MCsn cluster formation on organic surfaces: A novel way to depth-profile organics?

In this work, we investigated the bombardment of polymer surfaces (PC, PMMA) with very low energy (250 eV) Cs⁺ ions.In the positive mode, we observed many cations combining a molecular fragment of the polymer (M) with two Cs atoms, similar to the well-known MCs₂⁺ clusters commonly observed in inorganic depth profiling with Cs. For example, Cs₂COOH⁺ or Cs₂C₆H₅O⁺ were measured on PC and Cs₂CH₃O⁺ or Cs₂C₄H₅O₂⁺ were measured on PMMA. In fact, most of the polymer characteristic fragments measured in negative spectra also appear in the positive spectra, combined with two Cs atoms. It is remarkable that stable negative ions tend to combine not with one Cs, but with two Cs atoms to create the MCs₂⁺ cluster.This effect is, to some extent, similar to the well-known cationisation of polymers (with Ag or Au) although here few clusters with only one Cs atom are detected (MCs⁺ clusters), like in classical cationisation. The most abundant clusters are the MCs₂⁺ clusters, but heavier clusters (MCs₃⁺, MCs₄⁺ and above) are also measured with high yields in the spectrum.Surprisingly, some of those MCs₂⁺ clusters were still detected even after a very long sputtering fluence (above 10¹⁷ ions/cm²), proving that some molecular depth profiling is also possible in this “Cs₂-cationisation” mode. In other words, this work could open the way to an extension of the MCs_n⁺ cluster analysis, commonly used in inorganic depth profiling, to the in-depth molecular analysis of organic layers.     

Improved quantitative analysis of Cu(In,Ga)Se2 thin films using MCs+-SIMS depth profiling

The chalcopyrite semiconductor, Cu(InGa)Se₂ (CIGS), is popular as an absorber material for incorporation in high-efficiency photovoltaic devices because it has an appropriate band gap and a high absorption coefficient. To improve the efficiency of solar cells, many research groups have studied the quantitative characterization of the CIGS absorber layers. In this study, a compositional analysis of a CIGS thin film was performed by depth profiling in secondary ion mass spectrometry (SIMS) with MCs⁺ (where M denotes an element from the CIGS sample) cluster ion detection, and the relative sensitivity factor of the cluster ion was calculated. The emission of MCs⁺ ions from CIGS absorber elements, such as Cu, In, Ga, and Se, under Cs⁺ ion bombardment was investigated using time-of-flight SIMS (TOF-SIMS) and magnetic sector SIMS. The detection of MCs⁺ ions suppressed the matrix effects of varying concentrations of constituent elements of the CIGS thin films. The atomic concentrations of the CIGS absorber layers from the MCs⁺-SIMS exhibited more accurate quantification compared to those of elemental SIMS and agreed with those of inductively coupled plasma atomic emission spectrometry. Both TOF-SIMS and magnetic sector SIMS depth profiles showed a similar MCs⁺ distribution for the CIGS thin films.     

On the stoichiometry condition for the formation of cubic boron nitride films

The stoichiometry of boron nitride (BN) films, which are deposited with self-bias-assisted radio frequency (rf) magnetron sputtering of a hexagonal boron nitride (hBN) target, has been investigated with Auger electron spectroscopy (AES) and the MCs⁺-mode of secondary ion mass spectroscopy (MCs⁺-SIMS) for the sake of a better understanding of the growth mechanism of cubic boron nitride (cBN). The cubic fraction of the films is determined with Fourier-transform infrared spectroscopy (FTIR). It is shown that full stoichiometry of the deposited films is decisive for cBN-growth. A substrate bias voltage can increase the N concentration of a growing film under N-deficient deposition conditions. This effect is shown to be temperature dependent. PACS 52.77.Dq; 81.15.Cd; 68.55.Nq     

On the energy spectra of secondary ions emitted from silicon and graphite single crystals

Secondary ion emission from silicon and graphite single crystals bombarded by argon ions with energies E ₀ varied from 1 to 10 keV at various angles of incidence α has been studied. The evolution of the energy spectra of C⁺ and Si⁺ secondary ions has been traced in which the positions of maxima (E _max) shift toward higher secondary-ion energies E ₁ with increasing polar emission angle θ (measured from the normal to the sample surface). The opposite trend has been observed for ions emitted from single crystals heated to several hundred degrees Centigrade; the E _max values initially remain unchanged and then shift toward lower energies E ₁ with increasing angle θ. It is established that the magnitude and position of a peak in the energy spectrum of secondary C⁺ ions is virtually independent of E ₀, angle α, and the surface relief of the sample (in the E ₀ and α intervals studied). Unusual oscillating energy distributions are discussed, which have been observed for secondary ions emitted from silicon (111) and layered graphite (0001) faces. Numerical simulations of secondary ion sputtering and charge exchange have been performed. A comparison of the measured and calculated data for graphite crystals has shown that C⁺ ions are formed as a result of charge exchange between secondary ions and bombarding Ar⁺ ions, which takes place both outside and inside the target. This substantially differs from the ion sputtering process in metals and must be taken into account when analyzing secondary ion emission mechanisms and in practical applications of secondary-ion mass spectrometry.     

Secondary ion emission from Si under nitrogen ion bombardment

The yield and energy distribution of positive secondary ions emitted from Si under N₂⁺ ion bombardment were measured. The obtained mass peaks correspond to three types of secondary ion species, that is, physically sputtered ions (Si⁺, Si₂⁺), chemically sputtered ions (SiN⁺ Si₂N⁺) and doubly charged ions (Si²⁺). The dependence of secondary ion emission on the primary ion energy was studied in a range of 2.0–20.0 keV. The yields of physically and chemically sputtered ions were almost independent of the primary ion energy. The yield of the doubly charged ion strongly depended on the primary ion energy. The energy distribution of secondary ions of the three types showed the same dependence on the primary ion energy. The most probable energy of the distribution increased with the primary ion energy. On the other hand, for the energy distribution curves of sputtered ions, the tail factors N in E^?N were constant and showed a m/e dependence.     

Secondary ion mass spectra of alkali halides

Mass spectra of positive and negative secondary ions from various alkali halides have been measured in the Manitoba time-of-flight mass spectrometer. The ions were produced by Cs⁺ and K⁺ bombardment at primary ion energies of 3 to 19 keV for the positive spectra, and 11 to 28 keV for the negative spectra. The ions measured were those emitted within a time interval ～ 20 ns after the primary ion impact. The secondary ion yields are strongly dependent on the sample composition and treatment; prior irradiation may change the yield by an order of magnitude or more. The secondary ion yields also depend strongly on the energy loss of the primary ion, but the ratio of yields of different cluster ions from a given target is almost independent of this parameter. The results appear to be consistent with models in which the clusters are ejected directly from the target, but do not determine whether or not they possess the original surface structure. The results may also be described by a recombination model if the recombination is essentially complete.     

Comparison of secondary ion intensity enhancement from polymers on silicon and silver substrates by using Au-TOF-SIMS

The usefulness of the usage of cluster primary ion source together with an Ag substrate and detection of Ag cationized molecular ions was studied from the standpoint to realize high sensitivity TOF-SIMS analysis of organic materials. Although secondary ions from polymer thin films on a Si substrate can be detected in a higher sensitivity with Au₃⁺ cluster primary ion compared with Ga⁺ ion bombardment, it was clearly observed that the secondary ion intensities from samples on an Ag substrate showed quite a different tendency from that on Si. When monoatomic primary ions, e.g., Au⁺ and Ga⁺, were used for the measurement of the sample on an Ag substrate, [M+Ag]⁺ ions (M corresponds to polyethylene glycol molecule) were detected in a high sensitivity. On the contrary, when Au₃⁺ was used, no intensity enhancement of [M+Ag]⁺ ions was observed. The acceleration energy dependence of the detected secondary ions implies the different ionization mechanisms on the different substrates.     

Nuclear magnetic resonance and transferred hyperfine interaction study of the crystallographically inequivalent Cs(I) and Cs(II) in a Cs2CuCl4 single crystal

¹³³Cs (I=7/2) nuclear magnetic resonance in a Cs₂CuCl₄ single crystal grown by using the slow evaporation method was measured in its three mutually perpendicular crystal planes. The ¹³³Cs resonances of two different groups with two crystallographically inequivalent cesium nuclei, Cs(I) and Cs(II), in the unit cell were recorded. The transferred hyperfine fields for Cs(I) and Cs(II) calculated from the paramagnetic shift and the molecular susceptibility measurements could be expressed by the linear equation H_hf=AT+B. The angular dependence of the ¹³³Cs nuclear magnetic resonance spectra showed that the Cs(I) and the Cs(II) nuclei had different values for the quadrupole coupling constant. The electric field gradient tensors of Cs(I) and Cs(II) were symmetric, and the orientations of their principal axes did not coincide. The Cs(I) ion surrounded by 11 chlorine ions had a small quadrupole parameter, a smaller charge distribution, and a small value for the transferred hyperfine field. However, the Cs(II) ion surrounded by nine chlorine ions had a larger quadrupole parameter, a larger charge distribution, and a larger value for the transferred hyperfine field.     

Loading rate of Yb<Superscript>+</Superscript> loaded through photoionization in radiofrequency ion trap

We investigate the loading rate of Yb⁺ ions loaded through photoionization in a radiofrequency trap. The absolute or relative number of the loaded trapped ions is measured by use of an electric resonance of the secular motion. This method is applicable even in the presence of anharmonicity. In two-color photoionization, where the first-excitation laser drives the ¹S₀–¹P₁ transition in the Yb atom and the second one ionizes the atom from the ¹P₁ state, the loading rate is at its highest by the excitation of the ionization potential. A similar loading rate is observed at the second-laser wavelength around 369.5 nm, which is the wavelength for the cooling transition of Yb⁺. We estimate the loading cross section to be 40(15) Mb for the two-color excitation of the ionization potential. The excitation of the Yb atoms in the Rydberg states is detected by the enhancement of the loading rate. By irradiation with only the first-excitation laser, Yb⁺ is produced at a rate three orders of magnitude smaller than that when the non-resonant two-photon absorption from the ¹P₁ state is the dominant process. We also measure the charge-exchange rate between Yb⁺ and Yb, and discuss its effect on isotope-selective photoionization loading.     

Mixing of Au in Si induced by secondary and high-order recoil implantation

The mixing of Au in Si induced by secondary and high-order recoil implantation was investigated using 350 keV Ar⁺ and 350 keV Kr⁺ ions to fluences from 1?×?10¹⁶ to 3?×?10¹⁶ ions/cm² at room temperature. The thickness of the Au layer evaporated on Si substrate was ～2400 Å.The ranges of the Ar and Kr ions were chosen to be lower than the thickness of the Au layer in order to avoid the ballistic mixing produced by the primary knock-on atoms. Rutherford backscattering spectrometry (RBS) experiments were carried out to study the effects induced by Ar and Kr irradiation at the interface of Au–Si system. We observed that in the case of the irradiation with Ar⁺ ions, a broadening of the Au–Si interface occurred only at the fluence of 3?×?10¹⁶ Ar⁺/cm² and it is attributed to the surface roughening induced by ion bombardment. In contrast, the RBS analysis of a sample irradiated with 2?×?10¹⁶ Kr⁺/cm² clearly showed, in addition to the broadening effect, the formation of a mixed zone of Au and Si atoms at the interface. The mixing of Au in Si atoms can be explained by the secondary and high-order recoil implantation followed by subsequent collision cascades.     

Characterisation of molybdenum intermediate layers in Cu-C system with SIMS method

In the design of new high-speed chip generations a huge problem is bleeding off process heat during their operation. The installation of heat sinks onto such chips is necessary. Possible materials are copper-coated carbon composites. They combine high thermal conductivity with low density and a tailorable coefficient of thermal expansion (CTE). The low wettability of copper onto carbon necessitates a surface pretreatment.Flat slices of nitrogen-plasma etched vitreous carbon (Sigradur G) made up as a model system for carbon fiber material. The later serial fabrication of these fibers includes a hot pressing step after the deposition joining them to solid composites. It is simulated by a heat treatment step of the compound. The first sample series consisted of samples with 100 nm molybdenum and 500 nm copper layers (sputter deposited), as deposited and heat treated. The second run concludes samples without molybdenum layer but an additional 50 nm cap layer deposited after heat treatment.All samples were investigated with secondary ion mass spectrometry (SIMS), showing a diffusion of carbon into the molybdenum layer. Measuring MCs⁺ secondary ions, both matrix elements and trace elements were detectable sufficiently.     

Caesium/xenon dual beam depth profiling: Velocity of the sputtered atom and ionization probability

In this work, a caesium/xenon co-sputtering gun was used to perform depth profiles of a RhSi layer with varying caesium beam concentration. The positive ion yields were monitored with respect to the varying work function of the solid and the intensities of the ions were plotted with respect to the caesium surface concentration. As expected by the tunneling model, all the M⁺ signals decrease exponentially with the increasing caesium beam concentration. Moreover, the heaviest ion yields decrease faster than the lighter ion ones. This phenomenon can be explained by the different velocities of the departing atoms, which has an important impact on the ionization processes. We then studied the variations of the MCs⁺ yields with respect to the caesium surface concentration and with respect to the nature of the departing atom. Finally, we applied models based on the tunneling model in order to fit our results.     

Preferential sputtering of TIC under keV Ar+ ion bombardment: Simultaneous sputtering-ISS measurement with He+ and Ar+ ions

The composition change of the outermost atom layer of TiC(110) under ion bombardment with 1.5–3 keV He⁺ and He⁺ + Ar⁺ ions has been measured by ion scattering spectroscopy with He⁺ ions at different sample temperatures. It has been found that the preferential sputtering of C atoms takes place for both the He⁺ and Ar⁺ ion bombardment, however the preferred sputtering is more pronounced for Ar⁺ ions than for He⁺ ions. The ion bombardment with He⁺ ions at elevated sample temperatures hardly results in any change in surface composition below ～800°C, while Ar⁺ ion bombardment results in C enrichment for elevated temperatures as reported so far.     

Exact compositional analysis of SiGe alloys by matrix effect compensated MCs+-SIMS

SiGe alloy, owing to its high electron and hole mobility, has potential applications in high-speed microelectronic device technology. The optimization of such technology requires the precise determination of Ge concentration in the full range of composition and the understanding and control of the Ge–Si interdiffusion phenomenon. The most appropriate analytical technique with highest detection sensitivity (～subparts per billion) for measuring elemental concentration is secondary ion mass spectrometry (SIMS). However, strong compositional dependence of secondary ion yield, i.e. “matrix effect,” has always made SIMS quantification extremely difficult. A procedure for the accurate quantification of Ge concentration in molecular beam epitaxy (MBE)-grown Si_1?x Ge _x (0<x<0.72) alloys based on MCs⁺-SIMS approach has been proposed. The “matrix effect” is shown to be completely suppressed for all Ge concentrations irrespective of impact Cs⁺ ion energies. The novel methodology has successfully been applied for direct quantitative composition analysis of Si/Ge multilayer structure.     

Thermally stimulated desorption of Na<Superscript>+</Superscript> and Cs<Superscript>+</Superscript> ions from a NaAu alloy film grown on Au

The formation of Na⁺ and Cs⁺ ions on and their thermal desorption from the surface of a NaAu alloy film grown on metallic gold are studied. It is shown that thermionic emission from insulator-coated metallic substrates is governed by a sequence of processes, such as diffusion of Na and Cs adatoms into the film, ionization of these atoms at the insulator-metal interface, diffusion of the resulting ions toward the surface, and desorption of the ions. The effect of weak electric fields on ion diffusion and desorption is investigated.     

Cesium redeposition artifacts during low energy ToF-SIMS depth profiling

H-terminated Si samples were preloaded with Cs by performing ToF-SIMS depth profiles (250 eV Cs⁺, 15 keV Ga⁺) until the steady state was reached both with and without a bias of +40 V applied to the ion extraction electrode. Xe⁺ depth profiles (350 eV Xe⁺, 15 keV Ga⁺) were obtained inside and around the Cs craters with and without applying the 40 V bias. The results indicate that the maximum of the Cs⁺ signal of the Xe⁺ depth profiles shifts to the surface if no bias is applied, either during the Cs⁺ sputtering or during the Xe⁺ sputtering (i.e., the profiles are broadest with both biases (Cs⁺ and Xe⁺) on and narrowest and closest to the surface if both biases are off). This effect can be explained by the electric field, caused by the bias, deflecting the sputtered low energy Cs⁺ ions back to the surface.     

Characterisation of human hair surfaces by means of static ToF-SIMS: A comparison between Ga and C60 primary ions

This study deals with the secondary ion yield improvement induced by using C₆₀⁺ primary ions instead of Ga⁺ ones to characterize human hair surfaces by ToF-SIMS. For that purpose, a bunch of hair fibres has been analysed with both ion sources. A high improvement is observed for the detection of amino acids with C₆₀⁺ primary ions as compared to Ga⁺ ions. As an example, a yield enhancement factor greater than 3000 is found for the CNO⁻ peak. A similar gain is observed for the positive secondary ions characteristic of the amino acids. Most of the atomic ions, such as Ca⁺, O⁻ and S⁻, constitute minor peaks with C₆₀⁺ ions while they often dominate the spectrum in the case of Ga⁺ ions. However, with the C₆₀⁺ source, a series of inorganic combination peaks with the elements Ca, S and O are observed in the positive spectra (i.e. HCaSO₄⁺), while they are marginal with the Ga⁺ source. For the mass range beyond 100 m/z and in both polarities, the hair fingerprints are similar with both sources. In average, for a comparable number of primary ions per spectrum, the C₆₀⁺ ion source gives intensities between two and three orders of magnitude higher than the Ga⁺ one.     

An upgraded TOF-SIMS VG Ionex IX23LS: Study on the negative secondary ion emission of III-V compound semiconductors with prior neutral cesium deposition

A TOF-SIMS VG Ionex IX23LS with upgraded data acquisition and control system was used to study the secondary emission of negative atomic and cluster ions of non-metallic elements (P, As and Sb) upon a 19 keV Ga⁺ bombardment of non-degenerated III-V semiconductors (GaP, GaAs, GaSb, InP, InAs and InSb) with prior neutral Cs deposition from a getter dispenser. It was found that surface cesiation enhances the peak intensity of all negative ion species; in the case of atomic ions, the greatest increase (360) was observed for P⁻ emitted from InP. Such an enhancement was larger for In-based than for Ga-based compounds. We explained that in terms of an electronegativity difference between the composing atoms of III-V semiconductors. The greater electronegativity difference (bond ionicity) of In-based compounds resulted in the greater Cs-induced work function decrease leading to a higher increase in the ionization probability of secondary ions.     

Molecular depth profiling of polymers with very low energy ions

The need for a molecular depth profiling technique to study organic layers has become a strong incentive in the SIMS community in the last few years, especially with the recent successes obtained with cluster ion beam depth profiling. In this work, we have investigated a thoroughly different approach by using very low energy (down to 200 eV) monoatomic or diatomic ions to sputter organic matter. Quite surprisingly, we were able to retain specific molecular information on various polymers even at very high fluence.Polymethylmethacrylate (PMMA) and polyethylene terephthalate (PET) films were depth-profiled with 200 eV Cs⁺ and 500 eV O₂⁺ ions. With 200 eV Cs ions, the best profiles were obtained in the negative mode, due to a strong negative ionisation yield enhancement related to Cs retention in the polymer. A relatively high and stable signal from the most characteristic ions was measured all over the layer.With 500 eV O₂⁺, real molecular depth-profiles were also obtained in both the positive and the negative modes. Once again, the main characteristic fragments of PET or PMMA remain detectable with stable yields all over the profile.     

Preparation and Sorption Properties of Cadmium Hexacyanocobaltate(III)

The preparation of cadmium hexacyanocobaltate (III), CdHCC, is discussed. The product has been prepared by reacting cadmium nitrate and potassium hexacyanocobaltate (III) in a volume ratio of 2:1. The effect of the monovalent cations, H⁺, Na⁺, K⁺, and NH₄ ⁺ on the percentage retention and of pH on the loading capacity of CdHCC for cesium have been investigated. It has been found that the equilibrium behavior and the loading capacity of CdHCC after being soaked overnight in M NaCl are significantly improved. A loading capacities of 10, 30, and 60 g Cs/kg CdHCC have been achieved from simulated PWR waste, MAW and solutions of pH 12, respectively. A comparison of the distribution coefficients for cesium in different media is made.