Ag-TCNQ金属/有机双层膜中的扩散机制

研究了用真空分层蒸镀法获得的金属/有机双层膜(Ag-TCNQ)中的层间扩散行为.根据Cu、Ag在与TCNQ形成络合物时表现出的相似性,建立了异质元素标志法,以Cu为标志元素,研究了金属有机络合物Ag-TCNQ形成过程中Ag扩散的微观机制.使用二次离子质谱(SIMS)分析了Cu、Ag元素在不同样品膜中的浓度分布及变化情况.结果表明,不同于纯金属薄膜中Cu、Ag清晰的界面,在络合物中的Cu与Ag之间存在交叉,说明两种离子之间存在着交换现象.由此可以推断,薄膜中的扩散机制是Ag离子在Ag-TCNQ络合物中的换位扩散.     

Effects of annealing on the damage morphologies in BF 2 + ion implanted (1 0 0) silicon

The effects of annealing on the damage morphologies and impurity redistributions in BF ₂ ⁺ ion implanted (1 0 0) silicon were studied using secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM) and Rutherford backscattering (RBS) ion beam channelling technique. An amorphized silicon layer and a heavily-damaged crystal layer containing a high density of point-defect clusters, are formed on the silicon wafer by the ion implantation. SIMS depth profiles of both boron and fluorine are almost Gaussian distribution. Both furnace annealing and rapid thermal annealing cause recrystallization of the amorphized layer and formation of dislocation loop bands out of the point defects. SIMS depth profiles for both impurities show anomalous double peaks at the same depths. These facts suggest that the primary peak is due to the peak of the Gaussian distribution and the secondary peak due to the gettering effects of residual dislocation loop band.     

High-reactivity matrices increase the sensitivity of matrix enhanced secondary ion mass spectrometry

Secondary ion mass spectrometry (SIMS) is a desorption/ionization method in which ions are generated by the impact of a primary ion beam on a sample. Classic matrix assisted laser desorption and ionization (MALDI) matrices can be used to increase secondary ion yields and decrease fragmentation in a SIMS experiment, which is referred to as matrix enhanced SIMS (ME-SIMS). Contrary to MALDI, the choice of matrices for ME-SIMS is not constrained by their photon absorption characteristics. This implies that matrix compounds that exhibit an insufficient photon absorption coefficient have the potential of working well with ME-SIMS. Here, we evaluate a set of novel derivatives of the classical MALDI matrices α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) for usability in ME-SIMS. This evaluation was carried out using peptide mixtures of different complexity and demonstrates significant improvements in signal intensity for several compounds with insufficient UV absorption at the standard MALDI laser wavelengths. Our study confirms that the gas-phase proton affinity of a matrix compound is a key physicochemical characteristic that determines its performance in a ME-SIMS experiment. As a result, these novel matrices improve the performance of matrix enhanced secondary ion mass spectrometry experiments on complex peptide mixtures.     

Secondary ion mass spectrometry of dopant and impurity elements in wide bandgap semiconductors

Based on secondary ion mass spectrometry (SIMS) measurements, we have compiled state-of-the-art data concerning dopant elements and natural impurities in the wide bandgap semiconductor materials diamond, SiC, ZnSe, GaN and AlN. Samples were prepared by ion implantation of different elements into these materials and post-implantation thermal annealing. SIMS depth profiling techniques were used to determine atomic depth profiles of implanted elements and subsequent changes produced by annealing. Range statistics and SIMS relative sensitivity factors were established for major dopant and impurity elements in these wide bandgap materials. Results of these studies are presented in tabular form along with representative depth profile figures.     

Electron holographic characterization of ultra-shallow junctions in Si for nanoscale MOSFETs

This investigation attempts quantitative characterization of ultra-shallow junctions (USJs) in Si, useful for future generations of nanoscale MOSFETs as predicted by the Semiconductor Industry Association Roadmap. The USJs were fabricated using rapid thermal diffusion (RTD) from a heavily doped n-type surface source onto a heavily doped p-type substrate. The dopant profiles were analyzed using secondary ion mass spectrometry (SIMS), and were further used to calculate the metallurgical junction depth (MJD). One-dimensional (1-D) characterization of the electrical junction depth (EJD) associated with the electrically activated fraction of the incorporated dopants was performed using off-axis electron holography in a transmission electron microscope. 1-D potential profiles were derived from the unwrapped phase of the reconstructed holograms. The EJD was derived from the measured potential distribution across the p-n junction, and quantitative comparison is made with MJD derived from the SIMS profiles. The comparison between calculated electric field and total-charge distributions from the measured potential profiles and the simulated distributions using the SIMS profiles provides a quantitative estimate of the electrical activation of dopants incorporated by the RTD process, within the accuracy limits of this technique, which is discussed herein.     

Selective analysis of the elemental composition of InGaAs/GaAs nanoclusters by secondary ion mass spectrometry

New possibilities of the method of secondary ion mass spectrometry (SIMS) in application to quantitative analysis of the atomic composition of InGaAs nanoclusters in GaAs matrix are considered. Using In _x Ga_1–x As test structures, nonlinear calibration dependences of the yield of secondary In₂As and InAs ions on the concentration of indium have been determined, which do not involve normalization to the matrix elements (Ga or As) and make possible selective analysis of the composition of nanoclusters. Using these relations, quantitative depth profiles of indium concentration were measured and statistical characteristics of the arrays of nanoclusters in InGaAs/GaAs heterostructures were determined.     

Compositional analysis of pattern-plated permalloy films

The combination of scanning electron microscopy (SEM)—energy-dispersive spectroscopy (EDS) and secondary ion mass spectrometry (SIMS) is a powerful approach for the characterization of the lateral and depth homogeneity of pattern-electroplated permalloy (Ni_0.80Fe_0.20) films. SEM-EDS is particularly useful for providing highly accurate data on a large number of analysis points for lateral homogeneity characterization. SIMS proved particularly useful in providing depth profiles with high depth resolution.     

Accurate measurement and evaluation of the nitrogen depth profile in plasma nitrided iron

Nitrogen depth profile of plasma nitrided pure iron was measured and evaluated by accurate experimental techniques. Plasma nitriding cycles were carried out on high purity iron substrate in an atmosphere of 75% H₂-25% N₂. Nitrogen concentration depth profiles in the compound layer and the diffusion zone were characterized by glow discharge optical emission spectroscopy (GDOES) and secondary ion mass spectroscopy (SIMS), respectively. Nitrogen diffusion depths were measured accurately by optical and scanning electron microscopy as well as SIMS technique at different nitriding times. Experimental results indicated good agreement between SIMS data and microscopic evaluations for various nitriding cycles. The results of SIMS showed the nitrogen diffusion depth of about 2000 μm in the diffusion zone for 10 h plasma nitriding at 550 °C. Such high depth had not been detected in previous investigations in which the conventional methods such as EDS, GDS, XPS, EPMA or ion probe techniques were used.     

Effect of heating on the behaviors of hydrogen in C-TiC films with auger electron spectroscopy and secondary ion mass spectroscopy analyses

C-TiC films with a content of 75% TiC were prepared with magnetron sputtering deposition followed by Ar⁺ ion bombardment. Effect of heating on the behaviors of hydrogen in C-TiC films before and after heating was studied with Auger Electron Spectroscopy and Secondary Ion Mass Spectroscopy (SIMS) analyses. SIMS depth profiles of hydrogen after H⁺ ion implantation and thermal treatment show different hydrogen concentrations in C-TiC coatings and stainless steel. SIMS measurements show the existence of TiH, TiH₂, CH₃, CH₄, C₂H₂ bonds in the films after H⁺ ion irradiation and the changes in the Ti LMM, Ti LMV and C KLL Auger line shape reveal that they have a good hydrogen retention ability after heating up to the temperature 393 K. All the results show that C-TiC coatings can be used as a hydrogen retainer or hydrogen permeable barrier on stainless steel to protect it from hydrogen brittleness.     

Diffusion of iron into solar-grade CIGS layers from natural and radioactive front-side sources

Diffusion of Fe in CIGS was investigated on solar-grade CIGS layers using radiotracer sputter-profiling of ⁵⁹Fe or in-depth secondary ion mass spectrometry (SIMS) of natural iron isotopes. In both cases natural or radioactively labelled iron was deposited on the front-surface of CIGS/Mo/float-glass samples. Fe penetration profiles were measured after isothermal annealing in a lamp oven at different temperatures. A diffusivity of 4 × 10^− 13 cm² s^− 1 was deduced from Gaussian-type SIMS profiles originating from annealing at 300 °C. It was found that pronounced sputter-broadening effects may complicate the interpretation of the diffusion profiles.     

Three-dimensional compositional analysis of drug eluting stent coatings using cluster secondary ion mass spectrometry

Cluster secondary ion mass spectrometry (cluster SIMS) employing an SF5+ polyatomic primary ion sputter source in conjunction with a Bi3+ analysis source was used to obtain three-dimensional molecular information in polymeric-based drug-eluting stent coatings. The formulations of the coatings varied from 0% to 50% (w/w) sirolimus drug in poly(lactic-co-glycolic acid) and were prepared on both MP35N metal alloy coupons and bare metal stents. All cluster SIMS depth profiles obtained indicated a drug-enriched surface region, followed by a drug-depletion region, and finally a constant bulk composition region, similar to previous data obtained in polymeric blend systems. The drug overlayer thickness was determined to increase with increasing sirolimus content. Sample temperature was determined to play an important role in the resulting depth profiles, where it was shown that the best profiles were obtained at low temperatures (-100 degrees C). At these temperatures, molecular signals typically remained constant through the entire depth of the film (approximately 6.5 microm) in some cases, as opposed to the typical 1 microm-2 microm depth limit, which is achievable at room temperature. The 3-D imaging capabilities of cluster SIMS were successfully demonstrated and indicated a significant amount of subsurface domain formation in the 25% and 50% sirolimus samples, but not in the 5% sample, which was homogeneous. These results clearly illustrate the utility of cluster SIMS for probing the 3-D structure in polymeric-based drug delivery devices.     

On the application of SIMS to study the oxidation mechanisms of alumina formers

Abstract

Secondary ion mass spectrometry (SIMS) is widely used to investigate the oxidation mechanism of alumina formers, being various MeCrAl (Me=Fe, Ni, Co) alloys and β-NiAl intermetallic compound. Frequently, it is combined with dedicated oxidation exposures, mostly in atmospheres containing different amounts of oxygen tracer (¹⁸O₂) in order to investigate the scale growth mechanism. However, there are several practical aspects which have to be taken into account during planning the oxidation experiments as well as during interpretation of their results in order to avoid misleading conclusions. In particular, the effects related to the formation of non-uniform scales as well as to the relationship between the exposure conditions and the scale microstructure and morphology at various stages of its growth should be dealt with.

This paper discusses the implications of sputtering process with respect to elemental in-depth distribution profiling and the results of the oxidation mechanism investigation of various alumina formers by means of SIMS. It is shown that the obtained shapes of the SIMS profiles and images strongly depend on the choice of the exposure conditions and on the analysis parameters, including the spatial resolution. The exposure conditions are related to the scale microstructure and morphology, the evolution of which occurs during the oxidation process. Formation of duplex alumina scale is reported which comprises an inner more compact sub-layer and an outer ridged and less-compact sub-layer.     

Surface mass spectrometry of two component drug-polymer systems: novel chromatographic separation method using gentle-secondary ion mass spectrometry (G-SIMS)

In recent years, there has been an increase in the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) for characterizing material surfaces. A great advantage of SIMS is that the analysis is direct and has excellent spatial resolution approaching a few hundred nanometers. However, the lack of the usual separation methods in mass spectrometry such as chromatography or ion mobility combined with the complexity of the heavily fragmented ions in the spectra means that the interpretation of multicomponent spectra in SIMS is very challenging indeed. The requirements for high-definition imaging, with say 256 × 256 pixels, in around 10 min analysis time places significant constraints on the instrument design so that separation using methods such as ion mobility with flight times of milliseconds are incompatible. Clearly, traditional liquid and gas chromatographies are not at all possible. Previously, we developed a method known as Gentle-SIMS (G-SIMS) that simplifies SIMS spectra so that the dominant ions are simply related to the structure of the substances analyzed. The method uses a measurement of the fragmentation behavior under two different primary ion source conditions and a control parameter known as the g-index. Here, we show that this method may be used "chromatographically" to separate the mass spectra of a drug molecule from the matrix polymer. The method may be used in real-time and is directly compatible with the majority of TOF-SIMS instruments. The applicability to other imaging mass spectrometeries is discussed.     

Depth profiling of poly(L-lactic acid)/triblock copolymer blends with time-of-flight secondary ion mass spectrometry

Time-of-flight secondary ion mass spectrometry employing an SF5+ polyatomic primary ion source was utilized to obtain a series of in-depth profiles from PLLA/Pluronic-P104 (poly(ethylene oxide-co-propylene oxide) triblock copolymer) blends in attempts to quantify the in-depth surface segregated Pluronic region. The resultant in-depth profiles were consistent with theoretical models describing the surface segregated region in polymeric blends and copolymer systems, with a surface enriched Pluronic-P104 region, followed by a P104 depletion layer, and finally a constant composition bulk region. These results were consistent over a range of concentrations (1-25%). The depth profiles obtained using cluster SIMS were compared to information obtained using X-ray photoelectron spectroscopy. The results demonstrate that, with cluster primary ion bombardment, we are for the first time able to quantify the polymeric composition as a function of depth within certain multicomponent polymer blends. This success can be attributed to the sputter characteristics of polyatomic primary ion bombardment (SF5+) as compared to monatomic primary ion beams.     

SIMS and RBS analysis of leached glass: Reliability of RSF method for SIMS quantification

The reliability of the relative sensitivity factor (RSF) approach for secondary ion mass spectrometry (SIMS) quantification of the leached layers on glass was investigated by measuring comparable samples of glass with SIMS and RBS (Rutherford backscattering spectrometry). The RSF factors were calculated using the nominal bulk compositions. Accurate results can be obtained only when the leached layer and the bulk glass have the same major elemental compositions (Si and O) and the matrix effect is inhibited. The concentrations of the different elements in the leached layer obtained from the comparable samples measured by SIMS and RBS are coincident within a factor of 2This paper is a part of a thesis submitted in partial fulfilment of the requirements for the PhD degree at the University of Technology of Vienna, 1991. The paper was orally presented in a symposium, Analysis of Working Materials, held in Vienna, 22–29 May 1991.     

Highly sensitive detection of net hydrogen charged into austenitic stainless steel with secondary ion mass spectrometry

Secondary ion mass spectrometry (SIMS) is used to detect local distributions of hydrogen in various materials. However, it has been well-known that it is extremely difficult to analyze net hydrogen (H(N)) in metals with SIMS. This was because hydrogen, which is originated from moisture (H(2)O), hydrocarbon (C(x)H(y)) or other organic materials (C(x)H(y)O(z)) existing on a sample surface or in the SIMS chamber, is simultaneously detected in the SIMS measurement of the H(N), and the H(N) and the background-originated hydrogen (H(BG)) cannot be distinguished in a SIMS profile. The effective method for reductions and determinations of the H(BG) in hydrogen measurements of metallic materials with the SIMS method has not been established. The present paper shows an effective method for reduction and estimation of H(BG) in SIMS analyses of hydrogen charged into type 316 L austenitic stainless steel, and an accurate estimation method of the net charged hydrogen. In this research, a silicon wafer is sputtered by a primary ion beam of a SIMS near an analyzed area (silicon sputtering method) to reduce H(BG). An uncharged type 316 L sample was prepared for estimation of H(BG) in SIMS measurements of the hydrogen-charged sample. The gross intensities of hydrogen between the hydrogen-charged sample and the uncharged sample were compared. The gross intensities of hydrogen of the uncharged sample (26.8-74.5 cps) were much lower than the minimal gross intensities of hydrogen of the hydrogen-charged sample (462-1140 cps). Thus, we could reduce the H(BG) enough to estimate the hydrogen charged into the type 316 L sample. Moreover, we developed a method to determine intensities of H(BG) in the measurement of the hydrogen-charged sample by estimating the time-variation of hydrogen intensities in the measurements of the uncharged sample. The intensities of the charged hydrogen can be obtained by subtracting the estimated intensities of the H(BG) from the gross intensities of hydrogen of the hydrogen-charged sample. The silicon sputtering method used to reduce H(BG) and the determination method for H(BG) in this research can be applied to the accurate hydrogen analysis for other various metallic materials.     

SIMS analysis of ultrathin implanted arsenic layers in silicon

A new regime of secondary ion mass spectrometry (SIMS) is proposed, which allows a depth resolution of λ=1.4 nm to be achieved. The profiles of arsenic implanted into silicon, measured using this regime on a Cameca IMS-4f microprobe, were close to the true distributions. SIMS profiling of the samples of silicon implanted with 30-keV As⁺ ions to a total dose of (1.25–3.13)×10¹³ cm^?2 through a 20-nm-thick thermal oxide layer showed the presence of a sharp peak of arsenic accumulated at the oxide/silicon interface, which is explained by the diffusion of arsenic to this interface as a result of annealing.     

Study of Zn diffusion in n-type GaSb by cathodoluminescence and scanning tunneling spectroscopy

We report here the studies carried out in zinc diffused n-type GaSb by cathodoluminescence (CL) microscopy and by scanning tunneling spectroscopy. Samples with different diffusion profiles measured by secondary ion mass spectrometry (SIMS) were obtained. CL plan-view observations show high homogeneity in the diffused layers. Cross-sectional measurements of the Zn diffused layers were performed by current imaging tunneling spectroscopy (CITS). The junction border was revealed clearly in the CITS images and conductance spectra recorded at differents points of the layers provided information on the local surface band gaps and the conductive behaviour. The results were related to the diffusion profiles and were found to agree with diffusion models suggested previously.     

Quantitative static secondary ion mass spectrometry of molecular ions from 1-beta-3,4-dihydroxyphenylalanine (L-dopa) and indolic derivatives

Traditionally, static secondary ion mass spectrometry (SIMS) is believed to yield qualitative information and very little quantitative information. A method to obtain quantitative molecular ion data from organic static SIMS analysis of L-DOPA and related compounds is presented. Linear calibration curves have been constructed by integrating the protonated molecular ion to silver ion peak area ratios over a known ion dosage and plotting versus the original sample concentration.     

A dual beam gun for neutral or ionic primary beams in static SIMS

A dual primary beam gun for secondary ion mass spectroscopy (SIMS) is presented. The beam source produces, without any mechanical change, either an ion beam or a neutral beam generated by resonant charge transfer. The energy of the ion beam ranges from less than 1 keV up to 3.0 keV at beam currents from 10^?11 A to 1×10^?6A. The diameter of the ion beam can be focused additionally from 3.0 mm down to 0.4 mm FWHM. The particle density and the homogeneity of the neutral beam is of the same order as that of the ion beam. SIMS analysis of solid surfaces is possible without any restrictions arising from the conductivity of the specimen.