TY - GEN A1 - Rietig, Anja A1 - Acker, Jörg T1 - Development and validation of a new method for the precise and accurate determination of trace elements in silicon by ICP-OES in high silicon matrices T2 - Journal of Analytical Atomic Spectrometry N2 - A new method for the accurate and precise determination of impurities in silicon was developed and statistically validated. Particular attention was paid to the correct determination of the non-metals boron and phosphorus. Instead a time-consuming open vessel digestion under mild conditions, the dissolution of silicon took place in a microwave-assisted high-pressure system. The essential innovation of the presented method is the direct use of the concentrated digestion solution for ICP-OES measurements. This approach avoids the commonly used, time-consuming method that requires the removal of silicon and acid matrix by volatilisation, which is the most critical step in the determination of boron; however, the ICP-OES measurement in such high silicon matrices requires an entirely new optimisation of the measuring conditions, including the careful selection of emission lines with respect to selectivity and, spectral and non-spectral inferences. For quantification of the impurities contents, the methods of matrix matching (MMC) and multiple standard addition (MSA) were used. After optimisation of the spike concentrations for MSA, the qualities of both methods were compared through a statistical analysis. For the metallic impurities Al, Mg, Ca, Ti, Cr, Mn, Fe, Ni, Cu, and Zr and P, the validation was performed against certified reference materials (IPT134, IPT135, NIST57b). To validate boron, 9 silicon samples with different contents of boron from three interlaboratory comparisons were used. The new procedure allows for the determination of the impurities of 4N-silicon (12 elements). KW - impurities KW - inductively coupled plasma emission spectroscopy KW - silicon KW - microwave-assisted digestion KW - high silicon matrix KW - multiple standard addition KW - boron KW - phosphorus Y1 - 2017 UR - http://pubs.rsc.org/en/content/articlelanding/2017/ja/c6ja00241b#!divAbstract U6 - https://doi.org/10.1039/C6JA00241B VL - 32 IS - 2 SP - 322 EP - 333 ER - TY - GEN A1 - Grafe, Hans-Joachim A1 - Löser, Wolfgang A1 - Schmitz, Steffen A1 - Sakaliyska, Miroslava A1 - Wurmehl, Sabine A1 - Eisert, Stefan A1 - Reichenbach, Birk A1 - Acker, Jörg A1 - Rietig, Anja A1 - Ducke, Jana T1 - NMR investigation of boron impurities in refined metallurgical grade silicon T2 - Physica status solidi. A, Applications and Materials Science N2 - The nuclear magnetic resonance (NMR) method was applied for tracking boron impurities in the refining process of metallurgical grade (MG) silicon. From the NMR signal of the 11B isotope at an operating temperature 4.2 K, the boron concentration can be estimated down to the order of 110 wppm B. After melting and resolidification of MG-Si alloyed with Ca and Ti, a major fraction of B impurities remains in the Si solid solution as inferred from the characteristic NMR frequency. The alloying element Ti does not form substantial fractions of TiB2. Acid leaching of crushed powders of MG-Si alloyed with Ca and Ti can diminish the initial impurity content of B suggesting its accumulation in the grain boundary phases. KW - boron KW - impurity KW - intermetallic compounds KW - nuclear magnetic resonance KW - silicon KW - transition-metal diboride KW - Si-Al melt KW - removal KW - solidification Y1 - 2015 UR - http://onlinelibrary.wiley.com/doi/10.1002/pssa.201431908/full U6 - https://doi.org/10.1002/pssa.201431908 SN - 1862-6319 VL - 212 IS - 9 SP - 2031 EP - 2036 ER - TY - CHAP A1 - Rietig, Anja A1 - Acker, Jörg ED - Nygaard, Lars ED - Pachaly, Bernd ED - Page, Ingrid Gamst ED - Rong, Harry ED - Tangstad, Merete ED - Tveit, Halvard T1 - A new and fast method for determination of boron, phosphorus and other trace elements in metallurgical grade silicon T2 - Silicon for the Chemical and Solar Industry XIII, Kristiansand, 2016 N2 - A new method for accurate and precise determination of non-metallic and metallic impurities in silicon was developed and statistically validated. The first step is the fast dissolution of silicon in a microwave-assisted high pressure system to minimize a loss of phosphorus. The essential innovation is the use of the concentrated digestion solution for ICP-OES measurements. This approach avoids the common removal of the silicon and acid matrix by volatilization, which can cause considerable losses of boron. Finally, for the ICP-OES measurements in such high-silicon matrices the optimum measuring conditions were determined and a careful selection of emission lines with respect to selectivity, spectral and non-spectral inferences and matrix effects was performed. The method of matrix matched calibration (MMC) is used for quantification of the impurities’ contents. For Al, Mg, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zr and P the validation was performed against certified reference materials (IPT134, IPT135, NIST57b). To validate the determination of boron 9 silicon samples of different boron contents from three interlaboratory comparisons were used. The new procedure allows the determination of impurities of 4N-silicon (12 elements) with high precision and accuracy. KW - silicon KW - ICP-OES KW - impurity KW - chemical analysis KW - boron KW - phosphorus Y1 - 2016 UR - https://www.ntnu.no/trykk/publikasjoner/Silicon%20for%20the%20chemical%20and%20solar%20industry%20XIII/ SP - 95 EP - 106 PB - Department of Materials Science and Engineering, Norwegian University of Science and Technology CY - Trondheim ER - TY - GEN A1 - Rietig, Anja A1 - Grafe, Hans-Joachim A1 - Acker, Jörg T1 - New insights into boron species in acidic digestion solutions of boron-doped silicon T2 - Journal of Analytical Atomic Spectrometry N2 - The exact and precise determination of the boron concentration in silicon is still a challenge. A systematic investigation dealing with the digestions of 60 silicon samples with HF-HNO3 and subsequent boron determination by ICP-OES revealed that the concentration found could be up to 60% lower than the actual boron concentration depending on the composition of the sample solution. As the original boron–silicon compound that was identified was colloidally precipitated in the presence of an excess of hydrofluoric acid and then partially retained by filtration or by the sample introduction system, systematic lower boron concentrations were determined. In acidic, HF-free digestion solutions, this compound existed in a soluble form parallel to the borate in B(OH)4−. In an excess of hydrofluoric acid, the compound was converted into the colloidal form and, in parallel, B(OH)4− was converted to tetrafluoroborate, BF4−. For the composition of the colloidal compound, a molar ratio of boron to silicon of 1 : 4 could be determined. 11B-ss-NMR analysis revealed a tetrahedral geometry compound with a central boron atom surrounded by four silicon atoms. It is assumed that a soluble form with four –Si(OH)3 groups was present in the hydrofluoric acid-free solutions, while an insoluble form with four –SiF3 groups was present in HF-containing solution. KW - silicon KW - ICP-OES KW - etching KW - hydrofluoric acid KW - nitric acid KW - 11B-NMR KW - high-precision chemical analysis KW - boron KW - digestion Y1 - 2021 UR - https://pubs.rsc.org/en/content/articlelanding/2021/ja/d1ja00190f SN - 1364-5544 VL - 36 IS - 11 SP - 2492 EP - 2500 ER - TY - GEN A1 - Rietig, Anja A1 - Grafe, Hans-Joachim A1 - Acker, Jörg T1 - Understanding the Reasons for Erroneous Determinations of Boron in Silicon following Wet Chemical Digestion in HF/HNO3 T2 - Proceedings of the Silicon for the Chemical & Solar Industry XVI KW - boron KW - silicon KW - species KW - trace element Y1 - 2022 UR - https://ssrn.com/abstract=4123058 SN - 978-82-692919-0-2 U6 - https://doi.org/10.2139/ssrn.4123058 ER -