Monte Carlo calculation using a personal computer for electron probe microanalysis

Monte Carlo simulation for calculating x‐ray spectra under electron impact is carried out by a personal computer. Reduction of the CPU time by reducing the number of incident electrons for calculation is performed. One of the methods used to reduce the number of incident electrons to obtain the results within an acceptable error is provided. We limit the present report to five typical compounds: an oxide (Al₂O₃), a nitride (TiN), a carbide (Al₄C₃), a light–light element compound (BN), and a heavy–light element compound (PbS). We calculate the relative x‐ray intensity generated from the five compounds listed above with the change of the number of the incident electrons. The calculated x‐ray intensity is then converted into the mass % by the ZAF method. Comparisons are made between the calculation and experiment for Al₄C₃ and PbS. It is found that the present Monte Carlo method is useful for investigating a relationship between the number of incident electrons and the acceptable error. The results of 150 incident electrons can be applied in practical analysis, and the calculation time is less than 2 min. Copyright © 2004 John Wiley & Sons, Ltd.     

Elemental analysis by high‐energy electron excitation

The possibility of using high‐energy β‐particles (10²–10³ keV) to induce the emission of characteristic x‐rays from pure chemical elements, with important improvements with respect to conventional excitation methods, has been recently reviewed. An excitation procedure named BIXE (β‐induced x‐ray emission) is used for implementing a spectrometric technique along the lines developed for EPMA (electron probe microanalysis). We have found that by using BIXE it is possible to determine binary sample compositions of elements present at concentrations higher than 1%, by comparisons with reference samples to obtain calibration curves. Experience with EPMA shows that when ternary and higher order samples are analyzed, the use of reference samples is not enough and it is necessary to perform theoretical corrections to the relationship between the line intensity and the corresponding concentrations, as a suitable complement to the analytical procedure. Semi‐quantitative results are thus obtained with corrections applied through the ZAF method usually used in EPMA. In this work we concentrated in finding whether calibration curves as used in EPMA (where the electron beam is monochromatic) can be used in BIXE, where the electron beam is polychromatic (the β spectrum). We expect that BIXE can be developed as a spectrometric technique whose main advantages are that it is a low‐cost technique suitable for in situ studies and that the experimental arrangement and data acquisition and its evaluation are comparatively simple. Copyright © 2004 John Wiley & Sons, Ltd.     

EPMA mapping method for small particles of Al3Fe,Al6Fe, α‐AlFeSi and β‐AlFeSi in 1050‐H18 aluminum sheets

We developed an EPMA mapping method for small Al_aFe_bSi_c particles in 1050‐H18 aluminum sheet, which is one of the base materials coated by photoresist in advance called PS plate (pre‐sensitized printing plate). In this method, we used the ratios of relative x‐ray intensities, I_Fe/I_Al and I_Fe/I_Si instead of the mass ratios, Fe/Al and Fe/Si, of the main elements which constitute the particles and tried to determine the ratios of relative x‐ray intensities using Monte Carlo calculations. Furthermore, using this developed mapping method, we performed the mapping of small Al_aFe_bSi_c particles such as Al₃Fe (0–3%Si as impurities), Al₆Fe (0–1%Si as impurities), α‐AlFeSi(Al_8.3Fe₂Si) and β‐AlFeSi(Al_8.9Fe₂Si₂) in 1050‐H18 aluminum sheets. We found that the discrimination of these particles was achieved with this mapping method. We confirmed that this method is useful for the mapping of Al_aFe_bSi_c particles in 1050‐H18 aluminum sheets. Copyright © 2004 John Wiley & Sons, Ltd.     

Standard‐free composition measurements of Alx In1–xN by low‐loss electron energy loss spectroscopy

We demonstrate a standard‐free method to retrieve compositional information in Al_x In_1–xN thin films by measuring the bulk plasmon energy (E_p), employing electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Two series of samples were grown by magnetron sputter epitaxy (MSE) and metal organic vapor phase epitaxy (MOVPE), which together cover the full com‐ positional range 0 ≤ x ≤ 1. Complementary compositional measurements were obtained using Rutherford backscattering spectroscopy (RBS) and the lattice parameters were obtained by X‐ray diffraction (XRD). It is shown that E_p follows a linear relation with respect to composition and lattice parameter between the alloying elements from AlN to InN allowing for straightforward compositional analysis. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of ceramic PVD thin films on AZ31 magnesium alloys

Ceramic thin films have been widely used to protect the metal substrate as coatings in the past years. In order to improve the poor corrosion resistance of AZ31 magnesium alloy, the study in this paper used the electron beam evaporation method to prepare ceramic PVD films on its surface with TiO₂ and Al₂O₃ as donors, respectively. Atomic force microscopy (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) were used to investigate the surface morphology, composition and microstructure of the thin films. Both films deposited on AZ31 took on compact top surface morphologies and grew as amorphous structures on substrate. AES test not only showed that films compositions deviated the standard stoichiometric ratios, but also found that element Mg diffused into films and existed as magnesium oxide in the TiO_x film as well as the AlO_x film. In the electrochemical corrosion test, the AlO_x coating on AZ31 exhibited the largest electrochemical impedance in a 3.5% NaCl solution. But it did not show better corrosion resistance than others for the poorer adhesion. Even if its thickness was small, the TiO_x coating on AZ31 exhibited the best corrosion resistance in this study. According to the observation and analysis, the damage of these films on AZ31 in aggressive solutions was mainly due to the existence of pores, microcracks, vacancies and poor adhesion between coating and substrate.     

The competitive growth of cubic domains in Ti1–xAlxN films studied by diffraction anomalous near‐edge structure spectroscopy

Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K‐edge X‐ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X‐ray diffraction anomalous fine structure, which is sensitive to short‐ and long‐range order within a given crystallized domain, are carried out on a set of Ti_1–xAl_xN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre‐edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face‐centred‐cubic Ti‐rich (TiN, Ti_0.54Al_0.46N) samples or tetrahedral in hexagonal‐close‐packed Al‐rich (Ti_0.32Al_0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy‐dependent structure factor for the Bragg reflections is applied to the pre‐edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre‐edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre‐edge spectra associated with face‐centred‐cubic 200 and 111 Bragg reflections of Ti_0.54Al_0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti_0.32Al_0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal‐close‐packed nitride.     

Thin‐film characterization with x‐ray microanalysis. Extending and improving invariant embedding results

Invariant embedding theoretical results for the recorded x‐ray intensities in electron probe microanalysis were used to develop a procedure for thin films. The method presented here gives the possibility of achieving thin‐film characterization directly from characteristic x‐rays intensities measurements, without the necessity to make an explicit calculation of the ?(ρz) function. Theoretical results are found to follow the general trend of experimental data. Copyright © 2003 John Wiley & Sons, Ltd.     

Sapphire hard X‐ray Fabry–Perot resonators for synchrotron experiments

Hard X‐ray Fabry–Perot resonators (FPRs) made from sapphire crystals were constructed and characterized. The FPRs consisted of two crystal plates, part of a monolithic crystal structure of Al₂O₃, acting as a pair of mirrors, for the backward reflection (0 0 0 30) of hard X‐rays at 14.3147 keV. The dimensional accuracy during manufacturing and the defect density in the crystal in relation to the resonance efficiency of sapphire FPRs were analyzed from a theoretical standpoint based on X‐ray cavity resonance and measurements using scanning electron microscopic and X‐ray topographic techniques for crystal defects. Well defined resonance spectra of sapphire FPRs were successfully obtained, and were comparable with the theoretical predictions.     

Determination of gold,platinum and uranium in South African ores by high‐energy XRF spectrometry

An automated energy‐dispersive x‐ray fluorescence spectrometer, called the AZTEC, was developed for the non‐destructive determination of gold, platinum and uranium in Witwatersrand ores, by utilizing the high‐energy spectral regions of the K x‐ray lines of these elements. It provides a viable alternative to fire assay, and measures gold concentrations down to <1 ppm. About 100 g of pulverized sample are presented for analysis in a 20 mm diameter tube, and the fluorescent x‐rays are detected by an array of up to 12 high‐purity germanium detectors. Count‐rates of up to 10⁶ counts per second per detector can be processed by the signal processing electronics. The AZTEC technique is a variant of the scattered radiation technique. Concentration is related to peak intensities corrected for background, matrix variations, density and line overlaps. Provided that the samples are finely pulverised, the AZTEC analyses compare well with those obtained by fire assay. Production instruments are being used mainly in the gold mining industry, where they have analysed over 10⁷ samples to date. Copyright © 2004 John Wiley & Sons, Ltd.     

Chemical analysis of phosphate rock using different methods—advantages and disadvantages

Many analytical methods are considered for chemical analysis of phosphate rock because the accuracy of analysis is very important. In the present investigations, spectrophotometric and x‐ray spectrometric methods were used to determine P₂O₅ whereas SiO₂, CaO, MgO, Al₂O₃ and Fe₂O₃ were determined by gravimetric and x‐ray spectrometric methods. Volumetric and x‐ray spectrometry methods are necessary for fluorine determination. The investigations revealed that x‐ray spectrometry is a precise and accurate technique, which is cost effective and so better than other methods. Spectrophotometric, volumetric and gravimetric methods are expensive, time consuming and laborious. X‐ray spectrometry is suggested for commercial companies using regular analyses to save chemicals, time and labour and to maintain quality. Copyright © 2006 John Wiley & Sons, Ltd.     

The effects of absorption edge structure of atoms in x‐ray fluorescence analysis

The effects of the absorption edge structure in x‐ray fluorescence (XRF) manifest themselves as a very strong attenuation of the analytical line radiation when it is in the x‐ray absorption near edge structure (XANES) range. In this paper, this effect is exemplified by an ultra‐strong Ba‐caused attenuation of the Ce Lβ₁ line. This case was experimentally studied. Comparison of measured and calculated relative intensities has shown that the actual mass attenuation coefficient of the Ce Lβ₁ line in Ba is 1.6 times greater than known values. This is due to that the Ce Lβ₁ line is within the initial range of L3 Ba absorption edge, i. e. the XANES range. Such an effect of the absorption edge structure of atoms must be considered using the fundamental parameters method in quantitative XRF analysis. This paper also presents some other possible cases of this effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhancing the thermal conductivity of polymer-assisted deposited Al2O3 film by nitrogen doping

<正>Polymer-assisted deposition technique has been used to deposit Al₂O₃ and N-doped Al₂O₃（AlON） thin films on Si（100） substrates.The chemical compositions,crystallinity,and thermal conductivity of the as-grown films have been characterized by X-ray photoelectron spectroscopy（XPS）,X-ray diffraction（XRD）,and 3-omega method,respectively. Amorphous and polycrystalline Al₂O₃ and AlON thin films have been formed at 700℃and 1000℃.The thermal conductivity results indicated that the effect of nitrogen doping on the thermal conductivity is determined by the competition of the increase of Al-N bonding and the suppression of crystallinity.A 67%enhancement in thermal conductivity has been achieved for the samples grown at 700℃,demonstrating that the nitrogen doping is an effective way to improve the thermal performance of polymer-assisted-deposited Al₂O₃ thin films at a relatively low growth temperature.     

X‐ray fluorescence analysis of sludge ash from sewage disposal plant

Glass bead/x‐ray fluorescence spectrometry of the sludge incineration ashes generated in sewage processing was developed for the determination of ten major components (Na₂O, MgO, Al₂O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, MnO, Fe₂O₃) and five minor elements (Zn, Cu, Cr, As, Pb). Sewage sludge ashes consisted of rock‐forming minerals and phosphate crystals that had been used for phosphorus removal. Ash samples were melted and molded with lithium tetraborate to 35 mm diameter glass disks in a Pt–Au crucible. Analytical results of ten major components and five minor elements agreed well with the recommended values of a phosphate rock standard reference material (NIST SRM 694). Elemental compositions of sewage sludge ash from seven sewage‐processing plants in Japan were determined using this method. Concentrations of Fe₂O₃, SiO₂, and CaO, along with loss of ignition in sewage sludge ash mutually differed among the sewage‐processing plant products. Seasonal variations in concentrations of ten major components and five minor components of ash samples produced from October 2001 to September 2002 were determined using the proposed method. Concentrations of SiO₂increased with the inflow of gravel by rainfall, thereby decreasing concentrations of P₂O₅ originating from excreta and microorganisms. Copyright © 2008 John Wiley & Sons, Ltd.     

On the characteristics of AlGaN films grown on (111) and (001) Si substrates

High Al-content Al_xGa_1−xN films were deposited on (001) and (111) Si substrates at 1000 °C using high temperature AlN buffer layers. Experimental results show that Al_xGa_1−xN films grown on (111) Si substrates exhibit better crystalline quality than that in the films deposited on (001) Si substrates. Cracks were found in the high Al-content Al_xGa_1−xN/(111) Si samples but they were not observed in the Al_xGa_1−xN films grown on (001) Si substrates having the same film thicknesses and Al compositions. Based upon the results of X-ray diffraction (XRD) and transmission electron microscopy (TEM), it appears that mono-crystalline Al_xGa_1−xN films were achieved on (111) Si substrates while columnar structure was observed in the Al_xGa_1−xN/(001) Si samples. According to the depth profiles of Al_xGa_1−xN/Si samples using secondary ion mass spectroscopic (SIMS) analyses, enhanced Al inter-diffusion in the Al_xGa_1−xN/(001) Si samples was identified. Room temperature (RT) photoluminescence (PL) measurements of the Al_xGa_1−xN (x≦0.10)/(111) Si samples exhibit strong near band edge luminescence. The PL emission linewidth was found to decrease with the decrement of Al-content.     

Determination of effective atomic numbers and mass attenuation coefficients of samples using in‐situ energy‐dispersive X‐ray fluorescence analysis

The matrix effect has a major impact on energy‐dispersive X‐ray fluorescence analysis (EDXRFA) and is difficult to be evaluated due to that the contents of some low‐atomic‐number elements cannot be identified by in‐situ EDXRFA. Up to today, the fundamental parameter algorithm proposed by Rousseau has been widely applied to correct the matrix effect. Accordingly, determining the matrix and mass attenuation coefficient (μ/ρ) of sample is a key issue for the fundamental parameter algorithm. In present work, the method to deduce μ/ρ by effective atomic number (Z_eff) was studied. First, the relationship between Z_eff and coherence to Compton scatting ratio (R) of the incident X‐ray was determined by standard samples. Then, we deduce Z_eff and their μ/ρ. The value of μ/ρ deduced by our method is in good agreement with that calculated by WinXCOM, and the relative change (Δ) is less than 7%. We also deduced Z_eff and their μ/ρ of Chinese national standard soil samples employing our method and good agreement with the calculated values were also obtained. We found that the agreement between experimental values of μ/ρ with theoretical values by WinXCOM still exists when the energy of the incident X‐ray is greater than 4 keV, and the Δ is less than 10%. The result indicates that our method may be applied directly to in‐situ EDXRFA.     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

含轻元素二元合金成分的无标样X光能谱定量分析

本文对利用试样中不同元素X光强度相对比值分析成分的无标样定量分析方法提出了改进。首先对电子散射的“完全扩散”模型进行适当的修正和简化,得到标识X光的台阶状深度分布曲线,从而得到试样成分和标识X光强度的定量关系。对Cu-Si,FeS₂,NaCl和GaAs等二元合金的成分分析得到比较满意的结果。本文比较了用此法和Russ法(利用计算得到的纯元素标识X光强度因子并且经ZAF修正分析成分)得到的结果,表明用我们的方法分析的结果有所改善,计算程序也更简单。 关键词：     

A theoretical practice on grazing‐exit energy dispersive X‐ray spectroscopy as a surface analysis strategy to investigate BiVO4 nano‐films

In the current work, a thin film of bismuth vanadate was defined over a silicon substrate, and a calculative Monte Carlo approach was followed to achieve the best grazing‐exit angle to acquire compositional data from top few nanometers of surface. This strategy is very beneficial in order to increase X‐ray signals originated from surface and diminish the background X‐ray signals started off from the substrate. In this regard, grazing‐exit energy dispersive X‐ray spectroscopy can be considered as an accessible and economical analytical tool to investigate thin films and nano‐layers. The major advantage of this method is that just by applying a re‐arrangement in a scanning electron microscope, it can be used to study compositional properties of thin layers. In this contribution, a theoretical approach using Monte Carlo models was used to simulate the behavior of electron beams impinging onto BiVO₄ nano‐layers with thickness of 50 nm and electron trajectories inside the film. Characteristic X‐rays and spatial energy distribution of the backscattered electrons were also calculated. Under grazing‐exit angle of around 0.5°, the best surface signal/background noise ratio was achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

Fe,Co共掺杂ZnO薄膜结构及发光特性研究

采用溶胶凝胶法在玻璃衬底上制备了Fe,Co共掺Zn0.9FexCo0.1-xO(x=0,0.03,0.05,0.07)系列薄膜.通过扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子谱(XPS)和光致发光(PL)谱对薄膜样品的表面形貌、晶体结构、成分和光学性能进行了研究.XRD结果表明所有ZnO薄膜样品都呈六方纤锌矿结构,在样品中没有观察到与Fe和Co相关的团簇,氧化物及其他杂相的衍射峰,表明共掺杂改善了Fe或Co在ZnO的分散性.XPS测试结果揭示样品中Co离子的价态为+2价;Fe离子的价态为+2价和+3价共存,但Fe相对浓度的增大导致Fe3+含量增加.所有样品的室温光致发光谱(PL)均观察到紫外发光峰和蓝光双峰,其中Fe,Co共掺ZnO薄膜的紫外发光峰较本征ZnO出现蓝移,蓝光双峰峰位没有变化,但发光强度有所减弱;而掺杂ZnO薄膜的绿光发光峰几乎消失.最后,结合微结构和成分分析对薄膜样品的发光机理进行了讨论.     

Mössbauer spectroscopy of Al substituted Fe in holmium iron garnet

A Mössbauer spectroscopy study was made on Ho₃Fe_5-xAl_xO₁₂ (x=0.0, 0.05, 0.7). X‐ray diffraction patterns indicate that the samples with x=0.0 and 0.05 have the garnet structure, while the sample with x=0.7 has an additional noncubic structural phase. The room temperature spectrum for samples with x=0.0 and 0.05 consists of two magnetic components corresponding to the octahedral and tetrahedral sites with hyperfine magnetic fields (B_hf) of 50 T and 40 T, respectively. For x=0.7 we observe a new magnetic component with B_hf= 45 T, a reduction in the intensity and broadening of the tetrahedral component, and the evolution of a nonmagnetic central component. These variations are evidently due to the addition of aluminium to the system. At liquid nitrogen temperature the samples with x=0.0 and 0.05 are nearly identical. It was also observed that the increase in B_hf for the octahedral site is smaller than that for the tetrahedral site as the temperature is lowered to 80 K.