WO2023172150A1 - Procédé de vérification de la source d'un matériau contenant du silicium - Google Patents

Procédé de vérification de la source d'un matériau contenant du silicium Download PDF

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Publication number
WO2023172150A1
WO2023172150A1 PCT/NZ2023/050032 NZ2023050032W WO2023172150A1 WO 2023172150 A1 WO2023172150 A1 WO 2023172150A1 NZ 2023050032 W NZ2023050032 W NZ 2023050032W WO 2023172150 A1 WO2023172150 A1 WO 2023172150A1
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Prior art keywords
silicon
ratio
sample
source
containing material
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PCT/NZ2023/050032
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English (en)
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Russell David FREW
Samuel James LIND
Joshua WAKEFIELD
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Oritain Global Limited
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Publication of WO2023172150A1 publication Critical patent/WO2023172150A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers

Definitions

  • the present invention relates to a method for verifying the source of a silicon containing material.
  • the invention relates to determining the ratio of silicon isotopes in a sample of the material and then comparing the ratio against data for silicon of known source to verify the source of the material.
  • Verification of the source of silicon and silicon containing materials is becoming increasingly important worldwide.
  • Silicon is a strategic resource for many countries due to its importance as a semiconductor for computers and photovoltaics. There is growing political demand to verify the source of silicon. There are also growing concerns around a lack of sustainability, damage to the environment caused by silicon manufacturers, and damage to human health by some manufacturers of silicon and silicon containing materials.
  • Silicon and silicon containing materials are often highly refined, for example in the case of elemental silicon for the photovoltaic and semiconductor industries, or in the case of fumed silica. Governments and consumers are demanding that the source or location where the silicon containing material is refined can be verified. It is also useful to be able to verify the geographical or geological region where the silicon containing material was extracted.
  • forensic chemistry and statistics can be combined to establish an inherent "fingerprint" based on naturally occurring chemical elements and their isotopes contained in the material. For example, the geographic region where a particular mineral was extracted can sometimes be determined by analysis of trace elements or isotopic ratios. In other cases, the production process can impart a fingerprint that is unique to that batch or production unit.
  • isotopes of silicon in the natural environment There are four isotopes of silicon in the natural environment: 28 Si, 29 Si, 30 Si and 32 Si.
  • the isotopes 28 Si, 29 Si, 30 Si are stable isotopes and make up virtually the entirety of natural silicon in any terrestrial sample.
  • 32 Si is radiogenic with a half-life of about 153 years. Only traces of 32 Si are detectible in natural silicon samples.
  • Other isotopes of silicon have a half-life too short and abundances too low to detect in samples of silicon.
  • Elemental silicon is produced to a number of grades, depending on the intended use.
  • Metallurgical grade silicon has a purity of between about 95% and 99%. MGS may be refined to produce polycrystalline silicon (polysilicon) or monocrystalline silicon (monosilicon), in which impurities are less than about 1 part per million (ppm).
  • Polysilicon is made up of many silicon crystallites, and therefore comprises grain boundaries at adjacent crystallites.
  • Monosilicon is a single crystal of silicon, having a continuous crystal structure, and is substantially devoid of grain boundaries.
  • polysilicon or monosilicon generally have impurities of less than about 1 part per billion (ppb).
  • polysilicon and monosilicon are produced by chemical vapour deposition methods. Silicon is converted to a gaseous phase silicon compound, such as silane (SiF ) or trichlorosilane (SiHCh), and purified via distillation. Purified gas is then pyrolised to elemental silicon and collected.
  • the purified silicon may be polysilicon or monosilicon, depending on the deposition methodology. In some cases, the purified silicon may be recrystallised to increase its purity, reduce the number of grain boundaries, or to produce monosilicon.
  • a method of verifying the source of a silicon containing material comprising:
  • the ratio of silicon isotopes is any ratio of 28 Si, 29 Si and 30 Si.
  • the ratio is the ratio 29 Si/ 28 Si or the ratio 30 Si/ 28 Si, or a combination thereof.
  • the silicon is elemental silicon. In other embodiments, the silicon is in the form of a silicon dioxide, a silicate, or a silicic acid or a salt thereof.
  • the silicon containing material is at least 99.99999% silicon, for example at least 99.999999999% silicon.
  • the silicon containing material is polysilicon. In other embodiments, the silicon containing material is monosilicon.
  • the ratio of silicon isotopes is determined by any known method, including isotope ratio mass spectrometry (IRMS), thermal ionisation mass spectrometry (TIMS), or inductively coupled plasma mass spectroscopy (ICP-MS).
  • IRMS isotope ratio mass spectrometry
  • TMS thermal ionisation mass spectrometry
  • ICP-MS inductively coupled plasma mass spectroscopy
  • the preferred method is multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).
  • the source is a silicon refining facility, a polysilicon refining facility, or a monosilicon refining facility.
  • the silicon containing material is a silicon semiconductor, a silicon photovoltaic cell, a silicon chip, or a silicon integrated circuit.
  • the method further comprises determining a ratio of oxygen isotopes of oxygen present in the sample.
  • the ratio of oxygen isotopes is the ratio of 18 O/ 16 O.
  • the method further comprises determining the concentrations of one or more trace elements in the sample.
  • the trace elements include, but are not limited to, at least one of Li, B, Na, Mg, Al, K, Ca, Ti, Ni, As, Rb, Sr, Sn, Sb, Cs and Ba.
  • the sample comprises trace elements at a concentration of less than 100 ppm, preferably less than 10 ppb, more preferably less than 1 ppb.
  • the concentrations of one or more trace elements are obtained via analysis of a subsample of the sample of the silicon, wherein the subsample has a location in the sample that includes a grain boundary.
  • Figure 1 shows isotopic fingerprints of samples from different sources.
  • the squares represent samples obtained from USA Plant 1.
  • the open squares represent MGS samples and the filled squares represent polysilicon samples.
  • the circles represent samples obtained from USA Plant 2.
  • the open circles represent polysilicon samples and the filled circles represent monocrystal silicon wafer samples.
  • Figure 2 shows the Si isotopic values of samples from the same sources but at different stages of production.
  • the solid black symbols represent samples of 100% virgin silicon doped with phosphorus.
  • the open circles represent samples that are also 100% polysilicon doped with gallium.
  • isotope ratio means the ratio of atomic abundances of two isotopes of the same chemical element.
  • trace element means a chemical element having a very low concentration and includes, but is not limited to, an element having a concentration of less than 100 ppm or less than 100 pg/g.
  • trace metal has a correspnding meaning.
  • polycrystalline silicon or "polysilicon” means elemental silicon (Si) in the form of a solid made up of silicon crystallites and comprising grain boundaries at adjacent crystallites.
  • microcrystalline silicon or “monosilicon” means elemental silicon (Si) in the form of a single crystal of silicon and being substantially devoid of grain boundaries.
  • MGS metalurgical grade silicon
  • wafer means a thin slice of semiconductor material such as crystalline silicon.
  • composition of matter, group of steps or group of compositions of matter shall be taken to encompass one and a plurality (i.e. one or more) of those steps, compositions of matter, groups of steps or group of compositions of matter.
  • the invention is predicated, at least in part, on the finding that the sourcing and manufacturing process of silicon containing materials differs between providers with respect to 28 Si : 29 Si : 30 Si isotope ratios. Therefore, it is possible to verify the source of a silicon containing material by comparison of its silicon isotope ratio against corresponding data for silicon containing materials of known source.
  • Data relating to the silicon isotope ratio and/or trace element abundance in a sample of a silicon containing material can add relevant identifying information to a dataset (or 'silicon fingerprint') that may be used to determine the source of the silicon containing material.
  • the dataset obtained from a sample of silicon containing material of unknown source may be compared against data for silicon containing materials of known source to verify the source of the material.
  • silicon containing materials include elemental silicon, silicon dioxides, silicates, and silicic acids and their salts.
  • Elemental silicon includes monosilicon, polysilicon, as well as elemental silicon of lower purities such as metallurgical grade silicon (MGS) or raw extracted silicon ore.
  • MGS metallurgical grade silicon
  • the elemental silicon comprises trace elements at a concentration of less than 100 ppm. In some embodiments, the elemental silicon comprises trace elements at a concentration of less than 10 ppb. In some embodiments, the elemental silicon comprises trace elements at a concentration of less than 1 ppb.
  • Silicon dioxides can include natural and synthetic silicon dioxides, such as quartz, fused quartz, silica and fumed (or pyrogenic) silica.
  • Silicates can include natural and synthetic ionic forms of silicon, such as orthosilicates, metasilicates and pyrosilicates.
  • Silicon containing materials may also include silicic acids and their corresponding salts, such as hexafluorosilicic acid and hexafluorosilicates.
  • the silicon containing material includes manufactured, processed or semiprocessed silicon containing materials, such as silicon semiconductors, silicon photovoltaic cells, silicon chips, and silicon integrated circuits.
  • the source of silicon containing material to be verified by the method of the invention is preferably the facility where the silicon containing material was refined or purified.
  • the source of silicon containing material may also include the geographic or geological area in which the silicon containing material was extracted.
  • the silicon isotope ratio that is determined in the method of the invention is any ratio of 28 Si, 29 Si and 30 Si.
  • the 29 Si/ 28 Si and 30 Si/ 28 Si ratios are determined and the isotope data are reported as delta values which express the deviation from the accepted standard NBS28.
  • Isotopic ratios are conventionally determined via mass spectrometry (MS). However, in order to use isotopic ratios to verify the source of a silicon containing material, the determination of silicon isotope ratio must be sufficiently precise and sensitive to identify small differences.
  • Geological quartz (the starting product of polysilicon) is virtually homogenous globally. Measurable differences in Si isotopes have been observed in biogenic silica. Si isotopes undergo fractionation during the purification processes between quartz, MGS and polysilicon.
  • the inventors have now found that the key purification step, where the Si is purified in a gaseous intermediary (trichlorosilane) via distillation, enables isotopic fractionation of the Si isotopes ( 28 Si, 29 Si, 30 Si). As this step is specific to each manufacturer or manufacturing facility, the fractionation may show some specificity between different facilities (origins), observed as a difference in these isotope ratios ( 29 Si/ 28 Si and 30 Si/ 28 Si). Note that due to the low natural abundance of 29 Si and 30 Si, the isotope ratio of 29 Si/ 30 Si cannot be reliably determined.
  • MS techniques previously considered sufficiently sensitive for determining isotopic ratios required a sample of the material to be in gas phase, which required fluorination of the silicon sample and thus had the attendant hazards and disadvantages of working with fluorine.
  • the method of the invention involves techniques for determining silicon isotope ratios that include isotope ratio mass spectrometry (IRMS), thermal ionisation mass spectrometry (TIMS), and inductively coupled plasma mass spectroscopy (ICP-MS).
  • ICP- MS is a preferred technique. Examples of variations of ICP-MS that would be suitable for determining silicon isotope ratios include multi-collector ICP-MS (MC-ICP-MS).
  • the isotopic ratio of oxygen in the silicon containing material may be determined in addition to determining silicon isotope ratios.
  • the oxygen isotope ratio that is preferably determined in these embodiments of the invention is the ratio of 18 O/ 16 O.
  • Data relating to the oxygen isotope ratio in a silicon and oxygen containing sample can provide datapoints for comparison with data for oxygen isotope ratios of known silicon and oxygen containing materials to assist in verifying the source of the sample.
  • An example of a suitable method for determining the isotopic ratio of the oxygen atoms in the silicon containing material is gas source mass spectrometry.
  • the determined variation in isotope ratio can be modelled by either Rayleigh kinetics for a closed system, or steady-state model for an open system.
  • the method of the invention involves suitable techniques for determining trace element concentration that include X-ray fluorescence, glow discharge mass spectrometry (GDMS), thermal ionisation mass spectrometry, sensitive high-resolution ion microprobe (SHRIMP), and ICP-MS.
  • suitable techniques for determining trace element concentration include X-ray fluorescence, glow discharge mass spectrometry (GDMS), thermal ionisation mass spectrometry, sensitive high-resolution ion microprobe (SHRIMP), and ICP-MS.
  • suitable techniques for determining trace element concentration that include X-ray fluorescence, glow discharge mass spectrometry (GDMS), thermal ionisation mass spectrometry, sensitive high-resolution ion microprobe (SHRIMP), and ICP-MS.
  • Examples of variations of ICP-MS that would be suitable for determining the concentration of trace elements include multi-collector ICP-MS (MC-ICP- MS), time of flight (ICP-ToF), or laser ablation ICP-MS (LA
  • Determination of trace elements of a silicon containing material is preferably performed using LA-ICP-MS.
  • the LA-ICP-MS technique involves the irradiation of a sample with a laser (e.g. 193 nm excimer laser) causing melting and vaporisation of an irradiated portion of the sample and formation of a plasma plume containing ions of the sample.
  • the ions are ejected from the plume into a carrier gas stream connected to an ICP-MS instrument.
  • Elements such as Li, B, Na, Mg, Al, K, Ca, Ti, Ni, As, Rb, Sr, Sn, Sb, Cs and Ba may be measured via the LA-ICP-MS technique.
  • the step of determining the concentration of trace elements in a polysilicon sample may include the step of determining the concentration of trace elements at one or more grain boundaries.
  • Verification of the source of a silicon containing sample using an analysis of silicon isotopic ratios as a sole method may not be easily achievable due to the very small differences in isotopic ratios in samples derived from different sources. Accordingly, in some cases it may be necessary for the method of the invention to include both steps, i.e. determining trace element abundance and determining silicon isotopic ratios, in order to produce a more detailed dataset.
  • the silicon isotope ratio data is compared against data for silicon containing materials of known source to verify the source of the material.
  • a reference dataset is obtained or prepared for samples of silicon containing materials of different known sources.
  • the sources of samples of silicon containing materials may include a refinery, a foundry or a manufacturing facility for the silicon containing material.
  • the 28 Si : 29 Si : 30 Si silicon isotope ratio datapoint is obtained.
  • datapoints for trace element concentrations for at least one of Li, B, Na, Mg, Al, K, Ca, Ti, Ni, As, Rb, Sr, Sn, Sb, Cs and Ba are also obtained.
  • the silicon containing material comprises oxygen, such as silicon dioxide or silicate
  • oxygen such as silicon dioxide or silicate
  • an additional datapoint may be obtained for the 18 O/ 16 O isotope ratio.
  • the datapoints for each sample of silicon containing material of known source are compiled into a computer-accessible library suitable for multivariate statistical analysis.
  • the variations in silicon isotope ratios between silicon containing materials from different sources may be very small.
  • the variations in trace element concentrations in silicon containing materials from different sources may be very small.
  • multivariate statistical models are used to generate a probability value and error rate relating to each source in the reference dataset.
  • the silicon of unverified source is verified as being derived from that source.
  • data relating to the ratio of silicon isotopes in a sample of the silicon containing material can be analysed according to kinetic models for isotope fractionation, including Rayleigh kinetic models and steady state kinetic models.
  • Example 1 describes a method for determining the silicon isotope ratios in samples of MGS, polysilicon and silicon wafer. The results are shown in Figures 1 and 2.
  • Figure 1 shows a clear clustering of samples according to their source and differentiation of samples from different sources.
  • Figure 2 shows show that the fingerprint appears to be conserved through the manufacturing process. MGS samples from USA Plant 1 have a similar fingerprint to Polysilicon samples from USA Plant 1.
  • Silicon isotopes were determined using a modification of the method described in Wille et al. (2010), Earth and Planetary Science Letters, 292, 281-289. Each solid polysilicon sample was prepared by encasing the sample within 2 snap-lock bags. Using a hammer (or equivalent), each sample was crushed to form a powder to a consistency resembling castor sugar. Powdered samples (about 0.2 g) were accurately weighed and placed in a nickel crucible and powdered NaOH (1 g) added. Each mixture of sample and NaOH was then melted by heating in a muffle furnace according to the following program: 300 °C ramp o Hold 2 hours
  • each melt was transferred to a 50 ml DigiTube (or equivalent) and diluted to 50 mL with deionised water.
  • concentration of Si in each melt was determined using the method of Strickland & Parsons (1972), A Practical Handbook of Seawater Analysis, 2nd edition. Ottawa, Canada, Fisheries Research Board of Canada, 310pp. (Bulletin Fisheries Research Board of Canada, Nr. 167 (2nd ed)). DOI: http://dx.doi.org/10.25607/OBP-1791.
  • Each solution was purified using ion exchange columns.
  • a column was filled with 1 ml Dowex 50 W-X8 cation exchange resin (200-400 mesh).
  • the resin was prepared according to the following procedure: o Add 0.5 ml 8% v/v HF, leave for 1 hour and then add 0.75 ml MQ water (repeat twice more).
  • Each sample was diluted to 20 ppm Si using the results from the Si concentration analysis.
  • Each sample (0.5 ml) was pipetted into the cleaned column and the eluent collected.
  • the column was rinsed 4 times with MQ water (0.5 ml) collecting the eluent in the same vessel to give 4 ppm samples.
  • Concentrated QD HNO3 (50 pl) was added to each sample followed by dilution to 0.5 ppm (0.25 ml sample + 1.75 ml 2% HNO3).
  • Si isotope measurement of each sample was carried out by multi-collector inductively coupled plasma mass spectrometry. 28 Si was set to the centre cup and the 29 Si peak set at 28.966 to avoid NO interference.
  • Stable isotope data are reported as delta values which express the deviation from an accepted standard.
  • the standard used is NBS28 as which serves as the primary reference material for silicon 3 2S Si ⁇ 3 3C Si measurements defining the zero point of the 3- scaie.
  • the delta values are defined as: where SAN refers to the sample values. Results are multiplied by 1000 and reported in units of per mille (%o).
  • the source of a sample of polysilicon of unverified source may be verified according to the following methodology.
  • a reference dataset in computer-accessible format is prepared for several samples of polysilicon of different known sources.
  • the 28 Si/ 29 Si/ 30 Si silicon isotope ratio is obtained. Trace element concentrations for at least one of Li, B, Na, Mg, Al, K, Ca, Ti, Ni, As, Rb, Sr, Sn, Sb, Cs and Ba may also be obtained.
  • a sample of polysilicon of unverified source is analysed to obtain its 28 Si/ 29 Si/ 30 Si silicon isotope ratio. Trace element concentrations for at least one of Li, B, Na, Mg, Al, K, Ca, Ti, Ni, As, Rb, Sr, Sn, Sb, Cs and Ba may also be obtained.
  • the data for the polysilicon of unverified source and the reference dataset is analysed in two or more discriminatory and non-discriminatory multivariate statistical models to generate a probability value and error rate relating to each source in the reference dataset. Where the probability value and error rate meet a predetermined threshold for one source, the polysilicon of unverified source is verified as being derived from that source.

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Abstract

L'invention concerne un procédé de vérification de la source d'un matériau contenant du silicium par détermination des rapports des isotopes de silicium 28Si, 29Si et 30Si dans un échantillon du matériau, puis comparaison des données de rapport avec des données pour le silicium d'une source géographique ou de fabrication connue pour vérifier la source du matériau.
PCT/NZ2023/050032 2022-03-11 2023-03-10 Procédé de vérification de la source d'un matériau contenant du silicium WO2023172150A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025348A1 (fr) * 2005-09-02 2007-03-08 Australian Nuclear Science & Technology Organisation Spectromètre de masse à proportion d’isotopes et procédés de détermination de proportions d’isotopes
JP2018100834A (ja) * 2016-12-19 2018-06-28 日本電信電話株式会社 コメ産地推定方法およびシステム
US20200124585A1 (en) * 2017-06-26 2020-04-23 Ids Group Isotopic marking and identification of animals and plants
US20220065836A1 (en) * 2019-01-02 2022-03-03 Ids Group Isotopic marking and identification of liquids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025348A1 (fr) * 2005-09-02 2007-03-08 Australian Nuclear Science & Technology Organisation Spectromètre de masse à proportion d’isotopes et procédés de détermination de proportions d’isotopes
JP2018100834A (ja) * 2016-12-19 2018-06-28 日本電信電話株式会社 コメ産地推定方法およびシステム
US20200124585A1 (en) * 2017-06-26 2020-04-23 Ids Group Isotopic marking and identification of animals and plants
US20220065836A1 (en) * 2019-01-02 2022-03-03 Ids Group Isotopic marking and identification of liquids

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SAVAGE PAUL S.; ARMYTAGE ROSALIND M.G.; GEORG R. BASTIAN; HALLIDAY ALEX N.: "High temperature silicon isotope geochemistry", LITHOS, vol. 190, 23 January 2014 (2014-01-23), AMSTERDAM, NL , pages 500 - 519, XP028666824, ISSN: 0024-4937, DOI: 10.1016/j.lithos.2014.01.003 *
WIEDERHOLD JAN G.: "Metal Stable Isotope Signatures as Tracers in Environmental Geochemistry", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 49, no. 5, 3 March 2015 (2015-03-03), US , pages 2606 - 2624, XP093091856, ISSN: 0013-936X, DOI: 10.1021/es504683e *
YANG XUEZHI, LIU XIAN, ZHANG AIQIAN, LU DAWEI, LI GANG, ZHANG QINGHUA, LIU QIAN, JIANG GUIBIN: "Distinguishing the sources of silica nanoparticles by dual isotopic fingerprinting and machine learning", NATURE COMMUNICATIONS, vol. 10, no. 1, pages 1 - 9, XP093091851, DOI: 10.1038/s41467-019-09629-5 *
ZAMBARDI THOMAS; POITRASSON FRANCK; CORGNE ALEXANDRE; MÉHEUT MERLIN; QUITTÉ GHYLAINE; ANAND MAHESH : "Silicon isotope variations in the inner solar system: Implications for planetary formation, differentiation and composition", GEOCHIMICA ET COSMOCHIMICA ACTA, vol. 121, 10 July 2013 (2013-07-10), US , pages 67 - 83, XP028739168, ISSN: 0016-7037, DOI: 10.1016/j.gca.2013.06.040 *

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