soluble polyelectrolyte samples containing mono-, bi- and trivalent metal ions were investigated without any pretreatment. Acid digestion of linear polymers may lead to a product insoluble in water so the digestion has to be avoided. The determination of analytical characteristics and limitations of the total reflection X-ray fluorescence (TXRF) analysis for poly(vinylalcohol-vinylsulfate) copolymers containing the following cations: Cs⁺; Ba²⁺; Cu²⁺ and La³⁺ are presented in this communication. On the basis of our results efficiency of ion-exchange during preparation of polyelectrolytes and stoichiometry of the end-product were determined. TXRF results were compared with data gained by inductively coupled plasma atomic emission spectrometry (ICP-AES) measurements except in the case of Cs⁺, which has poor sensitivity in ICP-AES. Good agreement was found between the results of the two techniques and calculations from titrimetric data. Concentration of Li⁺ and Mg²⁺ in polymer samples was measured only by ICP-AES.     

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.     

Cs+ -selective membrane electrodes based on ethylene glycol-functionalized polymeric microspheres

A new strategy for improving the robustness of membrane-based ion-selective electrodes (ISEs) is introduced based on the incorporation of microsphere-immobilized ionophores into plasticized polymer membranes. As a model system, a Cs⁺-selective electrode was developed by doping ethylene glycol-functionalized cross-linked polystyrene microspheres (P-EG) into a plasticized poly(vinyl chloride) (PVC) matrix containing sodium tetrakis-[3,5-bis(trifluoromethyl)phenyl] borate (TFPB) as the ion exchanger. Electrodes were evaluated with respect to Cs⁺ in terms of sensitivity, selectivity, and dynamic response. ISEs containing P-EG and TFPB that were plasticized with 2-nitrophenyl octyl ether (NPOE) yielded a linear range from 10⁻¹ to 10⁻⁵ M Cs⁺, a slope of 55.4 mV/decade, and a lower detection limit (log a_Cs) of −5.3. In addition, these membranes also demonstrated superior selectivity over Li⁺, Na⁺, and alkaline earth metal ion interferents when compared to analogous membranes plasticized with bis(2-ethylhexyl) sebacate (DOS) or membranes containing a lipophilic, mobile ethylene glycol derivative (ethylene glycol monooctadecyl ether (U-EG)) as ionophore.