Dynamic Secondary Ion Mass Spectrometry Research Articles

Steady-State Statistical Sputtering Model for Extracting Depth Profiles from Molecular Dynamics Simulations of Dynamic SIMS

Recently a “divide and conquer” approach was developed to model by molecular dynamics (MD) simulations dynamic secondary ion mass spectrometry (SIMS) experiments in order to understand the importan...

Molecular dynamic‐secondary ion mass spectrometry (D‐SIMS) ionized by co‐sputtering with C60+ and Ar+

Dynamic secondary ion mass spectrometry (D-SIMS) analysis of poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) was conducted using a quadrupole mass analyzer with various combinations of continuous C(60)(+) and Ar(+) ion sputtering. Individually, the Ar(+) beam failed to generate fragments above m/z 200, and the C(60)(+) beam generated molecular fragments of m/z ~1000. By combining the two beams, the auxiliary Ar(+) beam, which is proposed to suppress carbon deposition due to C(60)(+) bombardment and/or remove graphitized polymer, the sputtering range of the C(60)(+) beam is extended. Another advantage of this technique is that the high sputtering rate and associated high molecular ion intensity of the C(60)(+) beam generate adequate high-mass fragments that mask the damage from the Ar(+) beam. As a result, fragments at m/z ~900 can be clearly observed. As a depth-profiling tool, the single C(60)(+) beam cannot reach a steady state for either PET or PMMA at high ion fluence, and the intensity of the molecular fragments produced by the beam decreases with increasing C(60)(+) fluence. As a result, the single C(60)(+) beam is suitable for profiling surface layers with limited thickness. With C(60)(+)-Ar(+) co-sputtering, although the initial drop in intensity is more significant than with single C(60)(+) ionization because of the damage introduced by the auxiliary Ar(+), the intensity levels indicate that a more steady-state process can be achieved. In addition, the secondary ion intensity at high fluence is higher with co-sputtering. As a result, the sputtered depth is enhanced with co-sputtering and the technique is suitable for profiling thick layers. Furthermore, co-sputtering yields a smoother surface than single C(60)(+) sputtering.

Morphological Characterization of a Low‐Bandgap Crystalline Polymer:PCBM Bulk Heterojunction Solar Cells

AbstractUnderstanding the morphology of polymer‐based bulk heterojunction (BHJ) solar cells is necessary to improve device efficiencies. Blends of a low‐bandgap silole‐containing conjugated polymer, poly[(4,4′‐bis(2‐ethylhexyl)dithieno[3,2‐b;2′,3′‐d]silole)‐2,6‐diyl‐alt‐(4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole)‐5,5′‐diyl] (PSBTBT) with [6,6]phenyl‐C61‐butyric acid methyl ester (PCBM) were investigated under different processing conditions. The surface morphologies and vertical segregation of the “As‐Spun”, “Pre‐Annealed”, and “Post‐Annealed” films were studied by scanning force microscopy, contact angle measurements, X‐ray photoelectron spectroscopy, near‐edge X‐ray absorption fine structure spectroscopy, dynamic secondary ion mass spectrometry, and neutron reflectivity. The results showed that PSBTBT was enriched at the cathode interface in the “As‐Spun” films and thermal annealing increased the segregation of PSBTBT to the free surface, while thermal annealing after deposition of the cathode increased the PCBM concentration at the cathode interface. Grazing‐incidence X‐ray diffraction and small‐angle neutron scattering showed that the crystallization of PSBTBT and segregation of PCBM occurred during spin coating, and thermal annealing increased the ordering of PSBTBT and enhanced the segregation of the PCBM, forming domains ∼10 nm in size, leading to an improvement in photovoltaic performance.

Controlling Mn depth profiles in GaMnAs during high-temperature molecular beam epitaxial growth

Mn-doped GaAs thin films were grown at a high substrate temperature of 580 °C. During the growth process the Mn cell temperature was ramped at different rates, resulting in a variety of different Mn concentration depth profile slopes, as measured by dynamic secondary ion mass spectrometry (SIMS). Results show that controlling the Mn deposition rate via temperature during molecular beam epitaxy (MBE) growth can mitigate the effect of Mn atoms diffusing toward the surface. Most importantly, the slope of the Mn concentration as a function of depth inside the sample can be tuned from negative to positive.

Investigation of shrinkage and cracking of ophthalmic lens coating by a cycle test of UV radiation and high humidity

This paper presents some ophthalmic lens coating failures such as shrinkage, cracking, and cracking with delamination caused by UV radiation, elevated temperature, and moisture. These phenomena are caused by: 1) interactions at the interface between the plastic substrate and the hard coating (HC), and 2) plastic deformation with stress and relaxation of the HC/substrate interface. This phenomenon leads to an understanding of the mechanical properties of ophthalmic lenses through a QUV test which is found to be a useful method in developing better ophthalmic lens systems. The coating failures were investigated by means of different analysis techniques including optical microscope, scanning electron microscope, atomic force microscope, thermo mechanical analysis, and dynamic secondary ion mass spectrometry.

H2/N2 plasma damage on porous dielectric SiOCH film evaluated by in situ film characterization and plasma diagnostics

This study investigates the mechanism of H2/N2 plasma ashing damage of porous SiOCH films. Porous SiOCH films were treated by a H2/N2 plasma using a 100-MHz capacitively coupled plasma etcher. The impact of ions, radicals, and vacuum ultraviolet radiation on the porous SiOCH films was investigated using in situ bulk analysis techniques such as spectroscopic ellipsometry and Fourier-transform infrared spectroscopy and ex situ film characterization techniques such as dynamic secondary ion mass spectrometry and x-ray photoelectron spectroscopy. In addition, plasma analysis including vacuum ultraviolet absorption spectroscopy was performed. The film characterization and plasma analysis show that the extraction of methyl by H radicals was enhanced by light while N radicals were responsible for inhibit the extraction of Si-CH3 bonds by forming nitride layer. The H2/N2 plasma damage mechanism is discussed based on characterization of the film and plasma diagnostics.

Tuning the Vertical Phase Separation in Polyfluorene:Fullerene Blend Films by Polymer Functionalization

Achieving control over the nanomorphology of blend films of the fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester, PCBM, with light-absorbing conjugated polymers is an important challenge in the development of efficient solution-processed photovoltaics. Here, three new polyfluorene copolymers are presented, tailored for enhanced miscibility with the fullerene through the introduction of polymer segments with modified side chains, which enhance the polymer's polar character. The composition of the spincoated polymer:PCBM films is analyzed with dynamic secondary ion mass spectrometry (dSIMS). The dSIMS depth profiles demonstrate compositional variations perpendicular to the surface plane, as a result of vertical phase separation, directed by the substrate. These variations propagate to a higher degree through the film for the polymers with a larger fraction of modified side chains. The surface composition of the films is studied by Near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Quantitative analysis of the NEXAFS spectra through a linear combination fit with the spectra of the pure components yields the surface composition. The resulting blend ratios reveal polymer-enrichment of the film surface for all three blends, which also becomes stronger as the polar character of the polymer increases. Comparison of the NEXAFS spectra collected with two different sampling depths shows that the vertical composition gradient builds up already in the first nanometers underneath the surface of the films. The results obtained with this new series of polymers shed light on the onset of formation of lamellar structures in thin polymer:PCBM films prepared from highly volatile solvents.

Enhanced Detection of Copper Impurity in Silicon Wafer by Dynamic Secondary Ion Mass Spectrometry

Enhanced Detection of Copper Impurity in Silicon Wafer by Dynamic Secondary Ion Mass Spectrometry

Depth resolution enhancement by combined DSIMS and TOF-LEIS profiling

A combination of dynamic secondary ion mass spectroscopy (DSIMS) and time-of-flight low-energy ion scattering (TOF-LEIS) has been applied to acquire a composition depth profile of MoSi multilayers. During the sequential Ar + sputtering secondary ions were monitored while in-between the sputtering cycles the TOF-LEIS spectra of scattered He neutrals were acquired. All the measured TOF-LEIS spectra versus sputtering time were displayed in one bitmap from which the depth profiles for different scattering depths were derived and analyzed. Analyzing the TOF-LEIS spectra of He particles scattered from the areas below the layer altered by ion-beam mixing led to an improvement of the depth resolution. In this way the resolution limits due to mixing phenomena can be overcome. Finally, the direct comparison of the DSIMS and TOF-LEIS depth profiles was carried out.

An in vitro evaluation of a novel high fluoride daily mouthrinse using a combination of microindentation, 3D profilometry and DSIMS

Objectives Firstly, to evaluate the in vitro anti-erosion efficacy of a new mouthrinse formulation containing 450 ppm fluoride using profilometry and microindentation. Secondly, to compare fluoride uptake by erosive lesions from two mouthrinses containing different fluoride sources using dynamic secondary ion mass spectrometry (DSIMS). Methods Sound human enamel was treated (60s) with mouthrinses containing different fluoride concentrations, then immersed in 1.0% citric acid pH3.8 for either 300s or 30min (Studies 1 & 2 respectively). Surface roughness and erosion depth were determined profilometrically in Study 1, and surface microhardness monitored as a function of time in Study 2. Lesion rehardening was monitored following a 60 s rinse and immersion in artificial saliva for 48 h (Study 3), whilst Study 4 employed DSIMS to quantify fluoride uptake by lesions treated (60s) with rinses containing either sodium fluoride (NaF) or a NaF/Olaflur/stannous chloride combination. Results The test rinse (450 ppm fluoride) suppressed surface roughening and bulk tissue loss versus all comparators (p< 0.0001), except in the latter measure for the rinse containing 112 ppm fluoride. The test rinse significantly inhibited enamel surface softening versus the three rinses containing ≤112 ppm fluoride (as NaF) at 30min (p<0.05), but was not statistically significantly different from the 225 ppm fluoride rinse. The test rinse conferred statistically superior lesion rehardening versus all comparators at both 24 and 48 h (p< 0.0001). DSIMS demonstrated statistically significantly higher fluoride uptake by incipient erosive lesions treated with the test rinse versus the NaF/Olaflur/stannous rinse. Conclusions Anti-erosion efficacy was positively correlated with fluoride concentration. DSIMS showed significantly higher levels of fluoride uptake by incipient erosive lesions treated with the 450 ppm fluoride rinse versus the NaF/Olaflur/stannous rinse.

Studies on a novel combination polymer system: in vitro erosion prevention and promotion of fluoride uptake in human enamel

Objectives Firstly, determine the effect of pre-treating sound human enamel with a hydrosoluble combination polymer system (TriHydra™) comprising 0.20% carboxymethylcellulose, 0.010% xanthan gum and 0.75% copovidone, alone or in combination with fluoride, on in vitro erosion by citric acid. Secondly, investigate the effect of the polymers on fluoride uptake by incipient erosive lesions. Methods Study 1: Sound enamel specimens were treated (60s, 20°C, 150 rpm) with either (i) deionised water, (ii) polymers in deionised water, (iii) 300 mg/L fluoride or (iv) polymers in 300 mg/L fluoride. Specimen groups (n=5) were then immersed in 1.0% citric acid (pH 3.8, 300s, 20°C, 50rpm) and non-contact profilometry was used to determine surface roughness (Sa) and bulk tissue loss. Study 2: Incipient erosive lesions were similarly treated with (i)-(iv). Dynamic Secondary Ion Mass Spectrometry (DSIMS) was then used to determine the fluoride depth-distribution. Results Study 1: Mean±SD Sa and erosion depths for treatment groups (i)-(iv) were a657±243, b358±50, c206±72, d79±16nm and a19.73±8.70, b2.52±1.34, b0.49±0.34 and b0.31±0.21mm respectively (matching superscripts denote statistically equivalent groups). Study 2: Lesions treated with (iii) and (iv) exhibited similar fluoride penetration depths (∼60μm). Mean fluoride intensity ratios based on F/(F+P) at 1μm for treatment groups (i)-(iv) were a0.010±0.004, a0.011±0.004, b0.803±0.148 and c0.994±0.004 respectively. Conclusions The combination polymer system exhibited anti-erosion efficacy in its own right. The polymer/fluoride admixture statistically significantly reduced Sa, however suppression of bulk tissue loss was not statistically significantly different versus either treatment alone. The presence of polymer appears to promote fluoride uptake by erosive lesions most noticeably in the first 6μm.

Dendrites and pillars in spin cast blends of polyaniline or its oligomeric analogue

In the present work morphological structures were examined which are formed spontaneously during the spin-casting of polymer blends. Mixtures of polyaniline (PANI) (doped with camphorsulfonic acid, CSA) or its oligomeric counterpart (N,N′-diphenyl-p-phenylenediimine, DPI) and a conventional polymer (polystyrene, PS or poly(methyl methacrylate), PMMA) were studied. The samples were manufactured in controlled humidity conditions (relative humidity, RH = 10%, 60% or 95%). In case of PANI(CSA)/PS (or PMMA) blends, hierarchic structures arise. They are built of large (>10 μm) PS-rich (or PMMA-rich) dendrites and sub-micron PANI-rich pillars in the pores of PS (PMMA) host. In analogous PS/DPI films, DPI dendrites embedded in the PS film are observed. This microstructure formation route, based on solution blend processing, is an alternative to chemical synthesis of fibres and columns. Film structures were determined with microscopic (optical, Atomic Force Microscopy) and spectroscopic techniques (dynamic Secondary Ion Mass Spectroscopy and X-ray Photoelectron Spectroscopy). Structure formation models are presented. Diffusion-Limited Aggregation is postulated for solution droplets agglomerating as PS-rich fractals (with low attachment probability P) and for crystallizing DPI dendrites (with higher P value and hence larger and less compact fractals, as observed).

Electrodeposition of composite Ni–B coatings in a stirred heterogeneous system

The formation of composite electrochemical coatings of a nickel matrix with boron microparticles was investigated. Electrolytical nickel–boron layers were deposited on a paraffin-impregnated graphite electrode in a stirred heterogeneous system formed by a Watts-type nickel plating bath and dispersed boron powder particles. The polarisation behaviour of the composite plating bath as a function of the boron particle loading was examined. The effect of deposition conditions, as well as of the amount of boron powder in the plating bath on the boron content in the composite Ni–B coatings, was examined. The composite coating structure was established using scanning electron microscopy and light optical microscopy. The distribution of boron particles in the composite deposits was investigated by dynamic secondary ion mass spectrometry. The boron particles content was determined gravimetrically. The obtained results suggest that the content of incorporated boron particles increases with an increasing amount of boron in the plating bath. The potentiodynamic deposition method is demonstrated to be more suitable for production of composite coatings with a high content of boron particles than the potentiostatic one. Homogeneous distribution of boron particles in the nickel matrix without coagulation or sedimentation was associated with the electrochemical fabrication method in stirred heterogeneous systems.

Factors Affecting the Chemical Durability of Glass Used in the Pharmaceutical Industry

Delamination, or the generation of glass flakes in vials used to contain parenteral drug products, continues to be a persistent problem in the pharmaceutical industry. To understand all of the factors that might contribute to delamination, a statistical design of experiments was implemented to describe this loss of chemical integrity for glass vials. Phase I of this study focused on the effects of thermal exposure (prior to product filling) on the surface chemistry of glass vials. Even though such temperatures are below the glass transition temperature for the glass, and parenteral compounds are injected directly into the body, data must be collected to show that the glass was not phase separating. Phase II of these studies examined the combined effects of thermal exposure, glass chemistry, and exposure to pharmaceutically relevant molecules on glass delamination. A variety of tools was used to examine the glass and the solution contained in the vial including: scanning electron microscopy and dynamic secondary ion mass spectroscopy for the glass; and visual examination, pH measurements, laser particle counting, and inductively coupled plasma-optical emission spectrometry for the analysis of the solution. The combined results of phase I and II showed depyrogenation does not play a significant role in delamination. Terminal sterilization, glass chemistry, and solution chemistry are the key factors in the generation of glass flakes. Dissolution of silica may be an effective indicator that delamination will occur with a given liquid stored in glass. Finally, delamination should not be defined by the appearance of visible glass particulates. There is a mechanical component in the delamination process whereby the flakes must break away from the interior vial surface. Delamination should be defined by the observation of flakes on the interior surface of the vial, which can be detected by several other analytical techniques.

Desulfovibrio magneticus RS-1 contains an iron- and phosphorus-rich organelle distinct from its bullet-shaped magnetosomes

Intracellular magnetite crystal formation by magnetotactic bacteria has emerged as a powerful model for investigating the cellular and molecular mechanisms of biomineralization, a process common to all branches of life. Although magnetotactic bacteria are phylogenetically diverse and their crystals morphologically diverse, studies to date have focused on a few, closely related species with similar crystal habits. Here, we investigate the process of magnetite biomineralization in Desulfovibrio magneticus sp. RS-1, the only reported species of cultured magnetotactic bacteria that is outside of the alpha-Proteobacteria and that forms bullet-shaped crystals. Using a variety of high-resolution imaging and analytical tools, we show that RS-1 cells form amorphous, noncrystalline granules containing iron and phosphorus before forming magnetite crystals. Using NanoSIMS (dynamic secondary ion mass spectroscopy), we show that the iron-phosphorus granules and the magnetite crystals are likely formed through separate cellular processes. Analysis of the cellular ultrastructure of RS-1 using cryo-ultramicrotomy, cryo-electron tomography, and tomography of ultrathin sections reveals that the magnetite crystals are not surrounded by membranes but that the iron-phosphorus granules are surrounded by membranous compartments. The varied cellular paths for the formation of these two minerals lead us to suggest that the iron-phosphorus granules constitute a distinct bacterial organelle.

Characterisation of amorphous silica in air-oxidised Ti 3SiC 2 at 500–1000 °C using secondary-ion mass spectrometry, nuclear magnetic resonance and transmission electron microscopy

In this paper we have described the use of secondary-ion mass spectrometry (SIMS), solid state 29Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM) to detect the existence of amorphous silica in Ti 3SiC 2 oxidised at 500–1000 °C. The formation of amorphous SiO 2 and growth of crystalline TiO 2 with temperature was monitored using dynamic SIMS and synchrotron radiation diffraction. A duplex structure with an outer TiO 2-rich layer and an inner mixed layer of SiO 2 and TiO 2 was observed. Results of NMR and TEM verified for the first time the direct evidence of amorphous silica formation during the oxidation of Ti 3SiC 2 at the temperature range 500–1000 °C.

Surface Effects on the Thin Film Morphology of Block Copolymers with Bulk Order−Order Transitions

The morphology of poly(styrene-b-ethylene-r-butylene) (SEB) and poly(styrene-b-ethylene-r-butylene-b-styrene) (SEBS) thin films annealed both above (165 °C) and below (125 °C) the bulk order−order transition temperatures (OOT) (∼140 °C) was characterized with grazing incidence small-angle X-ray scattering (GISAXS), dynamic secondary ion mass spectrometry (d-SIMS), and atomic force microscopy (AFM). The SEBS thin film morphology is always spherical, regardless of film thickness or annealing temperature, leading us to conclude that the OOT for films up to five layers of spheres is depressed by at least 10 °C relative to the bulk. In contrast, the SEB film morphology at both 125 and 165 °C is always cylindrical, except when the film thickness is less than tcyl, a monolayer of cylinders. For SEB film thicknesses, t, less than tcyl at 165 °C either a partial or full monolayer of spheres forms (thickness tsph) with coexistence of patches of spheres and cylinders when tsph < t < tcyl. Thus, we conclude that the ...

Welding Kinetics in a Miscible Blend of High-Tg and Low-Tg Polymers

A model system consisting of poly(tetramethyl bisphenol A polycarbonate) (TMPC) and poly(ethylene oxide) (PEO) was used to study the adhesion between miscible blends of polymers with very different glass transition temperatures. Contact mechanics experiments were performed where identical miscible blend layers were held into contact and separated at elevated temperatures. These results were correlated with measurements of PEO diffusion using dynamic secondary ion mass spectrometry. For low PEO concentrations in the blend, adhesion was obtained above a critical temperature that was consistent with the Fox equation, but substantial adhesion was not obtained at any temperature for blends with higher PEO contents. The results indicate that adhesion requires sufficient mobility of the high-Tg TMPC component and can be enhanced by small additions of PEO. Larger additions of the highly mobile PEO lubricate the interface, eliminating the enhancement in adhesion that would otherwise result from diffusion of the hi...

Er-Doped Optical Waveguide Amplifiers in X-Cut Lithium Niobate by Selective Codiffusion

Positive small-signal net gain is demonstrated for the first time in optical waveguide amplifiers in X-cut Y-propagating lithium niobate by selective erbium (Er) and titanium (Ti) codiffusion. First, a planar codiffused sample was prepared for dynamic secondary ion mass spectrometry (SIMS) analysis. An erbium diffusion coefficient of 0.17 ¿m <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> /h was calculated from the SIMS results and from the diffusion theory. Furthermore, the fabrication of optical waveguide amplifiers and the characterization methods are described. In a 3.5-cm-long optical waveguide amplifier, an optical small-signal net gain of 1.4 dB at 1531 nm was measured for the transverse-magnetic mode by optical pumping at 1488 nm with a launched pump power of 90 mW. The codiffusion process shows good net gain efficiency (dB/mW) and an advantage for the fabrication of integrated optical passive and active functions in lithium niobate.

Detection of Amorphous Silica in Air-Oxidized Ti&lt;sub&gt;3&lt;/sub&gt;SiC&lt;sub&gt;2&lt;/sub&gt; at 500–1000°C by NMR and SIMS

The use of secondary-ion mass spectrometry (SIMS), nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM) to detect the existence of amorphous silica in Ti3SiC2 oxidised at 500–1000°C is described. The formation of an amorphous SiO2 layer and its growth in thickness with temperature was monitored using dynamic SIMS. Results of NMR and TEM verify for the first time the direct evidence of amorphous silica formation during the oxidation of Ti3SiC2 at 1000°C.