Comparative SNMS and SIMS studies of oxidized Ce and Gd

Polycrystalline Ce and Gd surfaces of various oxidation states have been investigated in situ and alternately by Sputtered Neutral Mass Spectrometry SNMS and by SIMS. For the bombardment with 4 keV Ar⁺ ions the dominating peaks in the mass spectra of postionized sputtered neutrals and positive secondary ions refer to metal atoms Me and monoxide molecules MeO. At oxygen concentrations of several atomic percent the sensitivity of SNMS and SIMS are of the same order. Characteristic differences are found between the behaviour of corresponding SNMS and SIMS signals: For SNMS the intensitiesI(MeO⁰) and I(Me⁰) in general vary complementarily when the oxygen is removed from the surface. The intensity ratios $\text{I(MeO}{}^0\text{)}\text{I(Me}{}^0\text{)}$ decrease monotonously by 1 to 2 orders of magnitude. With SIMS both I(MeO⁺) and I(Me⁺) are found to decrease with the oxygen content. The SIMS ratios $\text{I(MeO}{}^{\mathrm{+}}\text{I(Me}{}^{\mathrm{+}}\text{)}$ display an oscillatory behaviour with only little variation of their absolute values. As an example, quantitative results for the behaviour of the ionisation probability α⁺_Me for the secondary ions Ce⁺ and Gd⁺ are derived for low oxygen concentrations.     

Energy dependence of the ionization probability of sputtered Cu and Ni

Despite its great sensitivity, the usefulness of secondary ion mass spectrometry (SIMS) for many applications has been limited by an inadequate understanding of the probability of sputtering an atom in an ionized state. To determine this ionization probability for clean Cu and Ni surfaces, I have measured the energy distribution of sputtered neutrals and ions by quadrupole mass filtering and retarding potential analysis using potential modulation differentiation. Analysis of sputtered neutrals was accomplished by electron impact ionization. Because the neutrals outnumber the ions by at least two orders of magnitude, the ratio of sputtered ions to neutrals is an accurate measure of the ionization probability. For energies below 20 eV the dependence of the ionization probability on energy goes as P(E) α Eⁿ, where n = 0.65 for clean Cu. The absorption of oxygen on the Cu surface increases the total ion yield while causing a reduction in the value of the exponent n. Similar results are found for nickel, where n = 0.54 for the clean surface.     

Nmr and Mass Spectroscopic Studies of the Competitive-Angiotensin II Antagonist “Sarmesin”

Fast atom bombardment mass spectrometry (FAB-MS) and high resolution (400 Mz) proton nuclear magnetic resonance (NMR spectroscopy) on the competitive angiotensin II antagonist, |Sar¹, Tyr(Me)⁴ (ANGII (Sarmesin) and its he-ptapeptide homolog, [Tyr(Me)³ |ANGIII, yield spectra which provide confirmation of structure and molecular weight. The characteristics of the spectra are discussed and compared with the spectra of natural ANG II, ANG III and |Sar¹|ANG II. The NMR data are suggestive of interactions in angiotensin between: 1) the phenolic hydroxyl group and the imidazole ring, and 2) the N-terminal amino group and the Tyrring. These interactions may be important for the formation of the proposed charge transfer system in angiotensin II involving the phenoxyl and α-carboxylate groups.     

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.     

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.     

Sputtering of Ta2O5 by Ar+ ions at energies below 1 keV

The sputtering of anodically formed Ta₂O₅ layers of about 3500 Å thickness has been studied by Sputtered Neutral Mass Spectroscopy (SNMS). For perpendicular bombardment with Ar⁺ ions up to 900 eV the flux of ejected neutral particles is found to consist almost exclusively of metal atoms Ta and Oxide specific molecules TaO and TaO₂ with intensity ratios in the order 1 : 1 : 10^?1. From depth profiling measurements with SNMS, and from the intensity ratios in the SNMS spectra the total sputtering yield of Ta₂O₅ and the partial yields of Ta, TaO and of oxygen have been determined for normally incident Ar⁺ ions of 100 to 600 eV. After an initial increase the TaO intensity in the SNMS spectra remains constant during the sputter removal of the whole layer. A simple model is derived by which the preferred emission of TaO molecules, and the initial increase of the TaO intensity is referred to ion induced variations of the surface stoichiometry of Ta₂O₅. For optimum TaO production the model predicts equal atomic surface concentrations of Ta and O.     

HFC-152a的同步辐射真空紫外光电离和光解离研究

利用同步辐射真空紫外光，研究了HFC-152a(CH₃CHF₂)的光电离和光解离过程，通过测量各离子的光电离效率曲线，得到了该分子的电离能(11.94±0.04eV)和所有碎片离子的出现势，运用GAUSSIAN-03程序计算了母体和碎片及相应离子的结构、电子态和能量. 结合理论计算的结果，分析了母体离子可能的光电离解离通道及相关通道的解离能. 关键词： 同步辐射 光电离 出现势 HFC-152a     

Multivariate data analysis for depth resolved chemical classification and quantification of sulfur in SNMS

The quantification of elements in quadrupole based SNMS is hampered by superpositions of atomic and cluster signals. Moreover, the conventional SNMS data evaluation employs only atomic signals to determine elemental concentrations, which not allows any chemical specifications of the determined elements. Improvements in the elemental quantification and additional chemical information can be obtained from kinetic energy analysis and the inclusion of molecular signals into mass spectra evaluation. With the help of multivariate data analysis techniques, the combined information is used for the first time for a quantitative and chemically distinctive determination of sulfur. The kinetic energy analysis, used to solve the interference of sulfur with O₂ at masses 32-34 D, turned out to be highly important for the new type of evaluation.     

An examination of the initial oxidation of a uranium-base alloy (U–14.1 at.% Nb) by O2 and D2O using surface-sensitive techniques

The corrosion resistance of uranium is greatly enhanced by alloying with niobium. In this study the initial stages of corrosion of a specific uranium-base alloy (U–14.1 at.% Nb) by O₂ or D₂O have been examined using the surface specific techniques of X-ray photoelectron spectroscopy (XPS), thermal programmed desorption (TPD), static secondary-ion mass spectroscopy (SSIMS), and sputtered neutrals mass spectroscopy (SNMS). XPS studies of the U–14.1 at.% Nb surface following oxidation using O₂ at 300 K indicate production of a thin oxide overlayer of stoichiometric UO_2.0 intermixed with Nb₂O₅. The same stoichiometry is exhibited for uranium when the oxide is prepared at 500 K with O₂; although, niobium is much less oxidized exhibiting a mixture of NbO and Nb. Contrary to previous XPS literature, SNMS depth profiling studies reveal that oxidation by O₂ is much greater (as judged by oxide layer thickness) than that exhibited by D₂O. An oxide layer thickness of less than 20 Å was created using D₂O as an oxidant at 300 K with exposures >3500 L (oxide layers created from O₂ are significantly greater at much smaller exposures). Formation of a critical density of Nb₂O₅ is suggested to be responsible for the enhanced corrosion resistance by preventing diffusion of O⁻ (O²⁻) or OD⁻/OH⁻ into the oxide/metal interface region. The domains of stability of hydroxyl formation have also been followed using TPD, SSIMS and XPS. Maximal surface hydroxyl concentrations (Θ_rel=0.30) are obtained at a surface temperature of 175 K for these experimental conditions.     

Electronic-beam evaporation processed titanium oxide as an electron selective contact for silicon solar cells

This work is dedicated to the study of electronic-beam (e-beam) evaporated titanium oxide (TiO_x) contact for polycrystalline silicon hetero-junction solar cells. A TiO_x material obtained by e-beam evaporation method is suggested as a possible alternative to the atomic layer deposition (ALD) process. The purpose is to achieve corresponding passivation efficiency between e-beam evaporation of TiOx and the ALD method. However, the TiOx in question achieved a relatively low passivation performance of S_eff = 113 cm⁻¹ in comparison to the reported ALD results. Nonetheless, as e-beam evaporation is well-established and an environmentally friendly deposition technology, e-beam evaporated TiO_x passivation layer has potential for improvement. What is clearly demonstrated in our work is how such an improvement in contact resistance dropped from >55 Ω/cm² to 2.29 Ω/cm². Indeed, our study established a correlation between the main process parameters of e-beam evaporation and their influence on the quality of electron selective TiO_x layer. Moreover, we reveal a possible scenario for the implementation of e-beam evaporated Titanium oxide as electron selective contact for asymmetrical hetero-junction solar cells.     

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.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

Rapid growth of ultra thin SiO2 films by a large-area electron beam

Rapid growth of ultra thin oxide films (40–180Å) of silicon using a low-energy large-area electron beam has been performed with a pressure ratio of 31 (O₂/He) and a total pressure of 0.5–0.7 Torr. A higher oxidation rate of about 625Ų/s is found for shorter irradiation time of the e-beam in the e-beam dose range 0.75–3 Coulomb/cm² and at lower substrate temperature 540–740°C. AES and XPS demonstrated a rapid electron-stimulated oxidation process of the Si surface. For the grown ultra thin oxide films, C-V characteristics, dielectric strength, uniformity of the film over the entire Si wafer and its thickness as a function of the processing time of the e-beam are also presented.     

Ion-molecule reactions at thermal energies

Ion-molecule reactions is a generic word for reactions involving ions (both positive and negative), radicals and stable neutrals. In this presentation, use of the flowing afterglow technique to study ion-molecule reactions at thermal energies is demonstrated using the examples of positive ion-negative ion mutual neutralization of molecular nitrogen ion (N ₂ ⁺ ) with F⁻ and the reaction of atomic nitrogen with SF _n (n=1 to 5) to form NF.     

The chemisorption of nitrogen on the (001) surface of ruthenium

High resolution electron energy loss spectroscopy (EELS), thermal desorption mass spectrometry (TDMS) and low energy electron diffraction (LEED) have been used to investigate the molecular chemisorption of N₂ on Ru(001) at 75 K and 95 K. Adsorption at 95 K produces a single chemisorbed state, and, at saturation, a (√3x√3) R30° LEED pattern is observed. Adsorption at 75 K produces an additional chemisorbed state of lower binding energy, and the probability of adsorption increases by a factor of two from its zero coverage value when the second chemisorbed state begins to populate. EEL spectra recorded for all coverages at 75 K show only two dipolar modes — ν(RuN₂) at 280–300 cm^?1 and ν(NN) at 2200–2250 cm^?1 — indicating adsorption at on-top sites with the axis of the molecular standing perpendicular to the surface. The intensities of these loss features increase and ν(NN) decreases with increasing surface coverage of both chemisorbed states.     

SNMS investigations of platinum-doped nanogranular tin dioxide layers

Thin platinum-doped nanogranular SnO₂ layers are examined because of its high gas sensitivity and fast gas response to be applied in gas sensor microarrays. The nanogranular metal oxide layers were prepared from a colloidal dispersion using spin coating on silicon substrates. Field emission scanning electron microscopy (FE-SEM) investigations showed quite homogeneous layers of 20 nm particles, containing a few holes of some micron width, probably due to bubbles introduced into the layer during wet deposition. Depth resolved analysis with secondary neutral mass spectrometry (SNMS) was employed to characterize the elemental content and depth distribution of the 20 nm particle layers. A platinum content of approx. 1 at.%, homogeneously spread throughout the particles was found, as well as carbon and chlorine residues of a few atomic percent enriched at the surface of the particles.     

Determination and analysis of opiates in complex mixtures by surface-ionization mass spectrometry

The results of studies of the analytical opportunities of surface-ionization mass spectrometry (SIMS) for high-sensitivity and selective detection and analysis of opiate mixtures—natural opium, crude heroin, and narcotic analgesic omnopon—are presented. The experiments were carried out using an MX-1320 chemical mass spectrometer modernized for studying surface ionization (SI). It was ascertained that the opiate mixtures are ionized by highly efficient surface ionization. The bands of M⁺ (for papaverine), (M-H)⁺, (M-H-2nH)⁺, (M-R)⁺, and (M-R-2nH)⁺ ions, where M is a molecule, H is a hydrogen atom, R is a radical, are observed in the mass spectra; they are the sum of the SI mass spectra of components of the mixtures. The series of bands of ions with m/z of 144 and 146 that is characteristic of SI-morphinelike molecules is the main one in the mass spectrum of crude heroin, while for omnopon and natural opium this series is the main at low temperatures of a thermionic emitter (up to ∼900 K). At high temperatures of the thermionic emitter, the band series with m/z of 218 and 220 is the main series. Studies of natural opium, crude heroin, and omnopon have shown that the SIMS method allows analyzing mixtures without preliminary chromatographic separation thereof. The study also contains the results of comparative analyses of opiate mixtures by SIMS and chromate- and mass spectrometry (HP-6890) with electronic ionization.     

Experimental and theoretical investigations into the origin of cross-contamination effects observed in a quadrupole-based SIMS instrument

The minimum-detection limits achievable in SIMS analyses are often determined by transport of material from surrounding surfaces to the bombarded sample. This cross-contamination (or memory) effect was studied in great detail, both experimentally and theoretically. The measurements were performed using a quadrupole-based ion microprobe operated at a secondary-ion extraction voltage of less than 200 V (primary ions mostly 8keV O ₂ ⁺ ). It was found that the flux of particles liberated from surrounding surfaces consists of neutrals as well as positive and negative ions. Contaminant species condensing on the bombarded sample could be discriminated from other backsputtered species through differences in their apparent energy spectra and by other means. The apparent concentration due to material deposited on the sample surface was directly proportional to the bombarded area. For an area of 1 mm² the maximum apparent concentration of Si in GaAs amounted to 5 × 10¹⁶atoms/cm³. The rate of contamination decreased strongly with increasing spacing between the bombarded sample and the collector. The intensities of backsputtered ions and neutrals increased strongly with increasing mass of the target atoms (factor of 10 to 50 due to a change from carbon to gold). The effect of the primary ion mass (O ₂ ⁺ , Ne⁺, and Xe⁺) and energy (5–10keV) was comparatively small. During prolonged bombardment of one particular target material, the rate of contamination due to species not contained in the sample decreased exponentially with increasing fluence. In order to explain the experimental results a model is presented in which the backsputtering effect is attributed to bombardment of surrounding walls by high-energy particles reflected or sputtered from the analysed sample. The level of sample contamination is described by a formula which contains only measurable quantities. Cross-contamination efficiencies are worked out in detail using calculated energy spectra of sputtered and reflected particles in combination with the energy dependence of the sputtering yield of the assumed wall material. The experimental findings are shown to be good agreement with the essential predictions of the model.     

Effect of an aliphatic spacer group on the adsorption mechanism on the colloidal silver surface of L‐proline phosphonodipeptides

A comparative study of molecular structures of five L ‐proline (L ‐Pro) phosphonodipeptides: L ‐Pro‐NH‐C(Me,Me)‐PO₃H₂ (P1), L ‐Pro‐NH‐C(Me,iPr)‐PO₃H₂ (P2), L ‐Pro‐L ‐NH‐CH(iBu)‐PO₃H₂ (P3), L ‐Pro‐L ‐NH‐CH(PA)‐PO₃H₂ (P4) and L ‐Pro‐L ‐NH‐CH(BA)‐PO₃H₂ (P5) has been carried out using Raman and absorption infrared techniques of molecular spectroscopy. The interpretation of the obtained spectra has been supported by density functional theory calculations (DFT) at the B3LYP; 6–31 + + G** level using Gaussian 2003 software. The surface‐enhanced Raman scattering (SERS) on Ag‐sol in aqueous solutions of these phosphonopeptides has also been investigated. The surface geometry of these molecules on a silver colloidal surface has been determined by observing the position and relative intensity changes of the Pro ring, amide, phosphonate and so‐called spacer (−R) groups vibrations of the enhanced bands in their SERS spectra. Results show that P4 and P5 adsorb onto the silver as anionic molecules mainly via the amide bond (∼1630, ∼1533, ∼1248, ∼800 and ∼565 cm⁻¹), Pro ring (∼956, ∼907 and ∼876 cm⁻¹) and carboxylate group (∼1395 and ∼909 cm⁻¹). Coadsorption of the imine nitrogen atom and PO group with the silver surface, possibly by formation of a weaker interaction with the metal, is also suggested by the enhancement of the bands at 1158 and 1248 cm⁻¹. P1, P2 and P3 show two orientations of their main chain on the silver surface resulting from different interactions of the  C CH₃,  NH and  CONH fragments with this surface. Bonding to the Ag surface occurs mainly through the imino atom (1166 cm⁻¹) for P2, while for P1 and P3 it occurs via the methyl group(s) (1194–1208 cm⁻¹). The amide group functionality (CONH) is practically not involved in the adsorption process for P1 and P2, whereas the C_s P bonds do assist in the adsorption. Copyright © 2008 John Wiley & Sons, Ltd.     

Sputtering—a review of some recent experimental and theoretical aspects

After a brief outline of the present sputtering theory for a random solid, recent results of the sputtering yieldS for polycrystalline targets are discussed, in particular in view of the influence of the projectile mass and the bombarding angle. The angle dependence ofS at low bombarding energies, and results on the angular distribution of sputtered particles for oblique ion incidence point out necessary modifications of present sputtering theories with respect to the anisotropy of the collision cascades in the solid and the influence of the target surface. The energy distribution of the neutral particles ejected along the target normals is related to the theoretically predictedE ^?2-distribution of low energy recoils in the Recent mass spectrometric studies of postionized sputtered neutrals are discussed in view of the formation of sputtered molecules and the application of sputtered neutral mass spectroscopy for surface analysis. Finally, the paper deals with ion-induced surface effects on non-elementary sputtering targets, and the protracted removal of foreign atoms from a matrix.