WO2018110653A1 - ポリシリコン破砕物の付着樹脂の分析方法 - Google Patents
ポリシリコン破砕物の付着樹脂の分析方法 Download PDFInfo
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- WO2018110653A1 WO2018110653A1 PCT/JP2017/044936 JP2017044936W WO2018110653A1 WO 2018110653 A1 WO2018110653 A1 WO 2018110653A1 JP 2017044936 W JP2017044936 W JP 2017044936W WO 2018110653 A1 WO2018110653 A1 WO 2018110653A1
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- Prior art keywords
- resin
- polysilicon
- crushed
- temperature
- organic volatile
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- 239000011347 resin Substances 0.000 title claims abstract description 147
- 229920005989 resin Polymers 0.000 title claims abstract description 147
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 120
- 229920005591 polysilicon Polymers 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title description 60
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 238000004458 analytical method Methods 0.000 claims abstract description 26
- 238000011088 calibration curve Methods 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 64
- 239000000047 product Substances 0.000 claims description 49
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000007857 degradation product Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000004445 quantitative analysis Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 34
- 239000003463 adsorbent Substances 0.000 description 24
- 239000004698 Polyethylene Substances 0.000 description 23
- 229920000573 polyethylene Polymers 0.000 description 23
- 238000012856 packing Methods 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004696 Poly ether ether ketone Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920002530 polyetherether ketone Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
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- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JXUKFFRPLNTYIV-UHFFFAOYSA-N 1,3,5-trifluorobenzene Chemical compound FC1=CC(F)=CC(F)=C1 JXUKFFRPLNTYIV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 102100037114 Elongin-C Human genes 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 101001011859 Homo sapiens Elongin-A Proteins 0.000 description 1
- 101001011846 Homo sapiens Elongin-B Proteins 0.000 description 1
- 101000881731 Homo sapiens Elongin-C Proteins 0.000 description 1
- 101000836005 Homo sapiens S-phase kinase-associated protein 1 Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Images
Classifications
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- 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
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- G01N33/442—Resins; Plastics
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Definitions
- the present invention relates to a method for analyzing resin adhering to the surface of a crushed polysilicon. Specifically, the present invention provides an analysis method capable of quantifying the adhered resin of the crushed polysilicon with high sensitivity and qualitatively and with high accuracy.
- Polycrystalline silicon is used as a raw material for silicon single crystal growth necessary for manufacturing semiconductor devices and the like, and the demand for purity thereof is increasing.
- Polycrystalline silicon is often produced by the Siemens method.
- the Siemens method is a method in which polycrystalline silicon is vapor-phase grown on the surface of a core rod by bringing a silane source gas such as trichlorosilane into contact with a heated silicon core rod.
- Polycrystalline silicon produced by the Siemens method is obtained in the form of a rod.
- This rod-shaped polycrystalline silicon has a diameter of 80 to 150 mm and a length of 1000 mm or more. Therefore, when this rod-shaped polycrystalline silicon is used in another process, for example, a silicon single crystal growing facility by the CZ method, it is cut into rods of a predetermined length or crushed into an appropriate lump. The These crushed polysilicon are classified by a sieve or the like as necessary.
- a cleaning process for example, a method such as bringing hydrofluoric acid or an acidic solution containing hydrofluoric acid and nitric acid into contact with polycrystalline silicon, It is shipped in a high purity packing bag in the packing process.
- a highly chemical-resistant resin member such as polypropylene, polyethylene, PTFE, polyfluoride, etc. Vinylidene (PVDF) is used as a container for immersing the crushed polysilicon in an acidic solution containing hydrofluoric acid and nitric acid.
- a highly chemical-resistant resin member such as polypropylene, polyethylene, PTFE, polyfluoride, etc. Vinylidene (PVDF) is used as a container for immersing the crushed polysilicon in an acidic solution containing hydrofluoric acid and nitric acid.
- PVDF Vinylidene
- resin gloves such as polyvinyl chloride, nitrile rubber, polyethylene, and polyurethane are used in the packing process.
- polyethylene, polyethylene terephthalate, or polypropylene is used as the packaging bag. These may come into contact with the crushed polysilicon and the resin may adhere.
- the contamination source can be identified, and it is possible to improve the contamination source to prevent adhesion.
- the crushed polysilicon material obtained by crushing the polycrystalline silicon rod is heat-treated in an inert gas atmosphere at a temperature of 350 to 600 ° C., and the generated carbon dioxide is reddish.
- the above qualitative analysis results are easy to detect with respect to resin components adhering in large quantities, there is room for improvement in terms of detection sensitivity with respect to small amounts of resin components.
- the heating temperature has an upper limit of 350 ° C., and there is a high possibility that it will be used in the manufacturing process of polysilicon, such as fluorine resin, PEEK, etc. There is no awareness of the analysis for resins with decomposition onset temperatures above.
- JP 2013-170122 A Japanese Unexamined Patent Publication No. 2016-56066
- the present invention has been made in view of such problems, and the object of the present invention is to identify with high sensitivity the type of resin that adheres to the surface of the crushed polysilicon material that could not be grasped by the prior art. Furthermore, it is another object of the present invention to provide an analysis method capable of quantifying the adhesion amount of each resin with high accuracy as required.
- the process for producing the crushed polysilicon is performed in a clean room environment having a clean room filter having a PTFE membrane.
- the partition material, curtain, partition, and floor material of the clean room are made of polyvinyl chloride, epoxy, etc. Resin is used.
- the resin contains a plurality of additives such as a plasticizer, a lubricant, a solvent, and a colorant.
- a plasticizer such as polyvinyl chloride
- a lubricant such as a lubricant, a solvent, and a colorant.
- organic volatile components those having volatility (hereinafter also referred to as organic volatile components) are relatively low temperature in the atmosphere. It is thought that it will be released gradually.
- the present invention removes organic volatile components from the crushed polysilicon, then raises the temperature of the crushed polysilicon under the flow of inert gas, and collects the resin decomposed material generated at the heating temperature. And analyzing the degradation product specific to the resin contained in the degradation product of the resin to identify the type of resin adhering to the crushed polysilicon product, and analyzing the surface organic impurities of the crushed polysilicon product Is to provide.
- the removal of the organic volatile component is performed at 180 ° C. or higher while maintaining a temperature lower than the decomposition start temperature of the resin that is assumed to be in contact with the polysilicon in the manufacturing process of the crushed polysilicon. This is preferable for reliably removing organic volatile components.
- the temperature of the crushed polysilicon after the removal of the organic volatile components is increased in stages, and each heating temperature decomposes the resin that is supposed to come into contact with the polysilicon in the manufacturing process of the crushed polysilicon. It is preferable to raise the temperature stepwise in the temperature range from the start temperature to 800 ° C. in accordance with the decomposition start temperature of the resin, because a decomposition product unique to the attached resin can be reliably detected.
- the type of resin adhering to the surface of the crushed polysilicon can be identified with higher accuracy, and the amount of adhering resin can be accurately determined for each type of resin. .
- the polysilicon crushed material to be analyzed is obtained by crushing rod-shaped polycrystalline silicon produced by the Siemens method, and includes the following crushing steps. All of the processing steps, that is, (a) crushing step, (b) washing step, and (c) packing step, which have undergone any step, are included.
- (A) Crushing process Polycrystalline silicon is produced by the Siemens method, fluidized bed method or the like. Among them, the polycrystalline silicon obtained by the Siemens method is usually obtained in a rod shape, so that it can be easily put into a crucible for producing single crystal silicon, for example. As described above, the rod-like polycrystalline silicon is crushed to an appropriate size after being cut as necessary. The crushing is processed into a polysilicon crushed material, for example, by crushing with a crusher such as a jaw crusher or a roll crusher, or by crushing manually with a hammer or a chisel.
- a crusher such as a jaw crusher or a roll crusher
- the shape of the polysilicon crushed material obtained by the above crushing is not particularly limited, but an indeterminate (non-uniform direction state) lump obtained by crushing or the like is common.
- the size of the crushed polysilicon is generally 0.1 to 20 cm, preferably 1 to 10 cm in particle size represented by the maximum length of the crushed pieces.
- the crushed pieces may be sized by a sieve or the like as necessary to adjust the particle size.
- the silicon crushed material may come into contact with the resin such as the resin cover of the crusher and the resin cover of the crushing stand, and may be contaminated.
- the polysilicon crushed material obtained from the crushing process is a process of removing the metal, oil, etc. adhering to the surface during crushing and handling, and purifying the polysilicon crushed material. Is done. For example, what was provided with the pickling process by an acid solution and the subsequent water-washing process by a pure water is mentioned.
- the pickling step the surface of the polysilicon crushed material is dissolved to remove the contaminants by immersing the cleaning basket holding the crushed polysilicon in advance in a chemical bath containing an acid solution. Examples of the acid solution used in the pickling step include a mixed solution of hydrofluoric acid and nitric acid.
- the water washing step after the pickling step it is preferable to use ultrapure water.
- the polycrystalline silicon after washing with ultrapure water is preferably dried by blow drying (aeration drying), and this drying is preferably performed at a temperature of 80 to 150 ° C. for 0.5 to 24 hours.
- the silicon crushed material may come into contact with the cleaning basket and the resin of the conveyor and may be contaminated.
- the packing step is a step of packing the polysilicon crushed material with a resin packing material typified by polyethylene, and a known method is also used without particular limitation for such a packing method.
- the packing material made from polyethylene is used as a packing material
- the method of filling this with the polysilicon crushed material manually or using a filling apparatus is mentioned to this.
- shapes, such as a flat bag and a gusset bag, are generally employ
- the inside of the package is reduced in pressure or vacuum.
- the packaging bag may be double wrapped.
- the crushed silicon may come into contact with packing materials such as packaging bags and resin such as inspection gloves.
- the crushing process, the cleaning process, and the packing process are usually performed in a clean room, but are released from volatile organic substances that are slightly present in the clean room, for example, polyvinyl chloride curtains and flooring materials in the clean room.
- the crushed polysilicon is contaminated by the additive.
- the organic volatile component is removed from the polysilicon crushed material obtained in any of the above steps, and then the temperature of the polysilicon crushed material is increased under the flow of an inert gas. This is carried out by collecting the resin decomposition products generated in the above process and analyzing the decomposition products specific to the resin contained in the resin decomposition products, thereby specifying the type of resin adhered to the polysilicon crushed material.
- the heating temperature in removing these organic volatile components is preferably 180 ° C. or more in order to effectively remove the organic volatile components.
- the organic volatile component in the present invention means, for example, a low molecular weight compound that vaporizes at a normal pressure of 250 ° C. or lower.
- the upper limit of the heating temperature is set to be lower than the decomposition start temperature of the resin having the lowest decomposition temperature among the resins expected to adhere to the crushed polysilicon in the above process. Accordingly, the heating temperature may be, for example, 300 ° C. or lower, 280 ° C. or lower, 250 ° C. or lower, or 200 ° C. or lower. At low temperature, it is held for a sufficient time to remove organic volatile components.
- the organic volatile component in the present invention does not include a resin component.
- the heating for removing the organic volatile component is performed in an inert gas atmosphere such as helium gas, argon gas, nitrogen gas or the like in order to prevent the attached resin from burning.
- an inert gas atmosphere such as helium gas, argon gas, nitrogen gas or the like.
- helium is most preferable as the inert gas.
- a furnace having a mechanism for heating the crushed polysilicon to a predetermined temperature and a mechanism for extracting the vaporized organic volatile component is used. Is done.
- the extraction is preferably performed using the inert gas as a carrier gas.
- a closed furnace equipped with an external heater and heating means such as high-frequency heating and having an inert gas supply port and a gas discharge port is preferably used.
- the polysilicon crushed material may be stored in a setter and set in the furnace.
- the setter is made of a material that is stable even at a heating temperature for removing the organic volatile component, preferably at a heating temperature for decomposition of the subsequent resin, for example, heat-resistant ceramics such as quartz and alumina.
- heat-resistant ceramics such as quartz and alumina.
- the setter or the furnace is pre-baked at a temperature equal to or higher than the maximum heating temperature in the analysis.
- the apparatus having the above structure can also be used for heating for subsequent decomposition of the resin. Generally, after the organic volatile component is removed, the temperature is continuously raised to the decomposition temperature of the resin. Done.
- the heating time for removing the organic volatile component is preferably until the organic volatile component is substantially absent in the extracted gas, and generally 30 to 100 minutes is appropriate. Yes, at 250 ° C., 60 minutes or less is sufficient. By such heat treatment, 90% or more of organic volatile components adhering to the crushed polysilicon are removed.
- the higher the removal rate of organic volatile components the higher the sensitivity. Therefore, the organic volatile components are preferably removed by 95% or more, more preferably 97% or more, and particularly preferably 99% or more.
- the removal rate of organic volatile components is determined by the following method. That is, first, a measurement sample collected from crushed polysilicon is heated in a temperature range of 180 ° C.
- the generated organic volatile components are adsorbent. Adsorb to. Thereafter, the components separated by heating the adsorbent are measured with a GC / MS apparatus, and the peak areas of the organic volatile components adhering to the measurement sample are summed from the obtained chromatogram, and the peak areas of the organic volatile components attached to the measurement sample Find the area value (A all ). Next, the same amount of another measurement sample is taken from the crushed polysilicon, and subjected to a heat treatment for removing the organic volatile component (n hours). The organic volatile component generated at that time is the same as described above.
- the peak area value of organic volatile components were removed by heating (an) determined from a n / a all, determine the removal rate of organic volatile components. At this time, record the time and the peak area value of the organic volatile component, create a calibration curve for obtaining the peak area value of the organic volatile component at any time for each heating temperature, from the heating temperature and the heating time, It is preferable to estimate the removal rate of organic volatile components. In actual operation, conditions until the peak of the organic volatile component is not detected may be obtained in advance, and the organic volatile component may be removed according to the condition.
- the polysilicon crushed material is heated to 250 ° C., the generated organic volatile components are adsorbed on the adsorbent, and then the adsorbent is heated to remove the desorbed components by GC / MS (quadrupole mass spectrometry type).
- GC / MS quadrature mass spectrometry type
- the crushed polysilicon material from which the organic volatile components have been removed is then raised in temperature of the polysilicon crushed material under the flow of an inert gas, and the resin decomposed material generated at the heating temperature is collected. .
- the heating temperature may be set to a temperature equal to or higher than the decomposition start temperature of the resin assumed in the manufacturing process of the crushed polysilicon product and less than a temperature at which the generated resin decomposition product is not further modified.
- the temperature is preferably set stepwise to a temperature 25 to 100 ° C. higher than the decomposition start temperature.
- the heating temperature is appropriately set according to the type of resin to be measured and the resin decomposition temperature. By setting the heating temperature according to each resin, it is possible to measure with high accuracy. Become.
- the heating time at the heating temperature is preferably performed until the generation of the decomposition product of the resin is substantially eliminated at the temperature for accurate determination. Such time is preferably determined appropriately by conducting an experiment in advance. According to confirmation by the present inventors, the heating time may be 30 minutes or more, and particularly 60 minutes is sufficient.
- the resin decomposition product obtained at the above heating temperature is collected and collected as a gas, and the contained decomposition product specific to the resin is analyzed.
- the inert gas is used as a carrier, the resin decomposed product is taken out as a gas, and this is collected by an adsorbent and used for analysis.
- the adsorbent used for collecting the decomposition product can be appropriately used depending on the target resin.
- Non-limiting specific examples include, in addition to polymer-based adsorbents such as Tenax TA, carbon-based adsorbents such as Carboxen 1000 (trade name: manufactured by Sigma-Aldrich), and Carbo Siveve SIII (trade name: Sigma-aldrich). Activated carbon).
- the adsorbent that adsorbs the organic volatile component and the adsorbent that adsorbs the resin decomposition product may be the same, or may be appropriately selected from the adsorbents described above.
- the column can be appropriately selected and used depending on the resin to be measured.
- a capillary column having a polysiloxane-based stationary phase such as ZB-1MS (trade name: manufactured by Agilent)
- a silica particle-based plot column for example, GC-GasPro (trade name: manufactured by Phenomenex)
- the length of the column is not limited as long as the above-mentioned resin decomposition product can be separated, and is preferably 20 to 60 m, more preferably 30 m or more.
- a known method can be adopted as a method for desorbing and analyzing the decomposition product of the resin from the adsorbent.
- a general method is a method in which a resin decomposed product desorbed by heating the adsorbent is concentrated and collected in a cooled secondary adsorbent in the GC apparatus and introduced into the column after the heat desorption of the secondary adsorbent. .
- the kind of resin adhered to the polysilicon crushed material is specified from the analysis result of the resin decomposed material obtained at each heating temperature.
- Table 2 below shows typical decomposition products specific to the resin, and is attached to the crushed polysilicon by comparing the compounds identified by the above analysis with the following decomposition products specific to the resin.
- the resin can be specified.
- the adhered resin can be similarly identified from the decomposition product.
- preferable decomposition products for the determination of each resin are 1-pentadecene for polyethylene, 2-isocyanate-1,3-bis (1-methylethyl) benzene for polyurethane, and 2,4-dimethyl- for polypropylene.
- a calibration curve for a unique characteristic decomposition product can be created for each resin, and the amount of adhered resin can be obtained based on the calibration curve.
- FIG. 2 shows that 200 ⁇ g of polyethylene as a resin is weighed, a resin decomposition product generated when the temperature is raised from 250 ° C. to 450 ° C. is adsorbed to the adsorbent, and then the adsorbent is heated to remove components separated by the GC / MS apparatus. It is an example of the chromatogram measured by. 5) From the chromatographic chart, obtain the peak area value of the degradation product characteristic of the resin. 6) The above measurements are performed on the resin samples having different weights, and the peak area value of the decomposition product characteristic of the resin is obtained.
- a graph of “resin weight” and “peak area value of characteristic decomposition product” is created, and a slope and R 2 are obtained from a linear approximation expression without an intercept.
- R 2 is a coefficient of determination, and is used as a measure of the goodness of fit of the linear approximate expression obtained from the sample value. 8) If R 2 is less than 0.9, the plot is increased by changing the weight of the resin sample until R 2 becomes 0.9 or more, and a calibration curve is obtained.
- the type of resin adhering to the surface of the crushed polysilicon can be identified with higher sensitivity, and the amount of adhering resin can be accurately determined for each type of resin. Is possible. Therefore, the following examination was performed to confirm the accuracy of quantification.
- a rod-shaped polycrystalline silicon having a diameter of 150 mm and a length of 1000 mm manufactured by the Siemens method is placed on a crushing table lined with silicon in a clean room, and crushed with a tungsten carbide hammer, A polysilicon crushed material containing 95% by weight of crushed material having a maximum piece length of 10 mm to 100 mm was obtained.
- the material of the gloves used for handling was polyurethane. Twenty pieces of the obtained crushed polysilicon, about 500 g, are taken out, and a polyethylene piece as a resin is weighed into the crushed material so that it becomes 100 ppbw per weight of the crushed polysilicon. Held on.
- the resin decomposition product generated when the temperature is raised from 250 ° C. to 450 ° C. is adsorbed to the adsorbent, and then The components separated by heating the adsorbent were measured with a GC / MS apparatus.
- the crushed polysilicon material containing the polyethylene piece is adsorbed to the adsorbent by the resin decomposition product generated when the temperature is raised directly to 450 ° C. without desorbing organic volatile components, and then the adsorbent is heated.
- the component released after the measurement was measured with a GC / MS apparatus. In addition, this operation was performed 5 times in each condition in order to confirm reproducibility.
- the adhering polyethylene was quantified using a calibration curve obtained in advance, and it was confirmed that any sample from which organic volatile components were desorbed could be quantified with a high accuracy of 90 to 110 ppbw.
- the peaks specific to polyethylene could be confirmed, there were samples in which the peaks of the organic volatile components overlapped and could not be separated. Further, the quantified value was greatly varied from 90 to 300 ppbw.
- the type of the resin adhering to the surface of the crushed polysilicon can be specified with higher sensitivity, and the amount of the adhering resin can be accurately obtained for each type of the resin. It was.
- the outline of the present invention is as follows. (1) After removing organic volatile components from the crushed polysilicon, raise the temperature of the crushed polysilicon under the flow of inert gas, collect the resin decomposed material generated at the heating temperature, A method for analyzing surface impurities of a crushed polysilicon product, wherein the kind of resin adhered to the crushed polysilicon product is specified by analyzing a decomposed product unique to the resin contained in the resin decomposed product.
- Heating device The muffle furnace which connected the gas flow path to the heating device was used.
- a quartz container was used as a setter for storing the crushed polysilicon.
- Tenax TA which is a polymer-based adsorbent, was used to collect degradation products of polyethylene, polyurethane, polypropylene, and PEEK.
- Carboxene 1000 was used to collect PTFE and PVDF degradation products.
- the heating temperature was 250 ° C. for the purpose of removing organic volatile components, and was maintained for 49 minutes. Further, heating for the purpose of decomposing the adhered resin was performed at 400 to 650 ° C., and held at the temperature described in the examples described later for 49 minutes.
- Helium is used as a carrier gas and aerated at a flow rate of 100 mL / min. The heating conditions are summarized in Table 3 below.
- Example 1 As a crushing process, rod-shaped polycrystalline silicon with a diameter of 150 mm and a length of 1000 mm manufactured by the Siemens method is placed on a crushing table lined with silicon and crushed with a tungsten carbide hammer. A polysilicon crushed material containing 95% by weight of crushed material having a length of 10 to 110 mm was obtained. Polyethylene gloves were used for handling.
- Example 2 In the above-described cleaning process, the material of the cleaning basket was changed to polypropylene, and the same conditions as in Example 1 were performed. The results are shown in Table 5.
- Example 3 In the above-described cleaning process, the material of the cleaning basket was changed to PTFE, and the heating temperature was held at 400 ° C. for 49 minutes, and then, further maintained at 650 ° C. for 49 minutes. . The results are shown in Table 5.
- Example 4 In the crushing step, the same conditions as in Example 1 were used except that the material of the gloves used for handling was changed to polyurethane. The results are shown in Table 5.
- Example 5 In the above crushing process, after crushing with a hammer, the crushed material with a maximum piece length of 10 mm to 110 mm is classified into a maximum piece length of 10 mm to 30 mm with a PEEK sieve, held at a heating temperature of 400 ° C. for 49 minutes, and then further 650 Except for holding at 49 ° C. for 49 minutes, it was carried out under the same conditions as in Example 1 except that. The results are shown in Table 5.
- Example 6 In Example 1 above, after crushing with a hammer to obtain a crushed polysilicon material containing 95% by weight of a crushed material having a maximum piece length of 10 mm to 110 mm, directly into the polyethylene packaging bag without manual cleaning. The test was performed under the same conditions as in Example 1 except that The results are shown in Table 5.
- Comparative Example 1 As a comparative example, the polysilicon crushed material that has undergone the crushing process, the cleaning process, and the packing process shown in Example 1 is held in a quartz chamber in a heating apparatus, and they are not subjected to the removal operation of organic volatile components, and helium gas The mixture was held at 400 ° C. for 49 minutes in an atmosphere with a flow rate of 100 mL / min, and the generated resin decomposition product was collected and an analysis chart was obtained in the same manner as in Example 1. However, as shown in Table 5, polyethylene could not be separated due to overlap of organic volatile components and peaks, and accurate quantification was not possible. Further, PVDF was buried in noise and no peak could be detected.
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Abstract
Description
本発明において、分析の対象となるポリシリコン破砕物は、シーメンス法にて製造されたロッド状の多結晶シリコンを破砕して得られるものであり、かかる破砕工程を含む、以下に示す代表的な処理工程、即ち、(a)破砕工程、(b)洗浄工程、(c)梱包工程のうち、任意の工程を経た状態のものを全て含む。
多結晶シリコンは、シーメンス法や流動床法等で製造されるが、その中でもシーメンス法で得られる多結晶シリコンは、通常棒状で得られるため、例えば、単結晶シリコン製造用の坩堝に投入し易いよう、この棒状の多結晶シリコンは、必要に応じて切断された後、適当な大きさに破砕される。上記破砕は、例えば、ジョークラッシャー、ロールクラッシャーなどの破砕機で破砕したり、ハンマー又はタガネを用いて手作業で破砕したりすることにより、ポリシリコン破砕物に加工される。
破砕工程より得られたポリシリコン破砕物は、破砕時や取り扱い時に表面に付着する金属、油類等を除去してポリシリコン破砕物を清浄化する工程であり、公知の方法が特に制限無く採用される。例えば、酸液による酸洗工程と、その後の純水による水洗工程とを備えたものが挙げられる。酸洗工程では、予めポリシリコン破砕物を保持した洗浄カゴを、酸液を含む薬液槽に浸漬させることで、ポリシリコン破砕物の表面を溶解して汚染物質を除去する。酸洗工程で用いられる酸液としては、フッ化水素酸と硝酸との混合液が挙げられる。酸洗工程の後の水洗工程においては、超純水を使用することが好ましい。超純水で洗浄した後の多結晶シリコンは、送風乾燥(通気乾燥)により、乾燥させることが好ましく、この乾燥は80~150℃の温度で、0.5~24時間行うことが好ましい。
梱包工程は、ポリエチレンを代表とする樹脂製梱包材でポリシリコン破砕物を包装する工程であり、かかる包装方法も、公知の方法が特に制限無く採用される。例えば、梱包材として、ポリエチレン製の包装袋を使用し、これに、ポリシリコン破砕物を、手作業により、または、充填装置を使用して充填する方法が挙げられる。上記包装袋としては、平袋、ガゼット袋などの形状が一般に採用され、また、袋を二重とした二重袋構造などが好適に使用される。また、ポリシリコン破砕物と梱包材との擦れや破損を抑制する為に、上記包装体内を減圧もしくは真空とすることも好ましい態様である。梱包袋が二重による包装をしても良い。
本発明の分析方法は、上記いずれかの工程において得られたポリシリコン破砕物より有機揮発成分を除去した後、不活性ガスの流通下、該ポリシリコン破砕物の温度を上昇せしめ、上記加熱温度において発生する樹脂分解物を捕集して、該樹脂分解物に含まれる前記樹脂固有の分解物を分析することにより、前記ポリシリコン破砕物の付着樹脂の種類を特定することにより実施される。
この際に、時間と有機揮発成分のピーク面積値とを記録し、加熱温度毎に任意の時間における有機揮発成分のピーク面積値を求める検量線を作成しておき、加熱温度と加熱時間から、有機揮発成分の除去率を見積もることが好ましい。また、実際の操業においては、有機揮発成分のピークが検出されなくなるまでの条件を予め求めておき、その条件に準じて、有機揮発成分の除去を行っても良い。
5)クロマトグラフのチャートより、樹脂に特徴的な分解物のピーク面積値を求める。
6)前記重量の異なる樹脂試料について、上記測定をそれぞれ行い、上記樹脂に特徴的な分解物のピーク面積値を求める。
7)「樹脂重量」と「特徴的な分解物のピーク面積値」のグラフを作り、切片を持たない線形近似式から傾きとR2を求める。なお、R2は決定係数であり、標本値から求めた線形近似式のあてはまりの良さの尺度として利用される。
8)R2が0.9未満であれば、R2が0.9以上になるまで樹脂試料の重量を変えて前記操作を行うことによりプロットを増やし、検量線を得る。
前記の通り、本発明の方法によれば、ポリシリコン破砕物の表面に付着する樹脂の種類をより感度よく特定することができ、また、上記樹脂の種類毎に付着樹脂量を正確に求めることが可能となる。そこで、定量の正確性を確認する為に以下の検討を行った。
(1)ポリシリコン破砕物より有機揮発成分を除去した後、不活性ガスの流通下、該ポリシリコン破砕物の温度を上昇せしめ、上記加熱温度において発生する樹脂分解物を捕集して、該樹脂分解物に含まれる前記樹脂固有の分解物を分析することにより、前記ポリシリコン破砕物の付着樹脂の種類を特定することを特徴とするポリシリコン破砕物の表面不純物の分析方法。
さらに、本発明は以下のように記述することもできる。
ポリシリコン破砕物から有機揮発成分を除去し、
不活性ガスの流通下、該ポリシリコン破砕物を加熱して、付着樹脂を分解し、該樹脂分解物を捕集し、
該樹脂分解物に含まれる前記樹脂固有の分解物を分析し、
前記ポリシリコン破砕物の付着樹脂の種類を特定することを含む、ポリシリコン破砕物の表面不純物の分析方法。
加熱装置にガス流路を接続したマッフル炉を用いた。ポリシリコン破砕物を収容するセッターには石英製容器を用いた。吸着剤は、ポリエチレン、ポリウレタン、ポリプロピレン、PEEKの分解物の捕集にポリマー系吸着剤であるTenax TAを用いた。また、PTFE、PVDFの分解物の捕集にCarboxene 1000を用いた。加熱温度は、有機揮発成分の除去を目的とする加熱を250℃で行い、49分保持した。また、付着樹脂の分解を目的とする加熱を400~650℃で行い、後述する実施例に記載の温度で49分保持した。ヘリウムをキャリアガスとして、流量100mL/minで通気する。加熱条件を以下表3にまとめた。
分析装置に四重極質量分析型のGC/MSを用いた。ポリエチレン、ポリウレタン、ポリプロピレン、PEEKの分解物の分析カラムには、シロキサンポリマー系の一般的なキャピラリーカラムのZB-1MSを採用した。PTFE、PVDFの分解物の分析カラムには、分解物が低沸点化合物であることから、低沸点成分の分離に優れたシリカ粒子系のプロットカラムのGC-GasProを採用した。分析条件を以下表4にまとめた。
シーメンス法にて製造された直径150mm、長さ1000mmのロッド状の多結晶シリコンを、破砕工程として、シリコンにてライニングされた破砕台の上に乗せ、タングステンカーバイド製のハンマーにて破砕し、最大片長10mm~110mmの破砕物を95重量%含むポリシリコン破砕物を得た。ハンドリングにはポリエチレンの手袋を使用した。
上記、洗浄工程にて、洗浄カゴの材質をポリプロピレンに変更し、実施例1と同様の条件で実施した。結果を表5に示す。
上記、洗浄工程にて、洗浄カゴの材質をPTFEに変更し、加熱温度を400℃で49分保持した後、更に650℃で49分保持した以外は、実施例1と同様の条件で実施した。結果を表5に示す。
上記、破砕工程にて、ハンドリングする際の手袋の材質をポリウレタンに変更した以外は、実施例1と同様の条件で実施した。結果を表5に示す。
上記、破砕工程にて、ハンマーによる破砕後に、PEEKの篩にて、最大片長10mm~110mmの破砕物を最大片長10mm~30mmに分類し、加熱温度が400℃で49分保持した後、更に650℃にて49分保持した以外は、以外は実施例1と同様の条件で実施した。結果を表5に示す。
上記、実施例1において、ハンマーにて破砕し、最大片長10mm~110mmの破砕物を95重量%含むポリシリコン破砕物を得た後、洗浄工程を行わず、直接ポリエチレンの梱包袋へ手作業にて投入した以外は、実施例1と同様の条件で実施した。結果を表5に示す。
比較例として、実施例1に示す破砕工程、洗浄工程、梱包工程を経たポリシリコン破砕物を、加熱装置内の石英チャンバー内に保持し、それらを有機揮発成分の除去操作を行わず、ヘリウムガス、流量100mL/minの雰囲気下にて400℃で49分保持し、実施例1と同様にして、発生する樹脂分解物を捕集、分析チャートを得た。しかし、表5に示すとおり、ポリエチレンは有機揮発成分とピークが重複して分離ができず、正確な定量ができなかった。また、PVDFはノイズに埋もれてピークが検出できなかった。
Claims (4)
- ポリシリコン破砕物より有機揮発成分を除去した後、不活性ガスの流通下、該ポリシリコン破砕物の温度を上昇せしめ、上記加熱温度において発生する樹脂分解物を捕集して、該樹脂分解物に含まれる前記樹脂固有の分解物を分析することにより、前記ポリシリコン破砕物の付着樹脂の種類を特定することを特徴とするポリシリコン破砕物の表面不純物の分析方法。
- 前記有機揮発成分の除去を、180℃以上、該ポリシリコン破砕物の製造工程においてポリシリコンとの接触が想定される樹脂の分解開始温度未満の温度に維持して行う請求項1記載の分析方法。
- 前記ポリシリコン破砕物の温度の上昇を樹脂分解開始温度に応じて段階的に行う、請求項1又は請求項2に記載の分析方法。
- 前記樹脂固有の分解物についてそれぞれ検量線を作成し、該検量線に基づいて前記付着樹脂毎の付着量を定量する請求項1~3のいずれか一項に記載の分析方法。
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WO2021182341A1 (ja) * | 2020-03-12 | 2021-09-16 | グローバルウェーハズ・ジャパン株式会社 | シリコン原料の洗浄装置 |
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