TW201718402A - Carbon analysis method - Google Patents
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- TW201718402A TW201718402A TW105123904A TW105123904A TW201718402A TW 201718402 A TW201718402 A TW 201718402A TW 105123904 A TW105123904 A TW 105123904A TW 105123904 A TW105123904 A TW 105123904A TW 201718402 A TW201718402 A TW 201718402A
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- carbon
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- hydrolyzate
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000004458 analytical method Methods 0.000 title claims abstract description 45
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 150000001721 carbon Chemical class 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- -1 metal halide compound Chemical class 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910001507 metal halide Inorganic materials 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 10
- 239000012433 hydrogen halide Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 28
- 230000007062 hydrolysis Effects 0.000 description 22
- 238000006460 hydrolysis reaction Methods 0.000 description 22
- 239000007787 solid Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- NYGCGFAXOYRSPR-UHFFFAOYSA-N 1,1,1-trichloroundecane Chemical compound CCCCCCCCCCC(Cl)(Cl)Cl NYGCGFAXOYRSPR-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KEPBYTKEUAZWQU-UHFFFAOYSA-N ClC(C(C)(C)Cl)CCCCCCCC Chemical compound ClC(C(C)(C)Cl)CCCCCCCC KEPBYTKEUAZWQU-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 4
- FVQJFPXYHWKHSC-UHFFFAOYSA-N 3-chloro-2,2-dimethylundecane Chemical compound CCCCCCCCC(Cl)C(C)(C)C FVQJFPXYHWKHSC-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YMEKHGLPEFBQCR-UHFFFAOYSA-N 2,2,3,3,5,5-hexachloro-1,4-dioxane Chemical compound ClC1(OC(C(OC1)(Cl)Cl)(Cl)Cl)Cl YMEKHGLPEFBQCR-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- YDJYMOXHELOFST-UHFFFAOYSA-N trichloromethylhydrazine Chemical compound NNC(Cl)(Cl)Cl YDJYMOXHELOFST-UHFFFAOYSA-N 0.000 description 2
- FRGJFERYCDBOQD-UHFFFAOYSA-N 1,1,1,2-tetrachlorodecane Chemical compound CCCCCCCCC(Cl)C(Cl)(Cl)Cl FRGJFERYCDBOQD-UHFFFAOYSA-N 0.000 description 1
- TXQJIMNDEHCONN-UHFFFAOYSA-N 3-(2-methoxyphenoxy)propanoic acid Chemical compound COC1=CC=CC=C1OCCC(O)=O TXQJIMNDEHCONN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WCKWXPBDKSOVOK-UHFFFAOYSA-H hexachlororuthenium Chemical compound Cl[Ru](Cl)(Cl)(Cl)(Cl)Cl WCKWXPBDKSOVOK-UHFFFAOYSA-H 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KBSJJSOGQSGFRD-UHFFFAOYSA-K trichlorotungsten Chemical compound Cl[W](Cl)Cl KBSJJSOGQSGFRD-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Combustion & Propulsion (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Silicon Compounds (AREA)
Abstract
Description
本發明係關於對含有具有水解性鹵素之鹵化金屬化合物之原料中所含之碳量進行分析之方法。 The present invention relates to a method for analyzing the amount of carbon contained in a raw material containing a halogenated metal compound having a hydrolyzable halogen.
半導體領域中，由於元件之微細化進展，故對於製造製程中使用之氣體的原料之液體材料要求更高純度化。迄今，作為液體材料中所含之雜質係針對金屬成分進行充分管理。 In the field of semiconductors, the liquid material of the raw material for the gas used in the manufacturing process is required to be more purified due to the progress of the miniaturization of components. Heretofore, the impurities contained in the liquid material have been sufficiently managed for the metal component.
然而，日本特開2007-5365號公報中，記載藉由使用具有特定構造之含矽之化合物的氣體與含金屬之化合物的氣體之原子層蒸鍍法，於基板上形成由金屬矽酸鹽構成之高介電率膜之方法中，於製造製程中使用之材料中含有較多碳時，容易於高介電率膜中殘留碳而發生洩漏電流，因此作為抑制洩漏電流發生之手段，使用碳原子對於矽原子之組成比被規定的材料之方法。 However, Japanese Laid-Open Patent Publication No. 2007-5365 discloses that an atomic layer vapor deposition method using a gas of a compound having a specific structure and a metal-containing compound is used to form a metal niobate on a substrate. In the method of the high dielectric film, when a material used in the manufacturing process contains a large amount of carbon, it is easy to cause a residual current in the high dielectric film and a leakage current occurs. Therefore, carbon is used as a means for suppressing leakage current. The method by which an atom is a specified material for the composition of a helium atom.
又，日本特開2014-67829號公報中，為了獲得洩漏電流少之層間絕緣膜，記載有半導體用絕緣材料，其特徵係使用碳原子對於矽原子之組成比被規定的材料。 Japanese Laid-Open Patent Publication No. 2014-67829 discloses an insulating material for a semiconductor in order to obtain an interlayer insulating film having a small leakage current, and is characterized in that a material having a composition ratio of carbon atoms to germanium atoms is used.
如此，源自半導體製造製程所使用之原料中所含之雜質等之碳量之管理變得必要。 In this way, management of the amount of carbon derived from impurities and the like contained in the raw materials used in the semiconductor manufacturing process is necessary.
另一方面，作為測定碳量之方法，於日本特開平11-281541號公報中，作為於燃料電池用各種金屬製零件及陶瓷製零件上附著殘留之油分的分析方法，記載有使構成油分之烴類與氧反應轉換成一氧化碳或二氧化碳，以紅外線檢測器對其進行測定而求出碳量之分析方法。 On the other hand, as a method of analyzing the amount of the oil, the method of analyzing the oil component remaining on various metal parts and ceramic parts for fuel cells is described in Japanese Laid-Open Patent Publication No. H11-281541. A method in which a hydrocarbon is converted into carbon monoxide or carbon dioxide by reaction with oxygen and measured by an infrared detector to determine the amount of carbon.
又，日本特開2002-122581號公報中，記載使附著於金線之有機物於高溫熱分解，以熱分解氣體層析裝置測定生成之甲烷與乙烯而定量全碳量之方法。 Japanese Laid-Open Patent Publication No. 2002-122581 discloses a method of quantifying the total amount of carbon by measuring the generated methane and ethylene by a thermal decomposition gas chromatography apparatus by thermally decomposing the organic substance adhering to the gold wire at a high temperature.
進而，於日本特開2006-28035號公報中，作為使用氣體層析分析碳之方法，揭示有以甲烷轉化劑處理試料，以氫還原試料中所含之一氧化碳、二氧化碳及有機化合物等，將碳轉換成甲烷，以氣體層析檢測該甲烷，而定量碳之方法。 Further, in JP-A-2006-28035, a method of analyzing carbon by gas chromatography reveals that a sample treated with a methane conversion agent is used to reduce carbon monoxide, carbon dioxide, and an organic compound contained in a sample by hydrogen reduction. A method of converting to methane, detecting the methane by gas chromatography, and quantifying carbon.
日本特開平11-281541號公報中記載之碳的定量方法，稱為燃燒紅外線吸收法，即使液體試料亦可分析，碳之檢測極限亦達至1質量ppm，為優異之碳的定量方法。然而，以該方法使含碳原子之鹵化金屬化合物原料燃燒，以日本特開2002-122581號公報之方法使含碳原子之鹵化金屬化合物原料熱分解時，由於有發生鹵素氣體或 鹵化氫氣體而腐蝕分析裝置之金屬部之虞，因此難以藉由燃燒紅外線吸收法或熱分解氣體層析定量鹵化金屬化合物原料所含之碳。 The method for quantifying carbon described in Japanese Laid-Open Patent Publication No. H11-281541 is called a combustion infrared absorption method. Even if the liquid sample can be analyzed, the detection limit of carbon is as high as 1 ppm by mass, which is an excellent method for quantifying carbon. However, in this method, the halogenated metal compound raw material containing a carbon atom is burned, and when the halogenated metal compound raw material containing a carbon atom is thermally decomposed by the method of JP-A-2002-122581, a halogen gas is generated or Since the hydrogen halide gas corrodes the metal portion of the analysis device, it is difficult to quantify the carbon contained in the halogenated metal compound raw material by combustion infrared absorption or thermal decomposition gas chromatography.
又，使用國際公開2006-28035號公報中記載之甲烷轉化劑將試料中之碳轉化成甲烷之方法，若應用於含碳原子之鹵化金屬化合物原料時，會以副產物生成腐蝕性高的鹵化氫或鹵素氣體。因此，由於例如使由鎳化合物等所成之還原觸媒失活，並發生分析裝置之金屬部的腐蝕，故難以使用甲烷轉化劑。進而，以氫使鹵化金屬化合物的氯化矽烷類還原時，由於成為起火或***等之反應性高的金屬氫化物的矽烷類，故亦有鹵化金屬化合物原料之分析作業危險性變得非常高的問題。 Moreover, the method of converting the carbon in the sample into methane by using the methane conversion agent described in International Publication No. 2006-28035, when applied to a halogenated metal compound raw material containing a carbon atom, generates a highly corrosive halogenation by-product. Hydrogen or halogen gas. Therefore, for example, the reduction catalyst formed of a nickel compound or the like is deactivated, and corrosion of the metal portion of the analysis device occurs, so that it is difficult to use a methane conversion agent. Further, when the chloroalkylene of the halogenated metal compound is reduced by hydrogen, the hydride of the metal hydride having high reactivity such as ignition or explosion is also caused, and the risk of analysis of the metal halide compound raw material is extremely high. The problem.
本發明之目的在於提供並無裝置之腐蝕或作業危險性之安全方法，且對含有具有水解性之鹵化金屬化合物與源自雜質等之有機成分之原料中所含之碳、或具有水解性且含有鹵原子及碳原子之金屬化合物中所含之碳進行定量之方法。 It is an object of the present invention to provide a safe method which does not have corrosion or work hazard of a device, and which is hydrolyzable or contained in a raw material containing a hydrolyzable metal halide compound and an organic component derived from impurities or the like. A method of quantifying carbon contained in a metal compound containing a halogen atom and a carbon atom.
本發明人等為解決上述課題而積極檢討之結果，發現利用鹵化金屬化合物之水解，可效率良好地對含有具有水解性之鹵化金屬化合物與源自雜質等之有機成分之原料中所含之碳、或具有水解性且含有鹵原子及碳原子之金屬化合物中所含之碳進行定量，因而完成本發明。 As a result of the active review of the above-mentioned problems, the inventors of the present invention have found that carbon contained in a raw material containing a hydrolyzable metal halide compound and an organic component derived from impurities can be efficiently used by hydrolysis of a metal halide compound. The carbon contained in the metal compound having hydrolyzability and containing a halogen atom and a carbon atom is quantified, and thus the present invention has been completed.
本發明係以下之第1發明及第2發明。 The present invention is the first invention and the second invention described below.
第1發明係一種碳分析方法，其特徵係將含有具有水解性之鹵化金屬化合物(以下稱為「鹵化金屬化合物(P)」)及有機成分之原料與水混合，使上述鹵化金屬化合物(P)水解，形成水解物後，回收該水解物及上述有機成分之混合物，藉由該混合物之碳分析獲得碳量。 The first invention is a carbon analysis method characterized in that a raw material containing a hydrolyzable metal halide compound (hereinafter referred to as "halogenated metal compound (P)") and an organic component is mixed with water to form the above-mentioned halogenated metal compound (P). After hydrolysis to form a hydrolyzate, the hydrolyzate and the mixture of the above organic components are recovered, and the amount of carbon is obtained by carbon analysis of the mixture.
第1發明中，較好上述水係全有機碳之含量為500ppb以下之純水。 In the first invention, it is preferred that the water-based total organic carbon content is 500 ppb or less of pure water.
第1發明中，較好構成上述鹵化金屬化合物(P)之金屬原子為矽原子、鍺原子或鎢原子，上述鹵原子為氯原子。 In the first invention, the metal atom of the halogenated metal compound (P) is preferably a ruthenium atom, a ruthenium atom or a tungsten atom, and the halogen atom is a chlorine atom.
第1發明中，較好獲得上述水解物時副生之鹵化氫係藉由30~180℃之加熱而去除。 In the first invention, it is preferred that the hydrogen halide which is by-produced when the hydrolyzate is obtained is removed by heating at 30 to 180 °C.
第1發明中，上述水解物為液體時，較好上述鹵化金屬化合物(P)係擔持於擔體上而使用。 In the first aspect of the invention, when the hydrolyzate is a liquid, the halogenated metal compound (P) is preferably used by being supported on a support.
第2發明係一種碳分析方法，其特徵係將具有水解性且含有鹵原子及碳原子之金屬化合物(以下稱為「鹵化金屬化合物(Q)」)藉由水予以水解，形成含上述碳原子之水解物後，碳分析該水解物而獲得碳量。 The second invention is a carbon analysis method characterized in that a metal compound having a hydrolyzable property and containing a halogen atom and a carbon atom (hereinafter referred to as "halogenated metal compound (Q)") is hydrolyzed by water to form a carbon atom-containing compound. After the hydrolyzate, carbon is analyzed for the amount of carbon.
第2發明中，較好上述水係全有機碳之含量為500ppb以下之純水。 In the second aspect of the invention, it is preferred that the water-based total organic carbon content is 500 ppb or less of pure water.
第2發明中，較好構成上述鹵化金屬化合物(Q)之金屬原子為矽原子或鍺原子，上述鹵原子為氯原子。 In the second aspect of the invention, the metal atom of the halogenated metal compound (Q) is preferably a ruthenium atom or a ruthenium atom, and the halogen atom is a chlorine atom.
第2發明中，較好獲得上述水解物時副生之鹵化氫係 藉由30~180℃之加熱而去除。 In the second invention, it is preferred to obtain a by-produced hydrogen halide system when the hydrolyzate is obtained. It is removed by heating at 30 to 180 °C.
第2發明中，上述水解物為液體時，較好上述鹵化金屬化合物(Q)係擔持於擔體上而使用。 In the second aspect of the invention, when the hydrolyzate is a liquid, the halogenated metal compound (Q) is preferably used by being supported on a support.
依據本發明之碳分析方法，由於生成之水解物不含有鹵素成分，故可使用以往之定量方法效率良好地分析碳量。而且，可避免碳分析裝置之金屬部之腐蝕等。依據第1發明，可獲得源自作為雜質等所含之有機成分的碳量，於鹵化金屬化合物(P)為含碳原子之化合物時，可獲得與源自作為雜質等所含之有機成分的碳量之合計碳量。且，依據第2發明，可獲得分析對象之鹵化金屬化合物(Q)之碳量。 According to the carbon analysis method of the present invention, since the produced hydrolyzate does not contain a halogen component, the amount of carbon can be efficiently analyzed using a conventional quantitative method. Moreover, corrosion of the metal portion of the carbon analysis device or the like can be avoided. According to the first aspect of the invention, the amount of carbon derived from an organic component contained as an impurity or the like can be obtained. When the halogenated metal compound (P) is a compound containing a carbon atom, it can be obtained from an organic component contained as an impurity or the like. The total amount of carbon in the amount of carbon. Further, according to the second invention, the amount of carbon of the halogenated metal compound (Q) to be analyzed can be obtained.
以下針對本發明詳細說明。 The invention is described in detail below.
本發明之分析對象係有必要進行碳量管理、於半導體等之製造所用之含有鹵原子與鍵結於該鹵原子之金屬原子之可水解之鹵化金屬化合物(P)或(Q)為主之原料。又，「具有水解性」及「可水解」意指藉由對象化合物與水之反應，而發生鹵化氫並形成水解物。 The object of analysis of the present invention is that it is necessary to carry out carbon amount management, and a hydrolyzable halogenated metal compound (P) or (Q) containing a halogen atom and a metal atom bonded to the halogen atom used in the manufacture of a semiconductor or the like is mainly used. raw material. Further, "hydrolyzable" and "hydrolyzable" mean that a hydrogen halide is generated by a reaction of a target compound with water to form a hydrolyzate.
作為水解性鹵原子舉例為氯原子、氟原子等。該等中，較好為氯原子。且構成鹵化金屬化合物(P)或(Q)之金屬原子舉例為矽原子、鈦原子、鍺原子、鋯原 子、鉬原子、錫原子、鉿原子、鎢原子等，該等中較好為矽原子、鍺原子或鎢原子。 The hydrolyzable halogen atom is exemplified by a chlorine atom, a fluorine atom or the like. Among these, a chlorine atom is preferred. And the metal atom constituting the metal halide compound (P) or (Q) is exemplified by a ruthenium atom, a titanium atom, a ruthenium atom, and a zirconium atom. A child, a molybdenum atom, a tin atom, a germanium atom, a tungsten atom or the like is preferably a germanium atom, a germanium atom or a tungsten atom.
上述鹵化金屬化合物(P)及(Q)可為固體及液體之任一者。 The above halogenated metal compounds (P) and (Q) may be either solid or liquid.
第1發明所用之鹵化金屬化合物(P)為含鹵原子及金屬原子且亦可含碳原子之化合物。本發明中，較好為具有鹵原子及金屬原子之鍵、或鹵原子及金屬原子之鍵及碳原子及金屬原子之鍵之氯化矽化合物、氯化鍺化合物或氯化鎢化合物。碳原子較好作為烴基含有。作為氯化矽化合物，舉例為三氯甲基矽烷、二氯二甲基矽烷、氯三甲基矽烷、四氯矽烷、六氯二矽烷等。且，作為氯化鍺化合物舉例為三氯甲基鍺、三氯二甲胺基鍺、氯化鍺(II)、氯化鍺(IV)等。進而，作為氯化鎢化合物舉例為氯化鎢(III)、氯化鎢(IV)、氯化鎢(VI)等。又，四氯矽烷、六氯二矽烷、三氯甲基矽烷、二氯二甲基矽烷、氯三甲基矽烷等之氯矽烷化合物之水解物通常為聚矽氧烷。 The halogenated metal compound (P) used in the first invention is a compound containing a halogen atom and a metal atom and may also contain a carbon atom. In the present invention, a ruthenium chloride compound, a ruthenium chloride compound or a tungsten chloride compound having a bond of a halogen atom and a metal atom, a bond of a halogen atom and a metal atom, and a bond of a carbon atom and a metal atom is preferred. The carbon atom is preferably contained as a hydrocarbon group. Examples of the ruthenium chloride compound include trichloromethyl decane, dichlorodimethyl decane, chlorotrimethyl decane, tetrachloro decane, and hexachlorodioxane. Further, examples of the ruthenium chloride compound include trichloromethyl hydrazine, trichlorodimethylamino hydrazine, ruthenium (II) chloride, and ruthenium (IV) chloride. Further, examples of the tungsten chloride compound include tungsten (III) chloride, tungsten (IV) chloride, and tungsten (VI) chloride. Further, the hydrolyzate of a chlorodecane compound such as tetrachloromethane, hexachlorodioxane, trichloromethyl decane, dichlorodimethyl decane or chlorotrimethyl decane is usually a polyoxy siloxane.
第1發明所用之鹵化金屬化合物(P)可僅為1種，亦可為2種以上。 The halogenated metal compound (P) used in the first invention may be used alone or in combination of two or more.
上述鹵化金屬化合物(P)較好為包含由鹵原子及金屬原子所成之化合物。 The halogenated metal compound (P) preferably contains a compound composed of a halogen atom and a metal atom.
又，第2發明所用之鹵化金屬化合物(Q)為含鹵原子、碳原子及金屬原子之化合物。本發明中，較好為氯化矽化合物及氯化鍺化合物。作為氯化矽化合物，舉 例為三氯甲基矽烷、二氯二甲基矽烷、氯三甲基矽烷等等。且，作為氯化鍺化合物舉例為三氯甲基鍺、三氯二甲胺基鍺等。 Further, the halogenated metal compound (Q) used in the second invention is a compound containing a halogen atom, a carbon atom and a metal atom. In the present invention, a ruthenium chloride compound and a ruthenium chloride compound are preferred. As a ruthenium chloride compound, Examples are trichloromethyl decane, dichlorodimethyl decane, chlorotrimethyl decane and the like. Further, examples of the ruthenium chloride compound include trichloromethyl hydrazine, trichlorodimethylamino hydrazine, and the like.
第2發明所用之鹵化金屬化合物(Q)可僅為1種，亦可為2種以上。 The halogenated metal compound (Q) used in the second invention may be used alone or in combination of two or more.
第1發明中之有機成分通常為油分，係作為雜質等微量含有之成分。該有機成分之水解物由於對定量性不造成影響，故未特別限定。 The organic component in the first invention is usually an oil component and is contained as a component contained in a trace amount such as an impurity. The hydrolyzate of the organic component is not particularly limited because it does not affect the quantitative properties.
第1發明及第2發明中，首先，藉由水使含有鹵化金屬化合物(P)及有機成分之原料或鹵化金屬化合物(Q)水解。水並未特別限制，較好為純水。該純水中之全有機碳(TOC)含量較好為500質量ppm以下，更好為100質量ppm以下，特佳為50質量ppm以下(超純水)。 In the first invention and the second invention, first, the raw material containing the halogenated metal compound (P) and the organic component or the halogenated metal compound (Q) is hydrolyzed by water. The water is not particularly limited, and is preferably pure water. The total organic carbon (TOC) content in the pure water is preferably 500 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 50 ppm by mass or less (ultra-pure water).
水解較好係將比鹵化金屬化合物(P)或(Q)所含之鹵原子之當量更過量之水收容於乾淨容器中，於其中逐次少量添加鹵化金屬化合物(P)或(Q)。此時激烈發熱時，較好根據發熱程度使內容物冷卻。水解所需時間係隨鹵化金屬化合物(P)或(Q)之種類或量而定，但較好於約25℃放置24小時以上。 The hydrolysis is preferably carried out in a clean container in a larger excess amount than the equivalent of the halogen atom contained in the metal halide compound (P) or (Q), and the halogenated metal compound (P) or (Q) is added in small portions. At the time of intense heat generation, it is preferred to cool the contents according to the degree of heat generation. The time required for the hydrolysis depends on the kind or amount of the metal halide compound (P) or (Q), but is preferably placed at about 25 ° C for 24 hours or more.
水的使用量，基於水解反應性之觀點，相對於鹵化金屬化合物(P)或(Q)1質量份，較好為1~100質量份，更好為5~50質量份。 The amount of use of the water is preferably from 1 to 100 parts by mass, more preferably from 5 to 50 parts by mass, per part by mass of the metal halide compound (P) or (Q), from the viewpoint of the hydrolysis reactivity.
水的使用量未達1質量份時，有水解未充分進行之情 況。又，水的使用量過多時，有於後續步驟之水去除麻煩之情況。 When the amount of water used is less than 1 part by mass, hydrolysis is not sufficiently carried out. condition. Moreover, when the amount of water used is too large, there is a case where the water removal in the subsequent step is troublesome.
藉由上述之鹵化金屬化合物(P)或(Q)之水解獲得之水解物一般為固體，於水解後，其水相成為含氯化氫等之鹵化氫之懸浮液。由於該鹵化氫對於分析裝置帶來不良影響，故藉由在常壓或減壓下進行懸浮液之加熱乾燥與水一起去除，獲得適於分析之固體物質。 The hydrolyzate obtained by the hydrolysis of the above-mentioned halogenated metal compound (P) or (Q) is generally a solid, and after hydrolysis, the aqueous phase becomes a suspension of hydrogen halide containing hydrogen chloride or the like. Since the hydrogen halide adversely affects the analysis device, the solid matter suitable for analysis is obtained by subjecting the suspension to heating and drying under normal pressure or reduced pressure together with water.
第1發明中，水解後，水解物及有機成分之混合物通常可成為於水解物中包含有機成分之形態。又，第1發明之有機成分具有水解性時，可獲得鹵化金屬化合物(P)之水解物及上述有機成分之水解物之混合物。 In the first invention, after the hydrolysis, the mixture of the hydrolyzate and the organic component may be in the form of containing an organic component in the hydrolyzate. Further, when the organic component of the first invention has hydrolyzability, a mixture of the hydrolyzate of the metal halide compound (P) and the hydrolyzate of the organic component can be obtained.
作為上述加熱乾燥之條件的溫度，基於不使水解物變質，效率良好地去除鹵化氫，較好為30~180℃，更好為80~120℃。加熱溫度未達30℃時，乾燥不充分且殘留鹵化氫而有對分析裝置造成不良影響之可能性，又，乾燥溫度超過180℃時，使水解物中所包含之有機成分揮發、分解之可能性變高故而不佳。 The temperature of the heating and drying conditions is such that the hydrogen halide is efficiently removed without deteriorating the hydrolyzate, and is preferably from 30 to 180 ° C, more preferably from 80 to 120 ° C. When the heating temperature is less than 30 ° C, the drying is insufficient and the hydrogen halide remains, which may adversely affect the analyzer. When the drying temperature exceeds 180 ° C, the organic components contained in the hydrolyzate may be volatilized and decomposed. Sex is getting worse.
進而，加熱乾燥之氛圍並未特別限制，較好為惰性氣體氛圍。藉由設為惰性氣體氛圍，可促進水解物之乾燥，亦可抑制有機成分之氧化分解。作為惰性氣體較好使用氮氣。 Further, the atmosphere to be heated and dried is not particularly limited, and is preferably an inert gas atmosphere. By setting it as an inert gas atmosphere, drying of a hydrolyzate can be accelerated, and oxidative decomposition of an organic component can also be suppressed. Nitrogen is preferably used as the inert gas.
上述加熱乾燥較好以經水濕潤之pH試紙碰觸排氣，卻認為pH6以上及成為恆量時結束。 It is preferable that the above-mentioned heat drying is carried out by touching the exhaust gas with a water-wet pH test paper, but it is considered to be completed when the pH is 6 or more and becomes a constant amount.
隨後，藉由將回收物供於碳分析，可獲得碳量。 Subsequently, the amount of carbon can be obtained by supplying the recovered matter to carbon analysis.
又，藉由鹵化金屬化合物(P)之水解所得之水解物有時不成為固體。水解物為液體時，較好併用鹵化金屬化合物(P)與擔體。 Further, the hydrolyzate obtained by hydrolysis of the halogenated metal compound (P) may not become a solid. When the hydrolyzate is a liquid, the halogenated metal compound (P) and the support are preferably used in combination.
擔體並未特別限制，但為了對於隨後之分析不造成阻礙，較好使用由碳含量未達分析裝置之定量下限之化合物所成之粉體。作為上述擔體，可使用例如以氨使高純度之四乙氧基矽烷水解後，燒成而得之粒徑為0.3~3μm之氧化矽。尤其較好為以燃燒紅外線吸收法求出之碳量為0.003~未達0.001質量%之氧化矽。 The support is not particularly limited, but in order not to hinder the subsequent analysis, it is preferred to use a powder obtained from a compound having a carbon content which does not reach the lower limit of the quantitative value of the analyzer. As the above-mentioned support, for example, cerium oxide having a particle diameter of 0.3 to 3 μm obtained by hydrolyzing high-purity tetraethoxysilane with ammonia and then calcining it can be used. In particular, it is preferably a cerium oxide having a carbon content of 0.003 to less than 0.001% by mass calculated by a combustion infrared absorption method.
使用擔體時，係於容器中添加擔體與含鹵化金屬化合物(P)之原料，添加過量水進行水解。又，藉由預先分析擔體之碳量，可獲得正確之碳量。 When the support is used, the support and the raw material containing the halogenated metal compound (P) are added to the vessel, and excess water is added to carry out hydrolysis. Further, by analyzing the amount of carbon in the support in advance, the correct amount of carbon can be obtained.
上述擔體之使用量，基於作業性之觀點，相對於鹵化金屬化合物，較好為5~100質量份，更好為10~50質量份。 The amount of use of the above-mentioned support is preferably from 5 to 100 parts by mass, more preferably from 10 to 50 parts by mass, based on the workability.
併用獲得液體之水解物之鹵化金屬化合物(P)與擔體時，於水解後，獲得由水、液體之水解物、擔體與有機成分所成之混合液(懸浮液)。接著，使該混合液加熱乾燥時，獲得液體之水解物及有機成分附著於擔體之複合物。 When the halogenated metal compound (P) and the support which obtain the hydrolyzate of the liquid are used together, after the hydrolysis, a mixed liquid (suspension) composed of water, a liquid hydrolyzate, a support and an organic component is obtained. Next, when the mixed solution is dried by heating, a hydrolyzate of the liquid and a composite of the organic component adhered to the support are obtained.
隨後，藉由將回收物供於碳分析，可獲得碳量。 Subsequently, the amount of carbon can be obtained by supplying the recovered matter to carbon analysis.
另一方面，第2發明中，水解物為固體時，水解後，如上述進行加熱乾燥，回收水解物，對其進行碳分析，藉此可獲得碳量。且，水解物為液體時，如上述， 併用擔體與鹵化金屬化合物(Q)進行水解，其次，進行加熱乾燥，而獲得水解物附著於擔體之複合物。 On the other hand, in the second aspect of the invention, when the hydrolyzate is a solid, after the hydrolysis, the mixture is dried by heating as described above, and the hydrolyzate is recovered and subjected to carbon analysis, whereby the amount of carbon can be obtained. And, when the hydrolyzate is a liquid, as described above, Further, the carrier is hydrolyzed with the halogenated metal compound (Q), and then heated and dried to obtain a composite in which the hydrolyzate adheres to the support.
隨後，藉由將回收物供於碳分析，可獲得碳量。 Subsequently, the amount of carbon can be obtained by supplying the recovered matter to carbon analysis.
第1發明及第2發明中，進行碳分析時，較好使用以高溫使回收物燃燒，以紅外線檢測器定量生成之二氧化碳之裝置。 In the first invention and the second invention, in the carbon analysis, it is preferred to use a device that burns the recovered material at a high temperature and quantitatively generates carbon dioxide by an infrared detector.
例如可使用LECO公司製碳．硫分析裝置(CS844型或CS744型)、堀場製作所製碳．硫分析裝置(EMIA-920V2或EMIA-810W)、ELEMENTAL公司製全有機碳測定裝置(Vario TOC cube)等。 For example, you can use the carbon produced by LECO. Sulfur analyzer (CS844 type or CS744 type), carbon produced by Horiba. A sulfur analyzer (EMIA-920V2 or EMIA-810W), a full organic carbon measuring device (Vario TOC cube) manufactured by ELEMENTAL.
由於與獲得液體水解物之鹵化金屬化合物併用之擔體、或有時於使用之容器中附著有作為雜質之有機成分，故水解及加熱乾燥後之回收物有時含有該有機成分。因此，依循擔體之碳分析、或水解及加熱乾燥操作後，使擔體、水及容器接觸後，較好事先進行去除水所得之擔體乾燥物之碳分析。以下顯示分析例。 The organic component which is an impurity is adhered to the carrier which is used together with the halogenated metal compound which obtains a liquid hydrolysate, or the container used may contain the organic component, and the recovered product after hydrolysis and heat drying may contain this organic component. Therefore, after the carbon analysis of the support, or the hydrolysis and the heating and drying operation, after the support, the water, and the container are brought into contact, it is preferred to perform carbon analysis of the dried product obtained by removing the water in advance. The analysis example is shown below.
以氨使高純度四乙氧基矽烷水解，使析出之氧化矽於900℃燒成，獲得粒徑2μm之球狀氧化矽。球狀氧化矽以超純水洗淨後乾燥者稱為「擔體X」。該擔體乾燥物之碳量以燃燒紅外線吸收法求得之結果為0.001質量%。 The high-purity tetraethoxysilane was hydrolyzed with ammonia, and the precipitated cerium oxide was fired at 900 ° C to obtain spherical cerium oxide having a particle diameter of 2 μm. The spherical cerium oxide is washed with ultrapure water and then dried as "support X". The carbon content of the dried product of the carrier was 0.001% by mass as a result of the combustion infrared absorption method.
於乾淨玻璃容器中，饋入1.10質量份之擔體X及20.00質量份之超純水，攪拌30分鐘後，連同玻璃容器於氮氣流下，於90℃乾燥8小時，進而於120℃乾燥19小時。其次，所得擔體乾燥物之碳量以燃燒紅外線吸收法求得之結果為0.003質量%。 In a clean glass container, 1.10 parts by mass of the support X and 20.00 parts by mass of ultrapure water were fed, stirred for 30 minutes, dried with a glass vessel under a nitrogen stream at 90 ° C for 8 hours, and further dried at 120 ° C for 19 hours. . Next, the carbon content of the obtained dried product of the support was 0.003 mass% as a result of the combustion infrared absorption method.
因此，伴隨水解及加熱乾燥增大之碳量為0.002質量%。進行再次重複同樣操作之試驗及將超純水添加量減低至5質量份之試驗，增大之碳量分別為0.001質量%及0.003質量%。 Therefore, the amount of carbon which increased with hydrolysis and heat drying was 0.002% by mass. The test of repeating the same operation and the test of reducing the amount of ultrapure water added to 5 parts by mass were carried out, and the increased carbon amounts were 0.001% by mass and 0.003% by mass, respectively.
以下藉由實施例具體說明本發明。 The invention will be specifically described below by way of examples.
於乾淨玻璃容器中，饋入20.04質量份之超純水(全有機碳含量：18質量ppb)。接著，使玻璃容器與冰水接觸邊冷卻超純水，邊逐次少量添加於常壓蒸餾純化之1.95質量份之六氯化矽原料(以下簡稱為「HCD原料」)。藉此使HCD水解，獲得因所生成之水解物(聚矽氧烷)而白濁之漿料。其次，密封玻璃容器於約25℃放置24小時後，連同開封之玻璃容器一起於氮氣流下，在90℃加熱8小時，進而於120℃加熱19小時。藉此獲得乾燥物(白色固體)。由與事先測定之風袋之質量差，得之白色固體質量為0.86質量份。以燃燒紅外線吸收法求出所得 之白色固體之碳量後，為0.001質量%。基於該分析值，由下述式(1)求出水解前之HCD原料中所含之碳量(A)為4質量ppm。 In a clean glass container, 20.04 parts by mass of ultrapure water (all organic carbon content: 18 mass ppb) was fed. Then, the ultra-pure water was cooled while being in contact with ice water, and 1.95 parts by mass of ruthenium hexachloride raw material (hereinafter abbreviated as "HCD raw material") purified by atmospheric distillation was added in small portions. Thereby, HCD is hydrolyzed, and a slurry which is white turbid due to the produced hydrolyzate (polyoxane) is obtained. Next, the sealed glass vessel was allowed to stand at about 25 ° C for 24 hours, and then, together with the unsealed glass vessel, was heated at 90 ° C for 8 hours under nitrogen flow, and further heated at 120 ° C for 19 hours. Thereby a dried product (white solid) was obtained. The mass of the white solid obtained was 0.86 parts by mass from the difference in mass from the air bag previously measured. Calculated by burning infrared absorption method The amount of carbon of the white solid was 0.001% by mass. Based on the analysis value, the amount of carbon (A) contained in the HCD raw material before hydrolysis was determined by the following formula (1) to be 4 ppm by mass.
A=[(B×C/100)/D]×1000000 (1) A=[(B×C/100)/D]×1000000 (1)
此處，A為HCD原料中所含之碳量(質量ppm)，B為使水解物加熱乾燥後之白色固體之質量，C為以燃燒紅外線吸收法求出之碳量(質量%)，D為供於水解之HCD原料之質量。 Here, A is the amount of carbon (ppm by mass) contained in the HCD raw material, B is the mass of the white solid obtained by heating and drying the hydrolyzate, and C is the amount of carbon (% by mass) determined by the combustion infrared absorption method, D It is the quality of the HCD raw material for hydrolysis.
然而，由分析例1及2，確認藉由水解操作，碳量之分析值提高0.001~0.002質量%。如上述，白色固體之碳量為0.001質量%，故認為HCD原料中所含之碳量實質上為零。因此，即使包含碳成分，碳量亦可決定為未達定量下限之4質量ppm。 However, from Analysis Examples 1 and 2, it was confirmed that the analysis value of the carbon amount was increased by 0.001 to 0.002% by mass by the hydrolysis operation. As described above, since the amount of carbon of the white solid is 0.001% by mass, it is considered that the amount of carbon contained in the HCD raw material is substantially zero. Therefore, even if the carbon component is contained, the amount of carbon can be determined to be 4 ppm by mass which is less than the lower limit of the quantitative amount.
除了使用於玻璃瓶中於室溫保存2年之HCD(以下簡稱「HCD試料」)以外，以與實施例1同樣方法，進行碳分析。以燃燒紅外線吸收法求出所得水解物的白色固體之碳量後，為0.054質量%。可知藉由水解操作碳量增加0.001~0.002質量%，因此自0.054質量%減去0.002質量%後之0.52質量%為白色固體之碳量。接著，藉由上述式(1)，求出水解前之HCD試料中所含之碳量後，為226質量ppm。 Carbon analysis was carried out in the same manner as in Example 1 except that HCD (hereinafter referred to as "HCD sample") which was stored in a glass bottle at room temperature for 2 years was used. The amount of carbon of the white solid of the obtained hydrolyzate was determined by a combustion infrared absorption method to be 0.054% by mass. It is understood that the amount of carbon in the hydrolysis operation is increased by 0.001 to 0.002% by mass, so that 0.52% by mass after subtracting 0.002% by mass from 0.054% by mass is the amount of carbon of the white solid. Then, the amount of carbon contained in the HCD sample before hydrolysis was determined by the above formula (1), and it was 226 ppm by mass.
又，保存HCD之玻璃瓶雖有聚乙烯製之內蓋，但仍變色為黑褐色且變硬，柔軟性完全消失。且內蓋係牢固固著於玻璃瓶之開口部內壁，於內蓋與玻璃之界面有白色附著物。因此，採取的HCD式料著色為淡黃色。 Further, although the glass bottle in which the HCD was stored had a polyethylene inner cover, it was still dark brown and hardened, and the softness completely disappeared. The inner cover is firmly fixed to the inner wall of the opening of the glass bottle, and has a white attachment at the interface between the inner cover and the glass. Therefore, the HCD type material taken is colored yellowish.
於實施例2檢測出226質量ppm之碳推測係伴隨聚乙烯製內蓋之劣化或變質而於HCD中混入有機物之故。 In Example 2, it was estimated that 226 ppm by mass of carbon was mixed with organic substances in HCD due to deterioration or deterioration of the polyethylene inner lid.
於乾淨玻璃容器中，饋入5.15質量份之超純水(全有機碳含量：18質量ppb)。接著，使玻璃容器與冰水接觸邊冷卻超純水，邊逐次少量於純水中添加於1.93質量份之蒸餾純化之HCD中添加0.02質量份之三氯甲基矽烷(以下簡稱「TCMS」)所得之混合液，全部添加後放置5小時。使HCD及TCMS水解，獲得白濁之漿料。以下，進行與實施例1同樣操作，獲得0.83質量份之白色固體。以燃燒紅外線吸收法求出所得之白色固體之碳量後，為0.161質量%。基於該分析值，由下述式(2)求出HCD及TCMS之混合液中所含之碳量(E)為690質量ppm。 In a clean glass container, 5.15 parts by mass of ultrapure water (all organic carbon content: 18 mass ppb) was fed. Next, the glass container was cooled with ultra-pure water while being in contact with ice water, and 0.02 parts by mass of trichloromethyl decane (hereinafter referred to as "TCMS") was added to 1.93 parts by mass of distilled purified HCD in a small amount in pure water. The resulting mixture was added and allowed to stand for 5 hours. The HCD and TCMS were hydrolyzed to obtain a white turbid slurry. In the same manner as in Example 1, 0.83 parts by mass of a white solid was obtained. The amount of carbon of the obtained white solid was determined by a combustion infrared absorption method and found to be 0.161% by mass. Based on the analysis value, the amount of carbon (E) contained in the mixed liquid of HCD and TCMS was determined by the following formula (2) to be 690 ppm by mass.
A=[(B×C/100)/(D+F)]×1000000 (2) A=[(B×C/100)/(D+F)]×1000000 (2)
此處，E為HCD及TCMS之混合液中所含之碳量(質量ppm)，B為使水解物加熱乾燥後之白色固體之質量，C為以燃燒紅外線吸收法求出之碳量(質量%)，D 與F為供於水解之HCD及TCMS之質量。 Here, E is the amount of carbon (ppm by mass) contained in the mixture of HCD and TCMS, B is the mass of the white solid after heating and drying the hydrolyzate, and C is the amount of carbon (quality) obtained by the combustion infrared absorption method. %), D And F is the mass of HCD and TCMS for hydrolysis.
於乾淨玻璃容器中饋入2.04質量份之擔體X及0.65質量份之二氯二甲基矽烷(DCDMS)，進而饋入5.09質量份之超純水(全有機碳含量：18質量ppb)，將該等攪拌30分鐘。隨後，密封玻璃容器於約25℃放置24小時。其次，連同開封之玻璃容器於氮氣流下，在90℃加熱8小時，進而於120℃加熱19小時。藉此獲得乾燥物2.27質量份。以燃燒紅外線吸收法求出所得之白色固體之碳量後，為4.32質量%。 2.04 parts by mass of the support X and 0.65 parts by mass of dichlorodimethyl decane (DCDMS) were fed into a clean glass vessel, and then 5.09 parts by mass of ultrapure water (all organic carbon content: 18 mass ppb) was fed. This was stirred for 30 minutes. Subsequently, the sealed glass container was allowed to stand at about 25 ° C for 24 hours. Next, it was heated at 90 ° C for 8 hours together with the opened glass vessel under a nitrogen stream, and further heated at 120 ° C for 19 hours. Thereby, 2.27 parts by mass of the dried product was obtained. The amount of carbon of the obtained white solid was determined by a combustion infrared absorption method and found to be 4.32% by mass.
由以上，由式(2)求出擔體X與DCDMS之混合物中所含碳量為3.65質量%。由於擔體X之碳量為0.001質量%之為量故而忽視時，可求出DCDMS中所含之碳量為15.1質量%。 From the above, the amount of carbon contained in the mixture of the support X and the DCDMS was determined by the formula (2) to be 3.65 mass%. When the amount of carbon of the support X was 0.001% by mass, the amount of carbon contained in the DCDMS was found to be 15.1% by mass.
本發明之碳分析方法由於為安全且簡易之方法，且為可正確定量半導體製作中所管理之碳量，故於半導體等之電子材料領域為有用之分析方法。 The carbon analysis method of the present invention is a useful and analytical method in the field of electronic materials such as semiconductors because it is a safe and simple method and can accurately quantify the amount of carbon managed in semiconductor fabrication.
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