Glow Discharge Mass Spectrometry Research Articles

Analysis of Elemental Impurities in Photovoltaic Silicon by Inductively Coupled Plasma Mass Spectrometry

A new, simple sample preparation method which results in minimal contamination has been developed for the ultratrace interference-free analysis of solar grade silicon wafers by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Using Dynamic Reaction Cell (DRC) technology with patented dynamic bandpass tuning (DBT) and robust hot plasma conditions, the determination of many critical elements, including boron and phosphorus, without impact from interfering species is shown. For method validation, the mean results of a PV silicon wafer sample (purity > 6N) prepared with this new methodology and analyzed by ICP-MS were cross-checked with the data obtained from Glow Discharge Mass Spectrometry (GDMS). The comparative data of these two different technologies highlights the advantage of the ELAN DRC II ICP-MS for the fast determination of impurities in the PV silicon, over GDMS - which was found to be not as cost effective or time efficient.

Study on the Realization of Zinc Point and the Zinc-Point Cell Comparison

Continuing our study on aluminum, tin, and silver points, a study on the realization of the zinc point was conducted. Zinc-point cells were newly fabricated using 6N-nominal grade zinc samples, impurity elements of which were analyzed extensively based on glow-discharge mass spectrometry (GDMS). The present paper reports the temperature measurements done using the newly fabricated cells during the zinc freezing process, under which the zinc fixed point is defined, and the analysis of the freezing curve obtained. Comparisons of zinc-point temperatures realized by the newly fabricated cells (cell-to-cell comparisons) were also conducted. Zinc-point depression due to impurity elements was calculated based on the sum of individual estimates and the impurity element analysis. One of the cells evaluated was drawn out from its crucible and analyzed by GDMS at four points, namely, at around the center of the top, of the middle, of the bottom, and around the outer part of the middle area. The purpose of this cell disassembly is to see whether or not there has been some difference before and after cell fabrication, as well as difference in impurity element distribution within the ingot. From the aforementioned studies, some findings were obtained. First finding is that the homogeneity of the zinc ingot was within 30%, except for Pb, which was more concentrated in the center part. Second finding is that the cell-to-cell temperature difference changes along with the progressing solidification process. As a consequence, for an accurate cell-to-cell comparison, the locus in the freezing plateau where the comparison is done should be determined. Third finding is that the slope analysis estimates accurately the cell-to-cell comparison, and is consistent with the impurity analysis. This shows that the slope analysis gives extensive information about the effect of impurity to the zinc-point realization, especially after the cell fabrication.

Impurity segregation in directional solidified multi-crystalline silicon

In this paper numerical results on the impurity segregation in directional solidified multi-crystalline silicon are presented and compared with experimental results. A solute transport model has been established to predict the final segregation pattern of impurities in the ingot. The segregation is analyzed experimentally on the basis of Fourier transform infrared (FTIR) spectroscopy and glow-discharge mass spectrometry (GDMS). Precipitates were located by IR-transmission microscopy (IRM). Qualitative agreement between simulation and experiment is found. It is demonstrated how the flow pattern can influence the final solute distribution. The simulation also shows that the solubility limit of carbon and nitrogen is reached locally in the ingot and SiC and Si 3N 4 precipitates are likely to form.

Hydrogen effect on refining of Mo metal by Ar–H2 plasma arc melting

The refining effect of Ar/Ar–H2 plasma arc melting (PAM) was investigated and the purity of Mo metals was evaluated by glow discharge mass spectrometry (GDMS). Most impurities in the Mo metals except for W were removed by Ar/Ar–H2 PAM down to a few mass ppm levels, and the purities of respective Mo metals refined by Ar/Ar–20%H2 PAM were improved up to 4N(99.9943%) and 5N(99.9996%). It is also found that Ar–H2 PAM provides excellent decarburization, deoxidation, and denitrogenization. This confirmed that the refining effect is chemically induced by activated hydrogen atoms during Ar–H2 PAM.

Residual impurities and electrical properties of undoped LEC InAs single crystals

Impurities and their influence on the properties of InAs single crystals have been studied by combining the results of glow discharge mass spectrometry (GDMS), Hall measurements, Raman scattering and infrared absorption. The results indicate that carbon is a major impurity in LEC-InAs single crystals and exhibits a significant influence on the electrical and optical properties.

Process methodology for the small scale production of m6N5 purity zinc using a resistance heated vacuum distillation system

Ultra high purity Zn (m6N5) was obtained through triple vacuum distillation using an m4N5 Zn as input material. High-volatile impurities were removed from the zinc matrix by vacuum evaporation, while traces having lower volatility than the matrix remained in the residual material after finishing of the entire purification process. The time required for the removal of the main high-volatile impurity (Cd) was monitored using a connected gas source mass spectrometer. During distillation the Zn vapor of the distillate was condensed on the cap of a glassy carbon crucible which was water cooled by a movable copper block. The temperatures were optimized for the removal of the volatiles and for the distillation process using vapor pressure data. High resolution glow discharge mass spectrometry was applied for the analysis and purity evaluation of the distilled and input zinc. The analysis confirmed the reduction of the metallic impurities from 43 mg kg −1 to 0.5 mg kg −1 (m6N5) after three consecutive vacuum distillations. An increase in the grain size and a decrease in the micro-hardness were observed for the purified Zn material.

Preparation and Evaluation of High-Purity La2O3

A separation procedure based on extraction chromatography using the di(2-ethylhexyl) phosphoric acid (D2EHPA) impregnated resin, anion exchange with DIAION SA 10 resin, and oxalate precipitation has been developed for the preparation of high-purity La2O3 in hydrochloric acid media at a high La concentration. The metallic impurities Ce, Pr, Nd, Sm, K, Mg, Ca, Zn, Cu, Co, Mn, Pb, Al, In, and Fe, but not Bi, were removed efficiently from La by extraction chromatography using a D2EHPA impregnated resin. The Bi was separated from the La by anion exchange (DIAION SA 10) separation. Thus, a high-purity LaCl3 solution was obtained by anion exchange separation and extraction chromatography. La2O3 was prepared from the purified LaCl3 solution by oxalate precipitation. Glow discharge mass spectrometry was applied for purity evaluation of the prepared La2O3. The purity of the prepared La2O3 was more than 99.9998 pct total rare earth oxide.

Analysis of Elemental Composition of Main Construction Materials in the Nuclear Power Plant “Fugen”

Elemental data for construction materials used in nuclear power plants are necessary for the prediction of radioactivity induced by neutron irradiation. To evaluate radioactivity in retired Japanese nuclear power plants, it is preferable to use elemental data of the structural materials actually used in each plant. However, since there is no such domestic database, NUREG elemental data are commonly used for this type of evaluation. It is, therefore, required to establish a domestic elemental database of the structural materials actually used in power plants. In order to obtain elemental data, more than 130 specimens were collected from the structural materials of the Fugen Nuclear Power Plant, which was constructed in the 1970s and whose operation was stopped in 2003. Seventy-six compositional elements in the specimens were analyzed using appropriate chemical analyses and measurement techniques, such as glow discharge mass spectroscopy and inductively coupled plasma mass spectroscopy. These obtained data were compared with NUREG elemental data and other standard or reference data. As a result, it was determined that the concentrations of major elements were not so different from NUREG elemental data and other standard or reference data. On the other hand, a slight difference was seen among the concentrations and their standard deviation in the analytical data of impurities, such as cobalt. These data are expected to become a reference in the establishment of domestic standard data, and they are also expected to be applied to the evaluation of irradiation-induced radioactivity in the structural materials of reactors that are subject to decommissioning in the future.

Characterization of solid standards prepared by freeze‐drying

AbstractSolid standards prepared by freeze‐drying consistently showed a high degree of homogeneity. The freezing process, completed in fractions of a second, preserves the original homogeneous distribution of the dopants, and the subsequent sublimation step would minimize any disturbance. Compared to those prepared by conventional methods such as blending and spiking, freeze‐dried standards exhibited superior lateral distribution and better uniform depth distribution. There is, however, a concentration constraint for achieving homogeneity. At 5% doping, segregation was observed in both lateral and depth distribution. Many tungsten standards doped with 10–28 elements ranging from 10 to 200 ppm were successfully prepared and used as controls for a number of analytical techniques including glow discharge mass spectrometry (GDMS) and d.c.‐arc optical emission spectroscopy (OES). Copyright © 2009 John Wiley & Sons, Ltd.

Formation of titanium carbide coating with micro-porous structure

Micro-porous titanium carbide coating was successfully synthesized in a vacuum gas carburizing furnace by using a sequential diffusion technology. The composition and structure of the as-synthesized TiC were examined by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and glow discharge mass spectrometry (GDMS), and scanning electron microscopy (SEM). All of the XRD, XPS and GDMS analysis results indicate that carbon atoms effectively diffused into the titanium alloys and formed a uniform acicular TiC coating with micro-porous structure.

Impurity behavior in Cu refined by Ar plasma-arc zone melting

Purification of a 4N grade Cu rod by argon plasma-arc zone melting (APZM) was carried out. Detailed impurity analysis of the Cu rod was performed using glow discharge mass spectrometry (GDMS). Three impurity behavior groups based on segregation and evaporation during APZM were discussed using the GDMS analysis. Although the impurities with segregation coefficient kℴ 1 had no significant reduction in their impurity concentrations. Some impurities, like Mg, S, Cd and Zn, were reduced much faster than the others in Cu. This was ascribed to the removal by zone refining coupled with the evaporation of impurities for Pimp/PCu > 102.

Inorganic mass spectrometry as a tool for characterisation at the nanoscale

Inorganic mass spectrometry techniques may offer great potential for the characterisation at the nanoscale, because they provide unique elemental information of great value for a better understanding of processes occurring at nanometre-length dimensions. Two main groups of techniques are reviewed: those allowing direct solid analysis with spatial resolution capabilities, i.e. lateral (imaging) and/or in-depth profile, and those for the analysis of liquids containing colloids. In this context, the present capabilities of widespread elemental mass spectrometry techniques such as laser ablation coupled with inductively coupled plasma mass spectrometry (ICP-MS), glow discharge mass spectrometry and secondary ion/neutral mass spectrometry are described and compared through selected examples from various scientific fields. On the other hand, approaches for the characterisation (i.e. size, composition, presence of impurities, etc.) of colloidal solutions containing nanoparticles by the well-established ICP-MS technique are described. In this latter case, the capabilities derived from the on-line coupling of separation techniques such as field-flow fractionation and liquid chromatography with ICP-MS are also assessed. Finally, appealing trends using ICP-MS for bioassays with biomolecules labelled with nanoparticles are delineated.

Purity determination as needed for the realisation of primary standards for elemental determination: status of international comparability

Within the National Metrology Institutes (NMIs) and designated laboratories, an interlaboratory comparison, CCQM-P107, was conducted to verify the degree of international comparability concerning the results of purity analysis. The mass fractions of Ag, Bi, Cd, Cr, Ni, Tl at the lower mg/kg-level in a high purity zinc material were determined, but the real measurand in metrological sense was the sum of the six mass fractions. Homogeneity was investigated by glow discharge mass spectrometry, reference values were obtained using isotope dilution mass spectrometry. Six NMIs participated, contributing eight independent data sets. The agreement amongst the results of the participants, their median and the agreement with the reference values were usually excellent and in almost all cases below the target uncertainty of 30% relative. In this manner, the accuracy of results and the comparability between the participants was demonstrated to be established.

Purification of niobium by multiple electron beam melting for superconducting RF cavities

In this work, purification of commercial grade (∼99.9 %) niobium by multiple Electron Beam Melting (EBM) is reported. Impurity removal of carbon, oxygen, nitrogen, aluminum, iron, molybdenum, zirconium and tungsten in niobium matrix is presented as a part of the ingot melting stages. The minor material loss of niobium during melting is attributed to the amount of decarburization based on the ratio of initial and critical content of oxygen to carbon. The analysis of nearly 60 impurity elements in niobium was carried out by glow discharge mass spectrometry. In the end, the purity of niobium after multiple electron beam meltings was found to be 4N while the purity enhanced from 99.9 % (3N) to 99.993 % (4N3), including gaseous impurities, and 99.98 % (3N8) to 99.998 % (4N8) without gaseous impurities. The glow discharge mass spectrometry analytical results of purified niobium indicated that the material is suitable as input material for further processing of fabricated superconducting radio-frequency cavities.

Influence of Interstitials Content on the Diffusion of Niobium in Alloy 718

Many studies have emphasized the beneficial effect of niobium on the physical metallurgy of Ni-Cr-Fe alloy 718. Among the different strengthening actions of niobium, such as solid solution hardening and carbide precipitation, the precipitation of niobium with nickel in a strengthening phase γ” (Ni3Nb) during the aging heat treatment has the largest influence on the mechanical properties of alloy 718. The improvement of the niobium distribution and diffusion in the Ni-matrix may allow a more homogenized repartition of γ” precipitates and seems then to be an effective way to upgrade the mechanical properties. As γ” precipitates decompose to the stable δ phase at very long aging times, the study of the effect of carbon, nitrogen and oxygen concentrations on precipitation and dissolution of the δ phase may give information on γ” precipitation and on niobium distribution. It is the purpose of the present work to examine the role that the alloy content of interstitial species plays with the niobium-rich δ phase evolution in alloy 718. Alloy 718 samples were heat treated under hydrogenated argon at 980°C for 0 to 96 hours in order to gradually curb the content of interstitial species by reaction with the reducing atmosphere. Chemical analyses realized by glow discharge mass spectrometry (GDMS) confirmed the reduction of the concentration of these species. Specimens were solution-treated for 1h at 1050°C in an inert atmosphere and furnace cooled. Some of the samples were then aged at 920°C for times ranging from 10 min to 1 hour. The precipitation was measured quantitatively in terms of volume fraction and the morphology of the precipitates was appreciated using scanning electron microscopy (SEM). The differences in the precipitation kinetics and in the microstructure evolution for each interstitial concentration are then discussed.

Numerical study and experimental investigation of zone refining in ultra-high purification of gallium and its use in the growth of GaAs epitaxial layers

A numerical study has been carried out to optimize the zone refining process parameters such as zone length, zone travel rate, number of passes and the effect of molten zone stirring in ultra-high purification of gallium. Theoretical interpretation of the impurity concentration profile along the refined gallium ingot is also ascertained. Based upon the optimized parameters obtained through the study, 5N2 (99.9992% pure) gallium is subjected to zone refining for 50 passes and mechanically stirred at 20–35 rpm by a rotational mechanism in the directional freezing system. The refined gallium has a purity level of 7N2 (99.999992%) and the total impurity concentration is reduced to 77.7 ppb with respect to 24 impurities, as analyzed by glow discharge mass spectrometry (GDMS). The purified gallium is used as the starting material to grow GaAs epitaxial layers by liquid phase epitaxy technique. The quality of the grown layer is tested by secondary ion mass spectroscopy (SIMS), Hall measurements and low-temperature photocapacitance techniques.

Critical revision of GD-MS, LA-ICP-MS and SIMS as inorganic mass spectrometric techniques for direct solid analysis

Inorganic mass spectrometric techniques and methods for direct solid analysis are widely required to obtain valuable information about the multi-elemental spatial distribution of the major and trace constituents and/or isotope ratio information of a sample in a wide variety of solid specimens, including environmental wastes, biological samples, geochemical materials, coatings and semiconductors. The increasing need to characterize complex materials in industry (e.g. production control and quality assurance processes), and in different fields of science is forcing the development of various inorganic mass spectrometric methods for direct solid chemical analysis. These methods allow the characterization of solid materials both in bulk and in spatially resolved analysis (with lateral and/or in-depth resolution). This review critically discusses the analytical performance, capabilities, pros and cons, and trends of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), secondary ion (neutral) mass spectrometry (SIMS/SNMS), and glow discharge mass spectrometry (GD-MS) because they represent the most widespread and powerful inorganic mass spectrometric methods currently further improved and applied for the direct characterization of solids.

Quantification of Trace and Ultra-trace Elements in Nuclear Grade Manufactured Graphites by Fast-Flow Glow Discharge Mass Spectrometry and by Inductively Coupled Plasma – Mass Spectrometry after Microwave – Induced Combustion Digestions

AbstractFF-GDMS and MIC-ICP-MS methods were developed for the determination of mg/kg- and μg/kg-level B, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Sb, W and Pb in nuclear-grade graphite. Consistent results have been achieved in determining trace elements like B, Ti, Cr, Mn, Zr, Sb and Pb by both methods, which vary mostly less than ±30%, and are in line with the manufacturer reference values. On Mg, Al, Fe, Co, Zn, Mo and W, FF-GDMS analyses also show good agreement with the manufacturer's data. Continuing efforts in identifying source of interference, which has limited the MIC-ICP-MS analysis of these elements, is currently underway.

Fast polymer fingerprinting using flowing afterglow atmospheric pressure glow discharge mass spectrometry

Flowing afterglow atmospheric pressure glow discharge mass spectrometry (FA-APGD-MS) was used to interrogate different polymer species such as biopolymers, synthetic homo- and co-polymers. The main advantages of FA-APGD-MS for polymer samples include speed (<30 s per sample) and analysis at atmospheric pressures. Moreover, there are essentially no restrictions as to the kind of polymer sample that can be analyzed because FA-APGD-MS can deal with liquid and solid (soluble or insoluble) bulk polymers and granulates, irrespective of their conductivity, without requiring any sample preparation prior to analysis. We will discuss the mechanism of ion formation as well as the limitation of the accessible mass range (m/z < 500) in view of what type of information can be gained from the mass spectra obtained. Monomer units and some fragments were detected for homopolymers, e.g.cis-polyisoprene (IR), poly(ethylene glycol) (PEG), poly(ethylene terephthalate) (PET), which allowed identification of the polymer composition. The mass spectra obtained were further processed using principal component analysis (PCA) for a better visualization and assessing of mass-spectral reproducibility. Combination with PCA even allowed differentiation of pectin, amylopectin, and cellulose, chemically very similar polysaccharides whose characteristic differences lie in the nature of the glycosidic linkage. Finally, we were able to detect and identify phthalate plasticizers, bis(2-ethylhexyl) phthalate (BEHP) and dibutyl phthalate (DBP), present in poly(vinyl chloride)-based food wraps.

Distribution of iron in multicrystalline silicon ingots

The distribution of iron in multicrystalline silicon ingots for solar cells has been studied. A p- and a n-type multicrystalline ingot were intentionally contaminated by adding 53ppmwt (μg∕g) of iron to the silicon feedstock and compared to a reference p-type ingot produced from ultrapure silicon feedstock. The vertical total iron distribution was determined by neutron activation analysis and glow discharge mass spectrometry. For the intentionally Fe-contaminated ingots, the distribution can be described by Scheil’s equation with an effective distribution coefficient of 2×10−5. The interstitial iron concentration was measured in the p-type ingots. In the Fe-contaminated ingot, it is almost constant throughout the ingot and constitutes about 50% of the total concentration, which is in conflict with the previous studies. Gettering had a large impact on the interstitial iron levels by reducing the concentration by two orders of magnitude. Considerable trapping was observed at crystal defects on as-cut wafers from the same ingot. The trapping was suppressed by gettering. The back diffusion of iron from the ingot top after complete solidification was modeled and found to affect the iron concentration up to a distance of approximately 17mm into the ingot. The interstitial as well as the total iron concentration of the reference ingot were extremely low and difficult to measure accurately.