JP6702325B2 - Carbon analysis method - Google Patents
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- JP6702325B2 JP6702325B2 JP2017532499A JP2017532499A JP6702325B2 JP 6702325 B2 JP6702325 B2 JP 6702325B2 JP 2017532499 A JP2017532499 A JP 2017532499A JP 2017532499 A JP2017532499 A JP 2017532499A JP 6702325 B2 JP6702325 B2 JP 6702325B2
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- 229910052799 carbon Inorganic materials 0.000 title claims description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 106
- 238000004458 analytical method Methods 0.000 title claims description 37
- -1 metal halide compound Chemical class 0.000 claims description 53
- 229910001507 metal halide Inorganic materials 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 12
- 150000001721 carbon Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012433 hydrogen halide Substances 0.000 claims description 11
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 description 23
- 238000006460 hydrolysis reaction Methods 0.000 description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 238000011002 quantification Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- APOOHHZPEUGNQX-UHFFFAOYSA-N n-methyl-n-trichlorogermylmethanamine Chemical compound CN(C)[Ge](Cl)(Cl)Cl APOOHHZPEUGNQX-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- TYSSWEJEOFKGFN-UHFFFAOYSA-N trichloromethylgermanium Chemical compound ClC(Cl)(Cl)[Ge] TYSSWEJEOFKGFN-UHFFFAOYSA-N 0.000 description 2
- TXQJIMNDEHCONN-UHFFFAOYSA-N 3-(2-methoxyphenoxy)propanoic acid Chemical compound COC1=CC=CC=C1OCCC(O)=O TXQJIMNDEHCONN-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- 238000007792 addition Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000593 degrading effect Effects 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
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 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
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- 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)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (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)
Description
本発明は、加水分解性ハロゲンを有するハロゲン化金属化合物を含有する原料に含まれる炭素量を分析する方法に関する。 The present invention relates to a method for analyzing the amount of carbon contained in a raw material containing a metal halide compound having a hydrolyzable halogen.
半導体の分野では、素子の微細化が進んでいるため、製造プロセスで使用されるガスの原料である液体材料に対してより一層高純度化が要求されている。これまで、液体材料に含まれる不純物として金属成分については十分管理されてきた。 In the field of semiconductors, the miniaturization of elements is progressing, so that liquid materials, which are raw materials of gases used in the manufacturing process, are required to be further highly purified. So far, metal components as impurities contained in liquid materials have been well controlled.
しかしながら、特許文献１には、特定の構造を有するシリコン含有化合物のガスと、金属含有化合物のガスとを用いた原子層蒸着法により、基板上に金属シリケートから構成された高誘電率膜を形成する方法において、製造プロセスに使用される材料に炭素が多く含まれていると、高誘電率膜に炭素が残留してリーク電流が発生しやすくなるため、リーク電流の発生を抑制する手段として、ケイ素原子に対する炭素原子の組成比を規定した材料を用いる方法が記載されている。 However, in Patent Document 1, a high dielectric constant film composed of a metal silicate is formed on a substrate by an atomic layer deposition method using a gas of a silicon-containing compound having a specific structure and a gas of a metal-containing compound. In the method described above, if the material used in the manufacturing process contains a large amount of carbon, carbon is likely to remain in the high dielectric constant film to cause a leak current. A method using a material having a defined composition ratio of carbon atoms to silicon atoms is described.
また、特許文献２には、リーク電流の少ない層間絶縁膜を得るため、ケイ素原子に対する炭素原子の組成比を規定した材料を用いることを特徴とする半導体用絶縁材料が記載されている。 Further, Patent Document 2 describes an insulating material for a semiconductor, which is characterized by using a material having a specified composition ratio of carbon atoms to silicon atoms in order to obtain an interlayer insulating film having a small leak current.
このように、半導体の製造プロセスで使用される材料に含まれる不純物等に由来する炭素量を管理することが必要となっている。 As described above, it is necessary to control the amount of carbon derived from impurities contained in the material used in the semiconductor manufacturing process.
一方、炭素量を測定する方法として、特許文献３には、燃料電池用各種金属製部品及びセラミック製部品に付着残留している油分の分析方法として、油分を構成する炭化水素類を酸素と反応させて一酸化炭素又は二酸化炭素に変換し、これを赤外線検出器で測定して炭素量を求める分析方法が記載されている。 On the other hand, as a method for measuring the amount of carbon, Patent Document 3 discloses a method for analyzing oil components adhering and remaining on various metal parts and ceramic parts for fuel cells by reacting hydrocarbons forming oil components with oxygen. An analysis method is described in which the carbon content is converted into carbon monoxide or carbon dioxide, and the carbon content is measured by an infrared detector.
また、特許文献４には、金線に付着した有機物を高温で熱分解して、生成したメタンとエチレンを熱分解ガスクロマトグラフ装置で測定して全炭素量を定量する方法が記載されている。 Further, Patent Document 4 describes a method of quantifying the total amount of carbon by thermally decomposing an organic substance attached to a gold wire at a high temperature and measuring the produced methane and ethylene with a pyrolysis gas chromatograph.
更に、特許文献５には、ガスクロマトグラフを用いて炭素を分析する方法として、試料をメタンコンバータで処理し、試料中に含まれる一酸化炭素、二酸化炭素及び有機化合物等を水素で還元して炭素をメタンに変換し、そのメタンをガスクロマトグラフで検出することによって炭素を定量する方法が開示されている。 Further, in Patent Document 5, as a method for analyzing carbon using a gas chromatograph, a sample is treated with a methane converter, and carbon monoxide, carbon dioxide, an organic compound, and the like contained in the sample are reduced with hydrogen to produce carbon. A method for quantifying carbon by converting methane to methane and detecting the methane with a gas chromatograph is disclosed.
特許文献３に記載された炭素の定量方法は、燃焼赤外線吸収法と称され、液体試料でも分析可能であり、炭素の検出限界も１質量ｐｐｍまで達しており、優れた炭素の定量分析方法である。しかしながら、この方法で炭素原子を含むハロゲン化金属化合物原料を燃焼させたり、特許文献４の方法で炭素原子を含むハロゲン化金属化合物原料を熱分解させたりすると、ハロゲンガスやハロゲン化水素ガスが発生して分析装置の金属部を腐食させるおそれがあるため、燃焼赤外線吸収法や熱分解ガスクロマトグラフによりハロゲン化金属化合物原料に含まれる炭素を定量することは困難である。 The carbon quantification method described in Patent Document 3 is referred to as a combustion infrared absorption method, and it is possible to analyze even a liquid sample, and the carbon detection limit reaches 1 mass ppm, which is an excellent carbon quantification analysis method. is there. However, when the metal halide compound raw material containing carbon atoms is burned by this method or when the metal halide compound raw material containing carbon atoms is thermally decomposed by the method of Patent Document 4, halogen gas or hydrogen halide gas is generated. Since it may corrode the metal part of the analyzer, it is difficult to quantify the carbon contained in the metal halide compound raw material by the combustion infrared absorption method or the thermal decomposition gas chromatograph.
また、特許文献５に記載されたメタンコンバータを用いて試料中の炭素をメタンに変換する方法を、炭素原子を含むハロゲン化金属化合物原料に適用すると、副生成物として腐食性の高いハロゲン化水素やハロゲンガスが生成する。これにより、例えば、ニッケル化合物等からなる還元触媒が失活したり、分析装置の金属部の腐食が発生したりするため、メタンコンバータの使用は困難である。更に、ハロゲン化金属化合物である塩化シラン類を水素で還元すると、発火や爆発等の反応活性の高い金属水素化物であるシラン類となるため、ハロゲン化金属化合物原料の分析作業の危険性が非常に高くなる問題もある。 Further, when the method for converting carbon in a sample into methane using a methane converter described in Patent Document 5 is applied to a metal halide compound raw material containing carbon atoms, a highly corrosive hydrogen halide as a by-product. And halogen gas is generated. As a result, for example, the reduction catalyst made of a nickel compound or the like is deactivated, or the metal part of the analyzer is corroded, which makes it difficult to use the methane converter. Furthermore, when chlorosilanes, which are metal halide compounds, are reduced with hydrogen, they become silanes, which are metal hydrides with high reaction activity such as ignition and explosion, so the risk of analyzing metal halide compound raw materials is extremely high. There is also the problem of becoming expensive.
本発明は、装置の腐食や作業の危険性のない安全な方法で、加水分解性を有するハロゲン化金属化合物と、不純物等に由来する有機成分とを含む原料に含まれる炭素、又は、加水分解性を有し、ハロゲン原子及び炭素原子を含む金属化合物に含まれる炭素を定量する方法を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention is a safe method without risk of corrosion of equipment or work, carbon contained in a raw material containing a hydrolyzable metal halide compound and an organic component derived from impurities, or hydrolysis. An object of the present invention is to provide a method for quantitatively determining carbon contained in a metal compound having a halogen atom and a carbon atom.
本発明者は、上記の課題を解決するために鋭意検討した結果、ハロゲン化金属化合物の加水分解を利用して、加水分解性を有するハロゲン化金属化合物と、不純物等に由来する有機成分とを含む原料に含まれる炭素、又は、加水分解性を有し、ハロゲン原子及び炭素原子を含む金属化合物に含まれる炭素の量を効率よく定量可能であることを見い出し、本発明を完成するに至った。 The present inventor, as a result of extensive studies to solve the above problems, utilizing hydrolysis of a metal halide compound, a metal halide compound having a hydrolyzable property, and an organic component derived from impurities and the like. It was found that the amount of carbon contained in the raw material containing, or having a hydrolyzable property, the carbon contained in the metal compound containing a halogen atom and a carbon atom can be efficiently quantified, and the present invention has been completed. ..
本発明は、以下の第１発明及び第２発明である。
第１発明は、加水分解性を有するハロゲン化金属化合物（以下、「ハロゲン化金属化合物（Ｐ）」という）及び有機成分を含む原料と、水とを混合して、上記ハロゲン化金属化合物（Ｐ）を加水分解させて、加水分解物を形成した後、該加水分解物及び上記有機成分の混合物を回収し、該混合物の炭素分析によって炭素量を得ることを特徴とする、炭素分析方法である。
第１発明において、上記水は、全有機炭素の含有量が５００ｐｐｂ以下の純水であることが好ましい。
第１発明において、上記ハロゲン化金属化合物（Ｐ）を構成する金属原子がケイ素原子、ゲルマニウム原子又はタングステン原子であり、上記ハロゲン原子が塩素原子であることが好ましい。
第１発明において、上記加水分解物を得た際に副生したハロゲン化水素を、３０〜１８０℃の加熱により除去することが好ましい。
第１発明において、上記加水分解物が液体の場合、上記ハロゲン化金属化合物（Ｐ）は、担体に担持させて用いることが好ましい。
第２発明は、加水分解性を有し、ハロゲン原子及び炭素原子を含む金属化合物（以下、「ハロゲン化金属化合物（Ｑ）」という）を、水により加水分解させて、上記炭素原子を含む加水分解物を形成した後、該加水分解物を炭素分析して炭素量を得ることを特徴とする、炭素分析方法である。
第２発明において、上記水は、全有機炭素の含有量が５００ｐｐｂ以下の純水であることが好ましい。
第２発明において、上記ハロゲン化金属化合物（Ｑ）を構成する金属原子がケイ素原子又はゲルマニウム原子であり、上記ハロゲン原子が塩素原子であることが好ましい。
第２発明において、上記加水分解物を得た際に副生したハロゲン化水素を、３０〜１８０℃の加熱により除去することが好ましい。
第２発明において、上記加水分解物が液体の場合、上記ハロゲン化金属化合物（Ｑ）は、担体に担持させて用いることが好ましい。The present invention is the following first invention and second invention.
A first invention is to mix a raw material containing a hydrolyzable metal halide compound (hereinafter referred to as “metal halide compound (P)”) and an organic component with water to prepare the metal halide compound (P ) Is hydrolyzed to form a hydrolyzate, a mixture of the hydrolyzate and the organic component is recovered, and carbon content is obtained by carbon analysis of the mixture. ..
In the first invention, the water is preferably pure water having a total organic carbon content of 500 ppb or less.
In the first invention, it is preferable that the metal atom constituting the metal halide compound (P) is a silicon atom, a germanium atom or a tungsten atom, and the halogen atom is a chlorine atom.
In the first invention, it is preferable to remove the hydrogen halide produced as a byproduct when the above hydrolyzate is obtained by heating at 30 to 180°C.
In the first invention, when the hydrolyzate is a liquid, the metal halide compound (P) is preferably used by supporting it on a carrier.
The second invention is a hydrolyzable metal compound containing a halogen atom and a carbon atom (hereinafter referred to as “halogenated metal compound (Q)”) that is hydrolyzed to give a hydrolyzate containing the carbon atom. After forming a decomposition product, the hydrolysis product is subjected to carbon analysis to obtain the amount of carbon, which is a carbon analysis method.
In the second invention, the water is preferably pure water having a total organic carbon content of 500 ppb or less.
In the second invention, it is preferable that the metal atom constituting the metal halide compound (Q) is a silicon atom or a germanium atom, and the halogen atom is a chlorine atom.
In the second invention, it is preferable to remove the hydrogen halide produced as a byproduct when the above hydrolyzate is obtained by heating at 30 to 180°C.
In the second invention, when the hydrolyzate is a liquid, the metal halide compound (Q) is preferably used by supporting it on a carrier.
本発明の炭素分析方法によれば、生成する加水分解物がハロゲン成分を含有しないので、炭素量を、従来の定量方法を用いて効率よく分析することができる。そして、炭素分析装置の金属部の腐食等を回避することができる。第１発明によれば、不純物等として含まれる有機成分に由来する炭素量を得ることができ、ハロゲン化金属化合物（Ｐ）が、炭素原子を含む化合物である場合には、不純物等として含まれる有機成分に由来する炭素量との合計炭素量を得ることができる。また、第２発明によれば、分析対象のハロゲン化金属化合物（Ｑ）の炭素量を得ることができる。 According to the carbon analysis method of the present invention, since the produced hydrolyzate does not contain a halogen component, the carbon content can be efficiently analyzed using a conventional quantification method. Then, it is possible to avoid corrosion of the metal part of the carbon analyzer. According to the first invention, the amount of carbon derived from the organic component contained as an impurity or the like can be obtained, and when the metal halide compound (P) is a compound containing a carbon atom, it is included as an impurity or the like. It is possible to obtain the total carbon amount together with the carbon amount derived from the organic component. Further, according to the second invention, the carbon content of the metal halide compound (Q) to be analyzed can be obtained.
以下、本発明について詳しく説明する。 Hereinafter, the present invention will be described in detail.
本発明における分析対象は、炭素量を管理する必要がある、半導体等の製造で用いられる、ハロゲン原子と、このハロゲン原子に結合する金属原子とを含む加水分解可能なハロゲン化金属化合物（Ｐ）又は（Ｑ）を主とする原料である。尚、「加水分解性を有する」及び「加水分解可能な」は、対象化合物と水との反応により、ハロゲン化水素を発生させつつ、加水分解物を形成することを意味する。
加水分解性ハロゲン原子としては、塩素原子、フッ素原子等が挙げられる。これらのうち、塩素原子が好ましい。また、ハロゲン化金属化合物（Ｐ）又は（Ｑ）を構成する金属原子としては、ケイ素原子、チタン原子、ゲルマニウム原子、ジルコニウム原子、モリブデン原子、スズ原子、ハフニウム原子、タングステン原子等が挙げられ、これらのうち、ケイ素原子、ゲルマニウム原子又はタングステン原子が好ましい。
上記ハロゲン化金属化合物（Ｐ）及び（Ｑ）は、固体及び液体のいずれでもよい。The object of analysis in the present invention is a hydrolyzable metal halide compound (P) containing a halogen atom and a metal atom bonded to the halogen atom, which is used in the production of semiconductors or the like, in which the amount of carbon needs to be controlled. Alternatively, it is a raw material mainly containing (Q). In addition, "having a hydrolyzable property" and "hydrolyzable" mean that a hydrolyzate is formed by generating a hydrogen halide by a reaction between a target compound and water.
Examples of the hydrolyzable halogen atom include chlorine atom and fluorine atom. Of these, chlorine atom is preferable. Examples of the metal atom constituting the metal halide compound (P) or (Q) include silicon atom, titanium atom, germanium atom, zirconium atom, molybdenum atom, tin atom, hafnium atom, and tungsten atom. Of these, a silicon atom, a germanium atom or a tungsten atom is preferable.
The metal halide compounds (P) and (Q) may be solid or liquid.
第１発明で用いられるハロゲン化金属化合物（Ｐ）は、ハロゲン原子及び金属原子を含み、炭素原子を含んでいてもよい化合物である。本発明においては、ハロゲン原子及び金属原子の結合、若しくは、ハロゲン原子及び金属原子の結合並びに炭素原子及び金属原子の結合を有する、塩化ケイ素化合物、塩化ゲルマニウム化合物又は塩化タングステン化合物が好ましい。炭素原子は、炭化水素基として含まれることが好ましい。塩化ケイ素化合物としては、トリクロロメチルシラン、ジクロロジメチルシラン、クロロトリメチルシラン、テトラクロロシラン、ヘキサクロロジシラン等が挙げられる。また、塩化ゲルマニウム化合物としては、トリクロロメチルゲルマニウム、トリクロロジメチルアミノゲルマニウム、塩化ゲルマニウム（ＩＩ）、塩化ゲルマニウム（ＩＶ）等が挙げられる。更に、塩化タングステン化合物としては、塩化タングステン（ＩＩＩ）、塩化タングステン（ＩＶ）、塩化タングステン（ＶＩ）等が挙げられる。尚、テトラクロロシラン、ヘキサクロロジシラン、トリクロロメチルシラン、ジクロロジメチルシラン、クロロトリメチルシラン等のクロロシラン化合物の加水分解物は、通常、ポリシロキサンである。
第１発明で用いられるハロゲン化金属化合物（Ｐ）は、１種のみであってよいし、２種以上であってもよい。
上記ハロゲン化金属化合物（Ｐ）は、ハロゲン原子及び金属原子からなる化合物を含むことが好ましい。The metal halide compound (P) used in the first invention is a compound containing a halogen atom and a metal atom, and optionally a carbon atom. In the present invention, a silicon chloride compound, a germanium chloride compound or a tungsten chloride compound having a bond of a halogen atom and a metal atom, or a bond of a halogen atom and a metal atom and a bond of a carbon atom and a metal atom is preferable. Carbon atoms are preferably included as hydrocarbon groups. Examples of the silicon chloride compound include trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetrachlorosilane and hexachlorodisilane. Examples of the germanium chloride compound include trichloromethylgermanium, trichlorodimethylaminogermanium, germanium (II) chloride, germanium (IV) chloride and the like. Furthermore, examples of the tungsten chloride compound include tungsten (III) chloride, tungsten (IV) chloride, and tungsten (VI) chloride. The hydrolyzate of a chlorosilane compound such as tetrachlorosilane, hexachlorodisilane, trichloromethylsilane, dichlorodimethylsilane and chlorotrimethylsilane is usually polysiloxane.
The metal halide compound (P) used in the first invention may be only one kind or two or more kinds.
The metal halide compound (P) preferably contains a compound composed of a halogen atom and a metal atom.
また、第２発明で用いられるハロゲン化金属化合物（Ｑ）は、ハロゲン原子、炭素原子及び金属原子を含む化合物である。本発明においては、塩化ケイ素化合物及び塩化ゲルマニウム化合物が好ましい。塩化ケイ素化合物としては、トリクロロメチルシラン、ジクロロジメチルシラン、クロロトリメチルシラン等が挙げられる。また、塩化ゲルマニウム化合物としては、トリクロロメチルゲルマニウム、トリクロロジメチルアミノゲルマニウム等が挙げられる。
第２発明で用いられるハロゲン化金属化合物（Ｑ）は、１種のみであってよいし、２種以上であってもよい。The metal halide 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 silicon chloride compound and a germanium chloride compound are preferable. Examples of the silicon chloride compound include trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane and the like. Further, examples of the germanium chloride compound include trichloromethylgermanium, trichlorodimethylaminogermanium and the like.
The metal halide compound (Q) used in the second invention may be only one kind or two or more kinds.
第１発明における有機成分は、通常、油分であり、不純物等として微量に含有する成分である。この有機成分の加水分解性は、定量性に影響を与えないことから、特に限定されない。 The organic component in the first invention is usually an oil component, which is a component contained in a trace amount as impurities and the like. The hydrolyzability of this organic component is not particularly limited because it does not affect the quantification.
第１発明及び第２発明では、初めに、ハロゲン化金属化合物（Ｐ）及び有機成分を含む原料又はハロゲン化金属化合物（Ｑ）を水により加水分解させる。水は、特に限定されないが、純水が好ましい。この純水における全有機炭素（ＴＯＣ）の含有量は、好ましくは５００質量ｐｐｂ以下であり、更に好ましくは１００質量ｐｐｂ以下、特に好ましくは５０質量ｐｐｂ以下（超純水）である。
加水分解では、ハロゲン化金属化合物（Ｐ）又は（Ｑ）に含まれるハロゲン原子の当量より過剰な量の水を清浄な容器に収容し、そこにハロゲン化金属化合物（Ｐ）又は（Ｑ）を少量ずつ添加することが好ましい。この時に発熱が激しい場合は、発熱の程度に応じて内容物を冷却することが好ましい。加水分解に要する時間は、ハロゲン化金属化合物（Ｐ）又は（Ｑ）の種類又は量によるが、一般に、約２５℃で２４時間以上放置することが好ましい。In the first invention and the second invention, first, the raw material containing the metal halide compound (P) and the organic component or the metal halide compound (Q) is hydrolyzed with water. The water is not particularly limited, but pure water is preferable. The content of total organic carbon (TOC) in this pure water is preferably 500 mass ppb or less, more preferably 100 mass ppb or less, and particularly preferably 50 mass ppb or less (ultra pure water).
In the hydrolysis, an amount of water in excess of the equivalent amount of the halogen atom contained in the metal halide compound (P) or (Q) is placed in a clean container, and the metal halide compound (P) or (Q) is placed therein. It is preferable to add it little by little. At this time, if the heat generation is intense, it is preferable to cool the contents according to the degree of heat generation. The time required for hydrolysis depends on the kind or amount of the metal halide compound (P) or (Q), but it is generally preferable to leave it at about 25° C. for 24 hours or more.
水の使用量は、加水分解の反応性の観点から、ハロゲン化金属化合物（Ｐ）又は（Ｑ）１質量部に対して、好ましくは１〜１００質量部、更に好ましくは５〜５０質量部である。
水の使用量が１質量部未満では、加水分解が十分に進まないことがある。尚、水の使用量が多すぎると、後工程で水の除去に手間がかかることがある。From the viewpoint of hydrolysis reactivity, the amount of water used is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, relative to 1 part by mass of the metal halide compound (P) or (Q). is there.
If the amount of water used is less than 1 part by mass, hydrolysis may not proceed sufficiently. If the amount of water used is too large, it may take time to remove the water in a later step.
上記ハロゲン化金属化合物（Ｐ）又は（Ｑ）の加水分解により得られる加水分解物は、一般に、固体であり、加水分解後には、その水相が、塩化水素等のハロゲン化水素を含む懸濁液となる。このハロゲン化水素は、分析装置に悪影響を及ぼすため、常圧又は減圧下、懸濁液の加熱乾燥を行い、水と共に除去することで、分析に適した固体物質を得る。 The hydrolyzate obtained by hydrolysis of the above metal halide compound (P) or (Q) is generally a solid, and after hydrolysis, the aqueous phase thereof is a suspension containing hydrogen halide such as hydrogen chloride. It becomes liquid. Since this hydrogen halide has an adverse effect on the analyzer, the suspension is heated and dried under atmospheric pressure or reduced pressure, and is removed together with water to obtain a solid substance suitable for analysis.
第１発明では、加水分解後に、加水分解物及び有機成分の混合物が、通常、加水分解物に有機成分が包含された形態となって得られる。尚、第１発明では、有機成分が加水分解性を有する場合、ハロゲン化金属化合物（Ｐ）の加水分解物、及び、上記有機成分の加水分解物の混合物が得られる。 In the first invention, after hydrolysis, a mixture of the hydrolyzate and the organic component is usually obtained in a form in which the hydrolyzate contains the organic component. In the first invention, when the organic component is hydrolyzable, a hydrolyzate of the metal halide compound (P) and a mixture of the hydrolysates of the organic component are obtained.
上記加熱乾燥の条件として温度は、加水分解物を変質させることなく、ハロゲン化水素を効率よく除去させられることから、好ましくは３０〜１８０℃、更に好ましくは８０〜１２０℃である。加熱温度が３０℃未満では乾燥が不十分でハロゲン化水素が残留して分析装置に悪影響を及ぼす可能性がある、また、乾燥温度が１８０℃を超えると加水分解物に包含された有機成分が揮発したり、分解したりする可能性が高くなるため好ましくない。
更に、加熱乾燥の雰囲気は、特に限定されないが、不活性ガス雰囲気が好ましい。不活性ガス雰囲気とすることで、加水分解物の乾燥が促進され、有機成分の酸化分解も抑制できる。不活性ガスとしては、窒素を用いることが好ましい。The temperature for heating and drying is preferably 30 to 180° C., more preferably 80 to 120° C., because hydrogen halide can be efficiently removed without degrading the hydrolyzate. If the heating temperature is lower than 30°C, the drying may be insufficient and hydrogen halide may remain to adversely affect the analyzer. Also, if the heating temperature exceeds 180°C, the organic components contained in the hydrolyzate may be deteriorated. It is not preferable because the possibility of volatilization or decomposition increases.
Furthermore, the atmosphere for heating and drying is not particularly limited, but an inert gas atmosphere is preferable. The inert gas atmosphere promotes the drying of the hydrolyzate and also suppresses the oxidative decomposition of the organic component. Nitrogen is preferably used as the inert gas.
上記加熱乾燥は、好ましくは、水で湿らせたｐＨ試験紙を排気ガスにかざして、ｐＨ６以上及び恒量となったことを確認して終了とする。
その後、回収物を、炭素分析に供することにより、炭素量を得ることができる。The above-mentioned heating and drying is preferably finished by holding a pH test paper moistened with water over exhaust gas and confirming that the pH becomes 6 or more and a constant weight.
After that, the carbon content can be obtained by subjecting the recovered material to carbon analysis.
尚、ハロゲン化金属化合物（Ｐ）の加水分解により得られる加水分解物が固体にならないことがある。加水分解物が液体の場合は、ハロゲン化金属化合物（Ｐ）と、担体とを併用することが好ましい。
担体は、特に限定されないが、後に分析の障害にならないようにするため、炭素の含有量が分析装置の定量下限未満の化合物からなる粉体を用いることが好ましい。上記担体としては、例えば、高純度のテトラエトキシシランをアンモニアで加水分解した後、焼成させて得られた粒径が０．３〜３μｍのシリカを用いることができる。特に、燃焼赤外線吸収法で求めた炭素量が０．００３〜０．００１質量％未満であるシリカが、好適である。
担体を用いる場合、容器に、担体と、ハロゲン化金属化合物（Ｐ）を含む原料とを加え、過剰な水を加えて加水分解を行う。尚、予め、担体の炭素量を分析しておくことにより、正確な炭素量を得ることができる。The hydrolyzate obtained by hydrolyzing the metal halide compound (P) may not be solid. When the hydrolyzate is a liquid, it is preferable to use the metal halide compound (P) in combination with a carrier.
The carrier is not particularly limited, but it is preferable to use a powder made of a compound having a carbon content less than the lower limit of quantification of the analyzer in order not to hinder the analysis later. As the carrier, for example, silica having a particle size of 0.3 to 3 μm, which is obtained by hydrolyzing high-purity tetraethoxysilane with ammonia and then calcining it, can be used. In particular, silica having a carbon content of 0.003 to less than 0.001 mass% determined by the combustion infrared absorption method is suitable.
When a carrier is used, the carrier and the raw material containing the metal halide compound (P) are added to a container, and excess water is added to carry out hydrolysis. An accurate carbon amount can be obtained by analyzing the carbon amount of the carrier in advance.
上記担体の使用量は、作業性の観点から、ハロゲン化金属化合物１質量部に対して、好ましくは５〜１００質量部、更に好ましくは１０〜５０質量部である。 From the viewpoint of workability, the amount of the carrier used is preferably 5 to 100 parts by mass, and more preferably 10 to 50 parts by mass with respect to 1 part by mass of the metal halide compound.
液体の加水分解物を与えるハロゲン化金属化合物（Ｐ）と、担体とを併用した場合、加水分解後には、水と、液体の加水分解物と、担体と、有機成分とからなる混合液（懸濁液）が得られる。そして、この混合液を加熱乾燥すると、液体の加水分解物及び有機成分が担体に付着した複合物が得られる。
その後、回収物を、炭素分析に供することにより、炭素量を得ることができる。When the metal halide compound (P) that gives a liquid hydrolyzate is used in combination with a carrier, after hydrolysis, a mixed solution of water, a liquid hydrolyzate, a carrier, and an organic component (suspended) A suspension) is obtained. Then, when this mixed liquid is heated and dried, a liquid hydrolyzate and a composite in which an organic component is attached to a carrier are obtained.
After that, the carbon content can be obtained by subjecting the recovered material to carbon analysis.
一方、第２発明において、加水分解物が固体である場合には、加水分解後に、上記のように、加熱乾燥を行って、加水分解物を回収し、これを炭素分析することにより、炭素量を得ることができる。また、加水分解物が液体である場合には、上記のように、担体と、ハロゲン化金属化合物（Ｑ）とを併用して加水分解を行い、次いで、加熱乾燥を行うことにより、加水分解物が担体に付着した複合物が得られる。
その後、回収物を、炭素分析に供することにより、炭素量を得ることができる。On the other hand, in the second invention, in the case where the hydrolyzate is a solid, after hydrolysis, heating and drying are performed as described above to recover the hydrolyzate, and the carbon content is analyzed by carbon analysis. Can be obtained. Further, when the hydrolyzate is a liquid, as described above, the carrier and the metal halide compound (Q) are used in combination for hydrolysis, and then the product is heated and dried to give the hydrolyzate. A composite is obtained in which is attached to the carrier.
After that, the carbon content can be obtained by subjecting the recovered material to carbon analysis.
第１発明及び第２発明において、炭素分析を行う場合には、回収物を高温で燃焼させ、生成する二酸化炭素を赤外線検出器で定量する装置が好適に用いられる。
例えば、ＬＥＣＯ社製炭素・硫黄分析装置（ＣＳ８４４型又はＣＳ７４４型）、堀場製作所製炭素・硫黄分析装置（ＥＭＩＡ−９２０Ｖ２又はＥＭＩＡ−８１０Ｗ）、エレメンタール社製全有機炭素測定装置（ｖａｒｉｏ ＴＯＣ ｃｕｂｅ）等を用いることができる。In the first invention and the second invention, when carbon analysis is performed, an apparatus in which the recovered material is burned at a high temperature and the produced carbon dioxide is quantified by an infrared detector is preferably used.
For example, LECO carbon/sulfur analyzer (CS844 type or CS744 type), Horiba carbon/sulfur analyzer (EMIA-920V2 or EMIA-810W), Elemental total organic carbon measuring device (vario TOC cube). Etc. can be used.
液体の加水分解物を与えるハロゲン化金属化合物と併用する担体や、使用する容器には、不純物としての有機成分が付着していることがあるため、加水分解及び加熱乾燥の後の回収物は、この有機成分を含むことがある。従って、担体の炭素分析、又は、加水分解及び加熱乾燥の操作に従って、担体、水及び容器を接触させた後、水を除去して得られた担体乾燥物の炭素分析、を前もって行っておくことが好ましい。以下、分析例を示す。 The carrier used in combination with a metal halide compound that gives a liquid hydrolyzate, and the container used may have organic components attached as impurities, so the recovered product after hydrolysis and heat drying is It may contain this organic component. Therefore, carbon analysis of the carrier, or carbon analysis of the dried carrier obtained by removing the water after contacting the carrier, water and the container according to the operation of hydrolysis and heat drying, should be performed in advance. Is preferred. Hereinafter, an analysis example will be shown.
分析例１
高純度のテトラエトキシシランをアンモニアで加水分解させ、析出したシリカを９００℃で焼成することで粒径２μｍの球状シリカを得た。球状シリカを超純水で洗浄してから乾燥させたものを「担体Ｘ」とした。この担体乾燥物の炭素量を、燃焼赤外線吸収法で求めた結果、０．００１質量％であった。Analysis example 1
High-purity tetraethoxysilane was hydrolyzed with ammonia, and the precipitated silica was calcined at 900° C. to obtain spherical silica having a particle size of 2 μm. The spherical silica was washed with ultrapure water and then dried to obtain "carrier X". The carbon content of this dried carrier product was 0.001% by mass as determined by the combustion infrared absorption method.
分析例２
清浄なガラス容器に、１．１０質量部の担体Ｘ及び２０．００質量部の超純水を入れて３０分間撹拌後、ガラス容器ごと窒素気流下、９０℃で８時間、更に１２０℃で１９時間乾燥させた。次いで、得られた担体乾燥物の炭素量を、燃焼赤外線吸収法で求めた結果、０．００３質量％であった。
したがって、加水分解及び加熱乾燥に伴って増大した炭素量は０．００２質量％であった。同様な操作をもう一度繰り返す試験、及び、超純水の添加量を５質量部に減らした試験を行ったが、増大した炭素量は、それぞれ０．００１質量％及び０．００３質量％であった。Analysis example 2
1.10 parts by mass of the carrier X and 20.00 parts by mass of ultrapure water were placed in a clean glass container and stirred for 30 minutes, and then the entire glass container was heated at 90° C. for 8 hours at 120° C. under a nitrogen stream. Allowed to dry for hours. Next, the carbon content of the obtained dried carrier was determined by the combustion infrared absorption method, and was found to be 0.003% by mass.
Therefore, the amount of carbon increased with hydrolysis and heat drying was 0.002 mass %. A test in which the same operation was repeated once and a test in which the amount of ultrapure water added was reduced to 5 parts by mass were carried out, but the increased amounts of carbon were 0.001% by mass and 0.003% by mass, respectively. ..
以下、実施例により、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
実施例１
清浄なガラス容器に２０．０４質量部の超純水（全有機炭素の含有量：１８質量ｐｐｂ）を入れた。そして、ガラス容器に氷水を接触させて超純水を冷却しながら、常圧で蒸留精製した１．９５質量部の六塩化二ケイ素原料（以下、「ＨＣＤ原料」と略す。）を少しずつ添加した。これによりＨＣＤは加水分解され、生成した加水分解物（ポリシロキサン）により白濁したスラリーを得た。次いで、ガラス容器を密封して約２５℃で２４時間放置した後、開封したガラス容器ごと窒素気流下、９０℃で８時間、更に１２０℃で１９時間加熱した。これにより乾燥物（白色固体）を得た。事前に測定しておいた風袋との質量差より、白色固体の質量は０．８６質量部であった。得られた白色固体の炭素量を燃焼赤外線吸収法で求めたところ、０．００１質量％であった。この分析値を基に、加水分解前のＨＣＤ原料に含まれる炭素量（Ａ）は、下記式（１）から４質量ｐｐｍとなった。
Ａ＝〔（Ｂ×Ｃ／１００）／Ｄ〕×１００００００ （１）
ここで、ＡはＨＣＤ原料に含まれる炭素量（質量ｐｐｍ）、Ｂは加水分解物を加熱乾燥させた後の白色固体の質量、Ｃは燃焼赤外線吸収法で求めた炭素量（質量％）、Ｄは加水分解に供したＨＣＤ原料の質量である。
しかしながら、分析例１及び２から、加水分解操作によって、炭素量の分析値が０．００１〜０．００２質量％高くなることが確認されている。上記のように、白色固体の炭素量は、０．００１質量％であるため、ＨＣＤ原料に含まれる炭素量は、実質的にゼロであると考えられる。従って、炭素成分が含まれていたとしても、炭素量を、定量下限未満の４質量ｐｐｍと決定した。Example 1
20.04 parts by mass of ultrapure water (content of total organic carbon: 18 parts by mass ppb) was put in a clean glass container. Then, while ice water was brought into contact with the glass container to cool the ultrapure water, 1.95 parts by mass of disilicon hexachloride raw material (hereinafter abbreviated as "HCD raw material") distilled and purified under normal pressure was added little by little. did. As a result, HCD was hydrolyzed, and a white turbid slurry was obtained due to the hydrolyzate (polysiloxane) produced. Then, after sealing the glass container and leaving it at about 25° C. for 24 hours, it was heated together with the opened glass container under a nitrogen stream at 90° C. for 8 hours and further at 120° C. for 19 hours. As a result, a dried product (white solid) was obtained. The mass of the white solid was 0.86 parts by mass from the mass difference with the tare measured in advance. The carbon content of the obtained white solid was determined by the combustion infrared absorption method to be 0.001% by mass. Based on this analysis value, the amount of carbon (A) contained in the HCD raw material before hydrolysis was 4 mass ppm from the following formula (1).
A=[(B×C/100)/D]×1000000 (1)
Here, A is the amount of carbon contained in the HCD raw material (mass ppm), B is the mass of the white solid after heating and drying the hydrolyzate, C is the amount of carbon (% by mass) determined by the combustion infrared absorption method, D is the mass of the HCD raw material subjected to hydrolysis.
However, it has been confirmed from Analysis Examples 1 and 2 that the analysis value of the carbon content is increased by 0.001 to 0.002 mass% by the hydrolysis operation. As described above, since the carbon content of the white solid is 0.001% by mass, the carbon content contained in the HCD raw material is considered to be substantially zero. Therefore, even if the carbon component was included, the amount of carbon was determined to be 4 mass ppm, which is less than the lower limit of quantification.
実施例２
ガラスビンに室温で２年間保管したＨＣＤ（以下、「ＨＣＤ試料」と略す。）を用いた以外は、実施例１と同様な方法で、炭素分析を行った。得られた加水分解物である白色固体の炭素量を燃焼赤外線吸収法で求めたところ、０．０５４質量％であった。加水分解操作で炭素量は０．００１〜０．００２質量％増えることが分かっているので、０．０５４質量％から０．００２質量％を引いた０．０５２質量％を白色固体の炭素量とした。そして、上記式（１）により、加水分解前のＨＣＤ試料に含まれた炭素量を求めると、２２６質量ｐｐｍであった。
尚、ＨＣＤを保管していたガラスビンにはポリエチレン製の内蓋があったが、黒褐色に変色して硬くなっており、全く柔軟性はなくなっていた。また、内蓋は、ガラスビンの開口部内壁に固く固着しており、内蓋とガラスの界面には白い付着物があった。そして、採取したＨＣＤ試料は薄く黄色に着色していた。
この実施例２で２２６質量ｐｐｍの炭素が検出されたのは、ポリエチレン製の内蓋の劣化や変質に伴って有機物がＨＣＤ中に混入したためと推察される。Example 2
Carbon analysis was performed in the same manner as in Example 1 except that HCD stored in a glass bottle at room temperature for 2 years (hereinafter abbreviated as “HCD sample”) was used. When the carbon content of the obtained white solid, which was a hydrolyzate, was determined by the combustion infrared absorption method, it was 0.054% by mass. It is known that the amount of carbon increases by 0.001 to 0.002 mass% by the hydrolysis operation, so 0.052 mass% obtained by subtracting 0.002 mass% from 0.054 mass% is regarded as the carbon content of the white solid. did. Then, the amount of carbon contained in the HCD sample before hydrolysis was calculated by the above formula (1) and found to be 226 mass ppm.
Incidentally, the glass bottle storing the HCD had an inner lid made of polyethylene, but it was discolored to blackish brown and hard, and had no flexibility at all. Further, the inner lid was firmly fixed to the inner wall of the opening of the glass bottle, and white deposits were present at the interface between the inner lid and the glass. Then, the collected HCD sample was colored light yellow.
The detection of 226 mass ppm of carbon in this Example 2 is presumed to be due to the inclusion of organic substances in the HCD due to deterioration and deterioration of the polyethylene inner lid.
実施例３
清浄なガラス容器に５．１５質量部の超純水（全有機炭素の含有量：１８質量ｐｐｂ）を入れた。そして、ガラス容器に氷水を接触させて超純水を冷却しながら、１．９３質量部の蒸留精製したＨＣＤに０．０２質量部のトリクロロメチルシラン（以下、「ＴＣＭＳ」と略す）を加えた混合液を超純水に少しずつ添加し、全て添加後５時間放置した。ＨＣＤ及びＴＣＭＳは加水分解され、白濁したスラリーを得た。以下、実施例１と同様の操作を行い、０．８３質量部の白色固体を得た。得られた白色固体の炭素量を燃焼赤外線吸収法で求めたところ、０．１６１質量％であった。この分析値を基に、ＨＣＤ及びＴＣＭＳの混合液に含まれる炭素量（Ｅ）は、下記式（２）から６９０質量ｐｐｍとなった。
Ｅ＝〔（Ｂ×Ｃ／１００）／（Ｄ＋Ｆ）〕×１００００００ （２）
ここで、ＥはＨＣＤ及びＴＣＭＳの混合液に含まれる炭素量（質量ｐｐｍ）、Ｂは加水分解物を加熱乾燥させた後の白色固体の質量、Ｃは燃焼赤外線吸収法で求めた炭素量（質量％）、ＤとＦはそれぞれ加水分解に供したＨＣＤ及びＴＣＭＳの質量である。Example 3
5.15 parts by mass of ultrapure water (content of total organic carbon: 18 parts by mass ppb) was put in a clean glass container. Then, while cooling the ultrapure water by bringing ice water into contact with the glass container, 0.02 parts by mass of trichloromethylsilane (hereinafter abbreviated as "TCMS") was added to 1.93 parts by mass of the distilled and purified HCD. The mixed solution was added little by little to ultrapure water, and after all the additions were left for 5 hours. HCD and TCMS were hydrolyzed to obtain a cloudy slurry. Then, the same operation as in Example 1 was performed to obtain 0.83 parts by mass of a white solid. The carbon content of the obtained white solid was determined by the combustion infrared absorption method to be 0.161% by mass. Based on this analysis value, the carbon amount (E) contained in the mixed liquid of HCD and TCMS was 690 mass ppm from the following formula (2).
E=[(B×C/100)/(D+F)]×1000000 (2)
Here, E is the amount of carbon (mass ppm) contained in the mixed liquid 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 obtained by the combustion infrared absorption method ( Mass%), D and F are the masses of HCD and TCMS subjected to hydrolysis, respectively.
実施例４
２．０４質量部の担体Ｘ及び０．６５質量部のジクロロジメチルシラン（ＤＣＤＭＳ）を清浄なガラス容器に入れ、更に、５．０９質量部の超純水（全有機炭素の含有量：１８質量ｐｐｂ）を入れて、これらを３０分間撹拌した。その後、ガラス容器を密封して約２５℃で２４時間放置した。次に、開封したガラス容器ごと窒素気流下、９０℃で８時間、更に１２０℃で１９時間加熱した。これにより乾燥物２．２７質量部を得た。この乾燥物の炭素量を燃焼赤外線吸収法で求めたところ、４．３２質量％であった。
以上より、担体ＸとＤＣＤＭＳの混合物に含まれる炭素量は、式（２）から３．６５質量％と求められた。担体Ｘの炭素量は０．００１質量％と微量なので無視すると、ＤＣＤＭＳに含まれる炭素量は１５．１質量％と求めることができた。Example 4
2.04 parts by mass of the carrier X and 0.65 parts by mass of dichlorodimethylsilane (DCDMS) were placed in a clean glass container, and further 5.09 parts by mass of ultrapure water (total organic carbon content: 18 parts by mass). ppb) was added and they were stirred for 30 minutes. Then, the glass container was sealed and left at about 25° C. for 24 hours. Then, the opened glass container was heated at 90° C. for 8 hours and further at 120° C. for 19 hours under a nitrogen stream. As a result, 2.27 parts by mass of a dried product was obtained. When the carbon content of this dried product was determined by the combustion infrared absorption method, it was 4.32% by mass.
From the above, the amount of carbon contained in the mixture of the carrier X and DCDMS was calculated from the formula (2) to be 3.65 mass %. Since the carbon content of the carrier X was a very small amount of 0.001% by mass, it could be determined that the carbon content contained in DCDMS was 15.1% by mass.
本発明における炭素分析方法は、安全かつ簡易な方法で、半導体の製造において管理される炭素の量を正確に定量できる方法であるため、半導体等の電子材料分野で有用な分析方法である。 The carbon analysis method of the present invention is a safe and simple method that can accurately quantify the amount of carbon controlled in the production of semiconductors, and is therefore a useful analysis method in the field of electronic materials such as semiconductors.
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