KR102581692B1 - Carbon Analysis Methods - Google Patents
Carbon Analysis Methods Download PDFInfo
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- KR102581692B1 KR102581692B1 KR1020187005774A KR20187005774A KR102581692B1 KR 102581692 B1 KR102581692 B1 KR 102581692B1 KR 1020187005774 A KR1020187005774 A KR 1020187005774A KR 20187005774 A KR20187005774 A KR 20187005774A KR 102581692 B1 KR102581692 B1 KR 102581692B1
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- carbon
- atom
- hydrolyzate
- metal compound
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 124
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000004458 analytical method Methods 0.000 title claims abstract description 45
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 150000001721 carbon Chemical group 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 12
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 10
- 239000012433 hydrogen halide Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 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
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 description 21
- 238000006460 hydrolysis reaction Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 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
- -1 polysiloxanes Polymers 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
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 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
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 206010037660 Pyrexia Diseases 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
- 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
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011344 liquid material 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
- 239000005416 organic matter Substances 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
- 238000004445 quantitative analysis Methods 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
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 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
- 239000005046 Chlorosilane 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
- 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
- 230000002411 adverse Effects 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
- 239000006227 byproduct Substances 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
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004880 explosion Methods 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
- 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
- 230000002452 interceptive effect Effects 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
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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)
Abstract
본 발명의 탄소 분석 방법은, 가수분해성을 갖는 할로겐화 금속 화합물 및 유기 성분을 포함하는 원료와, 순수를 혼합하여, 할로겐화 금속 화합물을 가수분해시켜, 가수분해물을 형성한 후, 얻어진 가수분해물 및 상기 유기 성분의 혼합물을 회수하고, 이 혼합물의 탄소 분석에 의해 탄소량을 얻는다. 다른 본 발명의 탄소 분석 방법은, 가수분해성을 갖고, 할로겐 원자 및 탄소 원자를 포함하는 금속 화합물을, 순수에 의해 가수분해시켜, 탄소 원자를 포함하는 가수분해물을 형성한 후, 얻어진 가수분해물을 탄소 분석하여 탄소량을 얻는다.The carbon analysis method of the present invention involves mixing a raw material containing a hydrolyzable halogenated metal compound and an organic component with pure water, hydrolyzing the halogenated metal compound to form a hydrolyzate, and then mixing the obtained hydrolyzate and the organic component. The mixture of components is recovered, and the carbon content is obtained by carbon analysis of this mixture. In another carbon analysis method of the present invention, a metal compound that has hydrolyzability and contains a halogen atom and a carbon atom is hydrolyzed with pure water to form a hydrolyzate containing a carbon atom, and then the obtained hydrolyzate is converted into a carbon atom. Analyze to obtain the carbon amount.
Description
본 발명은 가수분해성 할로겐을 갖는 할로겐화 금속 화합물을 함유하는 원료에 포함되는 탄소량을 분석하는 방법에 관한 것이다.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.
반도체의 분야에서는, 소자의 미세화가 진행되고 있기 때문에, 제조 프로세스에서 사용되는 가스의 원료인 액체 재료에 대하여 한층 더 고순도화가 요구되고 있다. 이제까지, 액체 재료에 포함되는 불순물로서 금속 성분에 대해서는 충분히 관리되어 왔다.In the field of semiconductors, as devices are becoming more miniaturized, there is a demand for even higher purity of liquid materials that are raw materials for gases used in manufacturing processes. Until now, metal components as impurities contained in liquid materials have been sufficiently managed.
그러나, 특허문헌 1에는, 특정한 구조를 갖는 실리콘 함유 화합물의 가스와, 금속 함유 화합물의 가스를 사용한 원자층 증착법에 의해, 기판 상에 금속 실리케이트로 구성된 고유전율막을 형성하는 방법에 있어서, 제조 프로세스에 사용되는 재료에 탄소가 많이 포함되어 있으면, 고유전율막에 탄소가 잔류하여 누설 전류가 발생하기 쉬워지기 때문에, 누설 전류의 발생을 억제하는 수단으로서, 규소 원자에 대한 탄소 원자의 조성비를 규정한 재료를 사용하는 방법이 기재되어 있다.However, Patent Document 1 discloses a method of forming a high dielectric constant film made of metal silicate 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, including the manufacturing process. If the material used contains a lot of carbon, the carbon will remain in the high dielectric constant film and leakage current is likely to occur. As a means of suppressing the generation of leakage current, a material in which the composition ratio of carbon atoms to silicon atoms is specified is used. How to use is described.
또한, 특허문헌 2에는, 누설 전류가 적은 층간 절연막을 얻기 위해, 규소 원자에 대한 탄소 원자의 조성비를 규정한 재료를 사용하는 것을 특징으로 하는 반도체용 절연 재료가 기재되어 있다.Additionally, Patent Document 2 describes an insulating material for semiconductors characterized by using a material with a specified composition ratio of carbon atoms to silicon atoms in order to obtain an interlayer insulating film with low leakage current.
이와 같이, 반도체의 제조 프로세스에서 사용되는 재료에 포함되는 불순물 등으로부터 유래하는 탄소량을 관리하는 것이 필요로 되고 있다.In this way, it is necessary to manage the amount of carbon derived from impurities and the like contained in materials used in the semiconductor manufacturing process.
한편, 탄소량을 측정하는 방법으로서, 특허문헌 3에는, 연료 전지용 각종 금속제 부품 및 세라믹제 부품에 부착 잔류되어 있는 유분의 분석 방법으로서, 유분을 구성하는 탄화수소류를 산소와 반응시켜 일산화탄소 또는 이산화탄소로 변환시키고, 이것을 적외선 검출기로 측정하여 탄소량을 구하는 분석 방법이 기재되어 있다.On the other hand, as a method for measuring the amount of carbon, Patent Document 3 describes a method for analyzing oil remaining attached to various metal parts and ceramic parts for fuel cells, in which hydrocarbons constituting the oil react with oxygen to produce carbon monoxide or carbon dioxide. An analysis method is described to determine the amount of carbon by converting it and measuring it with an infrared detector.
또한, 특허문헌 4에는, 금선에 부착된 유기물을 고온에서 열분해하여, 생성된 메탄과 에틸렌을 열분해 가스 크로마토그래프 장치로 측정하여 전체 탄소량을 정량하는 방법이 기재되어 있다.Additionally, Patent Document 4 describes a method of pyrolyzing organic matter attached to a gold wire at high temperature and measuring the produced methane and ethylene using a pyrolysis gas chromatograph to quantify the total carbon amount.
또한, 특허문헌 5에는, 가스 크로마토그래프를 사용하여 탄소를 분석하는 방법으로서, 시료를 메탄 컨버터로 처리하고, 시료 중에 포함되는 일산화탄소, 이산화탄소 및 유기 화합물 등을 수소로 환원하여 탄소를 메탄으로 변환시키고, 그 메탄을 가스 크로마토그래프로 검출함으로써 탄소를 정량하는 방법이 개시되어 있다.In addition, Patent Document 5 describes a method of analyzing carbon using a gas chromatograph, in which a sample is treated with a methane converter, carbon monoxide, carbon dioxide, and organic compounds contained in the sample are reduced with hydrogen, and carbon is converted into methane. , a method of quantifying carbon by detecting the methane using a gas chromatograph is disclosed.
특허문헌 3에 기재된 탄소의 정량 방법은, 연소 적외선 흡수법이라고 칭해지고, 액체 시료로도 분석 가능하고, 탄소의 검출 한계도 1질량ppm까지 달하고 있으며, 우수한 탄소의 정량 분석 방법이다. 그러나, 이 방법으로 탄소 원자를 포함하는 할로겐화 금속 화합물 원료를 연소시키거나, 특허문헌 4의 방법으로 탄소 원자를 포함하는 할로겐화 금속 화합물 원료를 열분해시키거나 하면, 할로겐 가스나 할로겐화수소 가스가 발생하여 분석 장치의 금속부를 부식시킬 우려가 있기 때문에, 연소 적외선 흡수법이나 열분해 가스 크로마토그래프에 의해 할로겐화 금속 화합물 원료에 포함되는 탄소를 정량하기가 곤란하다.The method for quantifying carbon described in Patent Document 3 is called combustion infrared absorption method, can be analyzed even with liquid samples, and has a carbon detection limit of up to 1 mass ppm, and is an excellent carbon quantitative analysis method. However, when a halogenated metal compound raw material containing a carbon atom is burned using this method or a halogenated metal compound raw material containing a carbon atom is thermally decomposed using the method of Patent Document 4, halogen gas or hydrogen halide gas is generated and cannot be analyzed. Because there is a risk of corroding the metal part of the device, it is difficult to quantify the carbon contained in the halogenated metal compound raw material by combustion infrared absorption method or pyrolysis gas chromatography.
또한, 특허문헌 5에 기재된 메탄 컨버터를 사용하여 시료 중의 탄소를 메탄으로 변환시키는 방법을, 탄소 원자를 포함하는 할로겐화 금속 화합물 원료에 적용하면, 부생성물로서 부식성이 높은 할로겐화수소나 할로겐 가스가 생성된다. 이에 의해, 예를 들어 니켈 화합물 등을 포함하는 환원 촉매가 실활되거나, 분석 장치의 금속부의 부식이 발생하거나 하기 때문에, 메탄 컨버터의 사용은 곤란하다. 또한, 할로겐화 금속 화합물인 염화실란류를 수소로 환원하면, 발화나 폭발 등의 반응 활성이 높은 금속 수소화물인 실란류가 되기 때문에, 할로겐화 금속 화합물 원료의 분석 작업의 위험성이 매우 높아지는 문제도 있다.In addition, when the method of converting carbon in a sample into methane using a methane converter described in Patent Document 5 is applied to a halogenated metal compound raw material containing carbon atoms, highly corrosive hydrogen halide and halogen gas are generated as by-products. . As a result, for example, the reduction catalyst containing a nickel compound or the like is deactivated or corrosion of the metal part of the analysis device occurs, making it difficult to use a methane converter. In addition, when chlorosilanes, which are halogenated metal compounds, are reduced with hydrogen, they become silanes, which are metal hydrides with high reaction activity such as ignition or explosion, so there is a problem that the risk of analysis of halogenated metal compound raw materials is greatly increased.
본 발명은 장치의 부식이나 작업의 위험성이 없는 안전한 방법으로, 가수분해성을 갖는 할로겐화 금속 화합물과, 불순물 등으로부터 유래하는 유기 성분을 포함하는 원료에 포함되는 탄소, 또는 가수분해성을 갖고, 할로겐 원자 및 탄소 원자를 포함하는 금속 화합물에 포함되는 탄소를 정량하는 방법을 제공하는 것을 목적으로 한다.The present invention is a safe method that does not cause corrosion of the equipment or the risk of operation. Carbon contained in raw materials containing hydrolyzable halogenated metal compounds and organic components derived from impurities, etc., or hydrolyzable, halogen atoms and The purpose is to provide a method for quantifying carbon contained in a metal compound containing carbon atoms.
본 발명자는, 상기 과제를 해결하기 위해 예의 검토한 결과, 할로겐화 금속 화합물의 가수분해를 이용하여, 가수분해성을 갖는 할로겐화 금속 화합물과, 불순물 등으로부터 유래하는 유기 성분을 포함하는 원료에 포함되는 탄소, 또는 가수분해성을 갖고, 할로겐 원자 및 탄소 원자를 포함하는 금속 화합물에 포함되는 탄소의 양을 효율적으로 정량 가능하다는 것을 알아내어, 본 발명을 완성하기에 이르렀다.As a result of intensive studies to solve the above problems, the present inventors have found that, by using hydrolysis of the halogenated metal compound, the carbon contained in the raw material containing the hydrolyzable halogenated metal compound and the organic component derived from impurities, etc. Alternatively, it has been discovered that the amount of carbon contained in a metal compound that is hydrolyzable and contains a halogen atom and a carbon atom can be efficiently quantified, thereby completing the present invention.
본 발명은 이하의 제1 발명 및 제2 발명이다.The present invention is the following first and second inventions.
제1 발명은, 가수분해성을 갖는 할로겐화 금속 화합물(이하, 「할로겐화 금속 화합물 (P)」라고 함) 및 유기 성분을 포함하는 원료와, 물을 혼합하여, 상기 할로겐화 금속 화합물 (P)를 가수분해시켜, 가수분해물을 형성한 후, 해당 가수분해물 및 상기 유기 성분의 혼합물을 회수하고, 해당 혼합물의 탄소 분석에 의해 탄소량을 얻는 것을 특징으로 하는, 탄소 분석 방법이다.In the first invention, a raw material containing a hydrolyzable halogenated metal compound (hereinafter referred to as “halogenated metal compound (P)”) and an organic component is mixed with water, and the halogenated metal compound (P) is hydrolyzed. This is a carbon analysis method characterized by forming a hydrolyzate, recovering the mixture of the hydrolyzate and the organic component, and obtaining the carbon amount by carbon analysis of the mixture.
제1 발명에 있어서, 상기 물은, 전체 유기 탄소의 함유량이 500ppb 이하인 순수인 것이 바람직하다.In the first invention, the water is preferably pure water with a total organic carbon content of 500 ppb or less.
제1 발명에 있어서, 상기 할로겐화 금속 화합물 (P)를 구성하는 금속 원자가 규소 원자, 게르마늄 원자 또는 텅스텐 원자이며, 상기 할로겐 원자가 염소 원자인 것이 바람직하다.In the first invention, it is preferable that the metal atom constituting the halogenated metal compound (P) is a silicon atom, a germanium atom, or a tungsten atom, and the halogen atom is a chlorine atom.
제1 발명에 있어서, 상기 가수분해물을 얻었을 때 부생된 할로겐화수소를, 30 내지 180℃의 가열에 의해 제거하는 것이 바람직하다.In the first invention, it is preferable to remove the hydrogen halide by-produced when the hydrolyzate is obtained by heating at 30 to 180°C.
제1 발명에 있어서, 상기 가수분해물이 액체인 경우, 상기 할로겐화 금속 화합물 (P)는, 담체에 담지시켜 사용하는 것이 바람직하다.In the first invention, when the hydrolyzate is a liquid, it is preferable to use the halogenated metal compound (P) while supporting it on a carrier.
제2 발명은, 가수분해성을 갖고, 할로겐 원자 및 탄소 원자를 포함하는 금속 화합물(이하, 「할로겐화 금속 화합물 (Q)」라고 함)을 물에 의해 가수분해시켜, 상기 탄소 원자를 포함하는 가수분해물을 형성한 후, 해당 가수분해물을 탄소 분석하여 탄소량을 얻는 것을 특징으로 하는, 탄소 분석 방법이다.In the second invention, a metal compound (hereinafter referred to as “halogenated metal compound (Q)”) that has hydrolyzability and contains a halogen atom and a carbon atom is hydrolyzed with water to produce a hydrolyzate containing the carbon atom. It is a carbon analysis method characterized in that, after forming, the hydrolyzate is analyzed for carbon to obtain the carbon amount.
제2 발명에 있어서, 상기 물은, 전체 유기 탄소의 함유량이 500ppb 이하인 순수인 것이 바람직하다.In the second invention, the water is preferably pure water with a total organic carbon content of 500 ppb or less.
제2 발명에 있어서, 상기 할로겐화 금속 화합물 (Q)를 구성하는 금속 원자가 규소 원자 또는 게르마늄 원자이며, 상기 할로겐 원자가 염소 원자인 것이 바람직하다.In the second invention, it is preferable that the metal atom constituting the halogenated metal compound (Q) is a silicon atom or a germanium atom, and the halogen atom is a chlorine atom.
제2 발명에 있어서, 상기 가수분해물을 얻었을 때 부생된 할로겐화수소를, 30 내지 180℃의 가열에 의해 제거하는 것이 바람직하다.In the second invention, it is preferable to remove the hydrogen halide by-produced when the hydrolyzate is obtained by heating at 30 to 180°C.
제2 발명에 있어서, 상기 가수분해물이 액체인 경우, 상기 할로겐화 금속 화합물 (Q)는, 담체에 담지시켜 사용하는 것이 바람직하다.In the second invention, when the hydrolyzate is a liquid, the halogenated metal compound (Q) is preferably used while being supported on a carrier.
본 발명의 탄소 분석 방법에 따르면, 생성되는 가수분해물이 할로겐 성분을 함유하지 않으므로, 탄소량을, 종래의 정량 방법을 사용하여 효율적으로 분석할 수 있다. 그리고, 탄소 분석 장치의 금속부의 부식 등을 피할 수 있다. 제1 발명에 따르면, 불순물 등으로서 포함되는 유기 성분으로부터 유래하는 탄소량을 얻을 수 있고, 할로겐화 금속 화합물 (P)가, 탄소 원자를 포함하는 화합물인 경우에는, 불순물 등으로서 포함되는 유기 성분으로부터 유래하는 탄소량과의 합계 탄소량을 얻을 수 있다. 또한, 제2 발명에 따르면, 분석 대상의 할로겐화 금속 화합물 (Q)의 탄소량을 얻을 수 있다.According to the carbon analysis method of the present invention, the produced hydrolyzate does not contain a halogen component, so the amount of carbon can be efficiently analyzed using a conventional quantitative method. In addition, corrosion of the metal part of the carbon analysis device can be avoided. According to the first invention, the amount of carbon derived from the organic component contained as an impurity, etc. can be obtained, and when the halogenated metal compound (P) is a compound containing a carbon atom, the amount of carbon derived from the organic component contained as an impurity, etc. You can obtain the total carbon amount of the carbon amount. Additionally, according to the second invention, the carbon content of the halogenated metal compound (Q) to be analyzed can be obtained.
이하, 본 발명에 대하여 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 있어서의 분석 대상은, 탄소량을 관리할 필요가 있는, 반도체 등의 제조에서 사용되는, 할로겐 원자와, 이 할로겐 원자에 결합하는 금속 원자를 포함하는 가수분해 가능한 할로겐화 금속 화합물 (P) 또는 (Q)를 주로 하는 원료이다. 또한, 「가수분해성을 갖는다」 및 「가수분해 가능한」이란, 대상 화합물과 물의 반응에 의해, 할로겐화수소를 발생시키면서, 가수분해물을 형성하는 것을 의미한다.The object of analysis in the present invention is a hydrolyzable halogenated metal compound (P) containing a halogen atom and a metal atom bonded to the halogen atom, which is used in the manufacture of semiconductors and the like, and whose carbon content needs to be controlled. Or, it is a raw material mainly made of (Q). In addition, “having hydrolyzability” and “capable of hydrolyzing” mean that a hydrolyzate is formed while generating hydrogen halide through a reaction between the target compound and water.
가수분해성 할로겐 원자로서는, 염소 원자, 불소 원자 등을 들 수 있다. 이들 중, 염소 원자가 바람직하다. 또한, 할로겐화 금속 화합물 (P) 또는 (Q)를 구성하는 금속 원자로서는, 규소 원자, 티타늄 원자, 게르마늄 원자, 지르코늄 원자, 몰리브덴 원자, 주석 원자, 하프늄 원자, 텅스텐 원자 등을 들 수 있고, 이들 중 규소 원자, 게르마늄 원자 또는 텅스텐 원자가 바람직하다.Examples of hydrolyzable halogen atoms include chlorine atoms and fluorine atoms. Among these, chlorine atoms are preferred. In addition, the metal atom constituting the halogenated metal compound (P) or (Q) includes a silicon atom, a titanium atom, a germanium atom, a zirconium atom, a molybdenum atom, a tin atom, a hafnium atom, and a tungsten atom, among which Silicon atoms, germanium atoms or tungsten atoms are preferred.
상기 할로겐화 금속 화합물 (P) 및 (Q)는, 고체 및 액체 중 어느 것이어도 된다.The halogenated metal compounds (P) and (Q) may be either solid or liquid.
제1 발명에서 사용되는 할로겐화 금속 화합물 (P)는, 할로겐 원자 및 금속 원자를 포함하고, 탄소 원자를 포함하고 있어도 되는 화합물이다. 본 발명에 있어서는, 할로겐 원자 및 금속 원자의 결합, 혹은 할로겐 원자 및 금속 원자의 결합, 그리고 탄소 원자 및 금속 원자의 결합을 갖는, 염화규소 화합물, 염화게르마늄 화합물 또는 염화텅스텐 화합물이 바람직하다. 탄소 원자는, 탄화수소기로서 포함되는 것이 바람직하다. 염화규소 화합물로서는, 트리클로로메틸실란, 디클로로디메틸실란, 클로로트리메틸실란, 테트라클로로실란, 헥사클로로디실란 등을 들 수 있다. 또한, 염화게르마늄 화합물로서는, 트리클로로메틸게르마늄, 트리클로로디메틸아미노게르마늄, 염화게르마늄(II), 염화게르마늄(IV) 등을 들 수 있다. 또한, 염화텅스텐 화합물로서는, 염화텅스텐(III), 염화텅스텐(IV), 염화텅스텐(VI) 등을 들 수 있다. 또한, 테트라클로로실란, 헥사클로로디실란, 트리클로로메틸실란, 디클로로디메틸실란, 클로로트리메틸실란 등의 클로로실란 화합물의 가수분해물은, 통상, 폴리실록산이다.The halogenated metal compound (P) used in the first invention is a compound that contains a halogen atom and a metal atom and may also contain a carbon atom. In the present invention, a silicon chloride compound, a germanium chloride compound, or a tungsten chloride compound having a bond between a halogen atom and a metal atom, or a bond between a halogen atom and a metal atom, and a bond between a carbon atom and a metal atom, is preferred. The carbon atom is preferably contained as a hydrocarbon group. Examples of silicon chloride compounds include trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetrachlorosilane, and hexachlorodisilane. Additionally, examples of germanium chloride compounds include trichloromethyl germanium, trichlorodimethylamino germanium, germanium(II) chloride, and germanium(IV) chloride. In addition, examples of tungsten chloride compounds include tungsten (III) chloride, tungsten (IV) chloride, and tungsten (VI) chloride. Additionally, hydrolysates of chlorosilane compounds such as tetrachlorosilane, hexachlorodisilane, trichloromethylsilane, dichlorodimethylsilane, and chlorotrimethylsilane are usually polysiloxanes.
제1 발명에서 사용되는 할로겐화 금속 화합물 (P)는, 1종만이어도 되고, 2종 이상이어도 된다.The number of halogenated metal compounds (P) used in the first invention may be one, or two or more types may be used.
상기 할로겐화 금속 화합물 (P)는, 할로겐 원자 및 금속 원자를 포함하는 화합물을 포함하는 것이 바람직하다.The halogenated metal compound (P) preferably contains a compound containing a halogen atom and a metal atom.
또한, 제2 발명에서 사용되는 할로겐화 금속 화합물 (Q)는, 할로겐 원자, 탄소 원자 및 금속 원자를 포함하는 화합물이다. 본 발명에 있어서는, 염화규소 화합물 및 염화게르마늄 화합물이 바람직하다. 염화규소 화합물로서는, 트리클로로메틸실란, 디클로로디메틸실란, 클로로트리메틸실란 등을 들 수 있다. 또한, 염화게르마늄 화합물로서는, 트리클로로메틸게르마늄, 트리클로로디메틸아미노게르마늄 등을 들 수 있다.Additionally, 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, silicon chloride compounds and germanium chloride compounds are preferred. Examples of silicon chloride compounds include trichloromethylsilane, dichlorodimethylsilane, and chlorotrimethylsilane. Additionally, examples of germanium chloride compounds include trichloromethyl germanium and trichlorodimethylamino germanium.
제2 발명에서 사용되는 할로겐화 금속 화합물 (Q)는, 1종만이어도 되고, 2종 이상이어도 된다.The number of halogenated metal compounds (Q) used in the second invention may be one, or two or more types may be used.
제1 발명에 있어서의 유기 성분은, 통상, 유분이며, 불순물 등으로서 미량 함유되는 성분이다. 이 유기 성분의 가수분해성은, 정량성에 영향을 주지 않는다는 점에서, 특별히 한정되지 않는다.The organic component in the first invention is usually oil and is contained in a trace amount as an impurity or the like. The hydrolyzability of this organic component is not particularly limited in that it does not affect quantification.
제1 발명 및 제2 발명에서는, 처음에, 할로겐화 금속 화합물 (P) 및 유기 성분을 포함하는 원료 또는 할로겐화 금속 화합물 (Q)를 물에 의해 가수분해시킨다. 물은 특별히 한정되지 않지만, 순수가 바람직하다. 이 순수에 있어서의 전체 유기 탄소(TOC)의 함유량은, 바람직하게는 500질량ppb 이하이고, 더욱 바람직하게는 100질량ppb 이하, 특히 바람직하게는 50질량ppb 이하(초순수)이다.In the first and second inventions, first, the raw material containing the halogenated metal compound (P) and the organic component or the halogenated metal compound (Q) is hydrolyzed with water. Water is not particularly limited, but pure water is preferable. The total organic carbon (TOC) content in this pure water is preferably 500 ppb by mass or less, more preferably 100 ppb by mass or less, and especially preferably 50 ppb by mass or less (ultrapure water).
가수분해에서는, 할로겐화 금속 화합물 (P) 또는 (Q)에 포함되는 할로겐 원자의 당량보다 과잉량의 물을 청정한 용기에 수용하고, 거기에 할로겐화 금속 화합물 (P) 또는 (Q)를 소량씩 첨가하는 것이 바람직하다. 이때 발열이 심한 경우에는, 발열의 정도에 따라 내용물을 냉각하는 것이 바람직하다. 가수분해에 요하는 시간은, 할로겐화 금속 화합물 (P) 또는 (Q)의 종류 또는 양에 따라 다르지만, 일반적으로 약 25℃에서 24시간 이상 방치하는 것이 바람직하다.In hydrolysis, water in excess of the equivalent weight of halogen atoms contained in the halogenated metal compound (P) or (Q) is placed in a clean container, and the halogenated metal compound (P) or (Q) is added thereto in small amounts. It is desirable. At this time, if the fever is severe, it is desirable to cool the contents depending on the degree of fever. The time required for hydrolysis varies depending on the type or amount of the halogenated metal compound (P) or (Q), but it is generally preferable to leave it at about 25°C for 24 hours or more.
물의 사용량은, 가수분해의 반응성의 관점에서, 할로겐화 금속 화합물 (P) 또는 (Q) 1질량부에 대하여, 바람직하게는 1 내지 100질량부, 더욱 바람직하게는 5 내지 50질량부이다.The amount of water used is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 1 part by mass of the halogenated metal compound (P) or (Q) from the viewpoint of hydrolysis reactivity.
물의 사용량이 1질량부 미만에서는, 가수분해가 충분히 진행되지 않는 경우가 있다. 또한, 물의 사용량이 지나치게 많으면, 후속 공정에서 물의 제거에 손이 많이 가는 경우가 있다.If the amount of water used is less than 1 part by mass, hydrolysis may not proceed sufficiently. Additionally, if the amount of water used is too large, it may be difficult to remove the water in subsequent processes.
상기 할로겐화 금속 화합물 (P) 또는 (Q)의 가수분해에 의해 얻어지는 가수분해물은, 일반적으로 고체이며, 가수분해 후에는, 그의 수상이 염화수소 등의 할로겐화수소를 포함하는 현탁액이 된다. 이 할로겐화수소는, 분석 장치에 악영향을 미치기 때문에, 상압 또는 감압 하, 현탁액의 가열 건조를 행하여, 물과 함께 제거함으로써, 분석에 적합한 고체 물질을 얻는다.The hydrolyzate obtained by hydrolysis of the above-mentioned halogenated metal compound (P) or (Q) is generally a solid, and after hydrolysis, its aqueous phase becomes a suspension containing a hydrogen halide such as hydrogen chloride. Since this hydrogen halide has a negative effect on the analysis device, the suspension is heated and dried under normal or reduced pressure and removed along with water to obtain a solid substance suitable for analysis.
제1 발명에서는, 가수분해 후에, 가수분해물 및 유기 성분의 혼합물이, 통상, 가수분해물에 유기 성분이 포함된 형태로 되어 얻어진다. 또한, 제1 발명에서는, 유기 성분이 가수분해성을 갖는 경우, 할로겐화 금속 화합물 (P)의 가수분해물, 및 상기 유기 성분의 가수분해물의 혼합물이 얻어진다.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. Furthermore, in the first invention, when the organic component has hydrolyzability, a mixture of a hydrolyzate of the halogenated metal compound (P) and a hydrolyzate of the organic component is obtained.
상기 가열 건조의 조건으로서 온도는, 가수분해물을 변질시키지 않고, 할로겐화수소를 효율적으로 제거시킨다는 점에서, 바람직하게는 30 내지 180℃, 더욱 바람직하게는 80 내지 120℃이다. 가열 온도가 30℃ 미만에서는 건조가 불충분하고 할로겐화수소가 잔류하여 분석 장치에 악영향을 미칠 가능성이 있고, 또한 건조 온도가 180℃를 초과하면 가수분해물에 포함된 유기 성분이 휘발되거나, 분해되거나 할 가능성이 높아지기 때문에 바람직하지 않다.The temperature as conditions for the heat drying is preferably 30 to 180°C, more preferably 80 to 120°C, in that hydrogen halide is efficiently removed without deteriorating the hydrolyzate. If the heating temperature is less than 30°C, drying is insufficient and hydrogen halides may remain, which may adversely affect the analysis device. Additionally, if the drying temperature exceeds 180°C, organic components contained in the hydrolyzate may volatilize or decompose. This is not desirable because it increases.
또한, 가열 건조의 분위기는, 특별히 한정되지 않지만, 불활성 가스 분위기가 바람직하다. 불활성 가스 분위기로 함으로써, 가수분해물의 건조가 촉진되고, 유기 성분의 산화 분해도 억제할 수 있다. 불활성 가스로서는, 질소를 사용하는 것이 바람직하다.In addition, the atmosphere for heat drying is not particularly limited, but an inert gas atmosphere is preferable. By using an inert gas atmosphere, drying of the hydrolyzate is promoted and oxidative decomposition of the organic components can also be suppressed. As the inert gas, it is preferable to use nitrogen.
상기 가열 건조는, 바람직하게는 물에 적신 pH 시험지를 배기 가스에 쐬여, pH6 이상 및 항량으로 되었음을 확인하고 종료한다.The heat drying is preferably completed by exposing the pH test paper soaked in water to exhaust gas to confirm that the pH has reached 6 or higher and a constant weight.
그 후, 회수물을, 탄소 분석에 제공함으로써, 탄소량을 얻을 수 있다.Thereafter, the amount of carbon can be obtained by subjecting the recovered product to carbon analysis.
또한, 할로겐화 금속 화합물 (P)의 가수분해에 의해 얻어지는 가수분해물이 고체로 되지 않는 경우가 있다. 가수분해물이 액체인 경우에는, 할로겐화 금속 화합물 (P)와, 담체를 병용하는 것이 바람직하다.Additionally, there are cases where the hydrolyzate obtained by hydrolysis of the halogenated metal compound (P) does not turn into a solid. When the hydrolyzate is a liquid, it is preferable to use the halogenated metal compound (P) and the carrier together.
담체는, 특별히 한정되지 않지만, 후에 분석의 장해가 되지 않도록 하기 위해, 탄소의 함유량이 분석 장치의 정량 하한 미만인 화합물을 포함하는 분체를 사용하는 것이 바람직하다. 상기 담체로서는, 예를 들어 고순도의 테트라에톡시실란을 암모니아로 가수분해한 후, 소성시켜 얻어진 입경이 0.3 내지 3㎛인 실리카를 사용할 수 있다. 특히, 연소 적외선 흡수법으로 구한 탄소량이 0.003 내지 0.001질량％ 미만인 실리카가 적합하다.The carrier is not particularly limited, but in order to avoid interfering with later analysis, it is preferable to use a powder containing a compound whose carbon content is less than the lower limit of quantification of the analysis device. As the carrier, for example, silica having a particle size of 0.3 to 3 μm obtained by hydrolyzing high-purity tetraethoxysilane with ammonia and then calcining can be used. In particular, silica having a carbon content of 0.003 to less than 0.001% by mass as determined by combustion infrared absorption method is suitable.
담체를 사용하는 경우, 용기에, 담체와, 할로겐화 금속 화합물 (P)를 포함하는 원료를 첨가하고, 과잉의 물을 첨가하여 가수분해를 행한다. 또한, 미리, 담체의 탄소량을 분석해 둠으로써, 정확한 탄소량을 얻을 수 있다.When using a carrier, a carrier and a raw material containing a halogenated metal compound (P) are added to a container, and hydrolysis is performed by adding excess water. Additionally, by analyzing the carbon content of the carrier in advance, an accurate carbon content can be obtained.
상기 담체의 사용량은, 작업성의 관점에서, 할로겐화 금속 화합물 1질량부에 대하여, 바람직하게는 5 내지 100질량부, 더욱 바람직하게는 10 내지 50질량부이다.From the viewpoint of workability, the amount of the carrier used is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 1 part by mass of the halogenated metal compound.
액체의 가수분해물을 제공하는 할로겐화 금속 화합물 (P)와, 담체를 병용하는 경우, 가수분해 후에는, 물과, 액체의 가수분해물과, 담체와, 유기 성분을 포함하는 혼합액(현탁액)이 얻어진다. 그리고, 이 혼합액을 가열 건조하면, 액체의 가수분해물 및 유기 성분이 담체에 부착된 복합물이 얻어진다.When a halogenated metal compound (P), which provides a liquid hydrolyzate, and a carrier are used together, after hydrolysis, a mixed solution (suspension) containing water, the liquid hydrolyzate, the carrier, and the organic component is obtained. . Then, when this liquid mixture is heated and dried, a composite in which the liquid hydrolyzate and the organic component are attached to the carrier is obtained.
그 후, 회수물을, 탄소 분석에 제공함으로써, 탄소량을 얻을 수 있다.Thereafter, the amount of carbon can be obtained by subjecting the recovered product to carbon analysis.
한편, 제2 발명에 있어서, 가수분해물이 고체인 경우에는, 가수분해 후에, 상기와 같이 가열 건조를 행하여 가수분해물을 회수하고, 이것을 탄소 분석함으로써, 탄소량을 얻을 수 있다. 또한, 가수분해물이 액체인 경우에는, 상기와 같이 담체와, 할로겐화 금속 화합물 (Q)를 병용하여 가수분해를 행하고, 이어서, 가열 건조를 행함으로써, 가수분해물이 담체에 부착된 복합물이 얻어진다.On the other hand, in the second invention, when the hydrolyzate is a solid, after hydrolysis, the hydrolyzate is recovered by heating and drying as described above, and the carbon amount can be obtained by analyzing this for carbon. In addition, when the hydrolyzate is a liquid, hydrolysis is performed using the carrier and the halogenated metal compound (Q) together as described above, and then heat-drying is performed, thereby obtaining a composite in which the hydrolyzate is attached to the carrier.
그 후, 회수물을, 탄소 분석에 제공함으로써, 탄소량을 얻을 수 있다.Thereafter, the amount of carbon can be obtained by subjecting the recovered product to carbon analysis.
제1 발명 및 제2 발명에 있어서, 탄소 분석을 행하는 경우에는, 회수물을 고온에서 연소시키고, 생성되는 이산화탄소를 적외선 검출기로 정량하는 장치가 적합하게 사용된다.In the first and second inventions, when carbon analysis is performed, an apparatus that combusts the recovered material at high temperature and quantifies the carbon dioxide produced with an infrared detector is suitably used.
예를 들어, LECO사제 탄소ㆍ황 분석 장치(CS844형 또는 CS744형), 호리바 세이사쿠쇼제 탄소ㆍ황 분석 장치(EMIA-920V2 또는 EMIA-810W), 엘레멘탈사제 전체 유기 탄소 측정 장치(vario TOC cube) 등을 사용할 수 있다.For example, carbon/sulfur analysis device (CS844 or CS744 type) manufactured by LECO, carbon/sulfur analyzer (EMIA-920V2 or EMIA-810W) manufactured by Horiba Seisakusho, and total organic carbon measuring device (vario TOC cube) manufactured by Elemental. etc. can be used.
액체의 가수분해물을 제공하는 할로겐화 금속 화합물과 병용하는 담체나, 사용하는 용기에는, 불순물로서의 유기 성분이 부착되어 있는 경우가 있기 때문에, 가수분해 및 가열 건조 후의 회수물은, 이 유기 성분을 포함하는 경우가 있다. 따라서, 담체의 탄소 분석, 또는 가수분해 및 가열 건조의 조작에 따라, 담체, 물 및 용기를 접촉시킨 후, 물을 제거하여 얻어진 담체 건조물의 탄소 분석을 미리 행해 두는 것이 바람직하다. 이하, 분석예를 나타낸다.Since organic components as impurities may adhere to the carrier used in combination with the halogenated metal compound that provides the liquid hydrolyzate or the container used, the recovered product after hydrolysis and heat drying contains these organic components. There are cases. Therefore, it is desirable to perform carbon analysis of the carrier in advance, or carbon analysis of the dried carrier product obtained by bringing the carrier, water, and container into contact through operations of hydrolysis and heat drying, and then removing the water. Below, an analysis example is shown.
분석예 1Analysis Example 1
고순도의 테트라에톡시실란을 암모니아로 가수분해시키고, 석출된 실리카를 900℃에서 소성함으로써 입경 2㎛의 구상 실리카를 얻었다. 구상 실리카를 초순수로 세정하고 나서 건조시킨 것을 「담체 X」로 하였다. 이 담체 건조물의 탄소량을, 연소 적외선 흡수법으로 구한 결과, 0.001질량％였다.High-purity tetraethoxysilane was hydrolyzed with ammonia, and the precipitated silica was calcined at 900°C to obtain spherical silica with a particle size of 2 μm. Globular silica was washed with ultrapure water and then dried, and was used as “Carrier X.” The carbon content of this carrier dried product was determined by combustion infrared absorption method and was found to be 0.001% by mass.
분석예 2Analysis Example 2
청정한 유리 용기에, 1.10질량부의 담체 X 및 20.00질량부의 초순수를 넣어 30분간 교반한 후, 유리 용기마다 질소 기류 하, 90℃에서 8시간, 추가로 120℃에서 19시간 건조시켰다. 이어서, 얻어진 담체 건조물의 탄소량을, 연소 적외선 흡수법으로 구한 결과, 0.003질량％였다.In a clean glass container, 1.10 parts by mass of carrier 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.
따라서, 가수분해 및 가열 건조에 수반하여 증대된 탄소량은 0.002질량％였다. 마찬가지의 조작을 한번 더 반복하는 시험, 및 초순수의 첨가량을 5질량부로 줄인 시험을 행하였지만, 증대된 탄소량은, 각각 0.001질량％ 및 0.003질량％였다.Therefore, the amount of carbon increased due to hydrolysis and heat drying was 0.002% by mass. A test in which the same operation was repeated once more and a test in which the addition amount of ultrapure water was reduced to 5 parts by mass were performed, but the increased carbon amounts were 0.001% by mass and 0.003% by mass, respectively.
<실시예><Example>
이하, 실시예에 의해, 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
실시예 1Example 1
청정한 유리 용기에 20.04질량부의 초순수(전체 유기 탄소의 함유량: 18질량ppb)를 넣었다. 그리고, 유리 용기에 빙수를 접촉시켜 초순수를 냉각하면서, 상압에서 증류 정제한 1.95질량부의 육염화이규소 원료(이하, 「HCD 원료」라고 약칭함)를 조금씩 첨가하였다. 이에 의해 HCD는 가수분해되고, 생성된 가수분해물(폴리실록산)에 의해 백탁된 슬러리를 얻었다. 이어서, 유리 용기를 밀봉하여 약 25℃에서 24시간 방치한 후, 개봉한 유리 용기마다 질소 기류 하, 90℃에서 8시간, 추가로 120℃에서 19시간 가열하였다. 이에 의해 건조물(백색 고체)을 얻었다. 사전에 측정해 둔 풍대와의 질량차로부터, 백색 고체의 질량은 0.86질량부였다. 얻어진 백색 고체의 탄소량을 연소 적외선 흡수법으로 구한바, 0.001질량％였다. 이 분석값을 기초로, 가수분해 전의 HCD 원료에 포함되는 탄소량(A)은, 하기 식 (1)로부터 4질량ppm이 되었다.20.04 parts by mass of ultrapure water (content of total organic carbon: 18 ppb by mass) was placed in a clean glass container. Then, while cooling the ultrapure water by bringing ice water into contact with the glass container, 1.95 parts by mass of silicon hexachloride raw material (hereinafter abbreviated as "HCD raw material") distilled and purified at normal pressure was added little by little. As a result, HCD was hydrolyzed, and a slurry that was cloudy due to the generated hydrolyzate (polysiloxane) was obtained. Next, the glass container was sealed and left at about 25°C for 24 hours, and then each 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, dried material (white solid) was obtained. From the mass difference with the windshield measured in advance, the mass of the white solid was 0.86 parts by mass. The carbon content of the obtained white solid was determined by combustion infrared absorption method and was found 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)A=[(B×C/100)/D]×1000000 (1)
여기서, A는 HCD 원료에 포함되는 탄소량(질량ppm), B는 가수분해물을 가열 건조시킨 후의 백색 고체의 질량, C는 연소 적외선 흡수법으로 구한 탄소량(질량％), D는 가수분해에 제공한 HCD 원료의 질량이다.Here, A is the amount of carbon contained in the HCD raw material (ppm by mass), B is the mass of the white solid after heating and drying the hydrolyzate, C is the amount of carbon (% by mass) determined by combustion infrared absorption method, and D is the amount of carbon contained in the HCD raw material (mass %). This is the mass of the provided HCD raw material.
그러나, 분석예 1 및 2로부터, 가수분해 조작에 의해, 탄소량의 분석값이 0.001 내지 0.002질량％ 높아지는 것이 확인되었다. 상기와 같이 백색 고체의 탄소량은 0.001질량％이기 때문에, HCD 원료에 포함되는 탄소량은, 실질적으로 제로라고 생각된다. 따라서, 탄소 성분이 포함되어 있었다고 해도, 탄소량을, 정량 하한 미만인 4질량ppm으로 결정하였다.However, from Analysis Examples 1 and 2, it was confirmed that the hydrolysis operation increased the analysis value of the carbon content by 0.001 to 0.002% by mass. 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 carbon amount was determined to be 4 mass ppm, which is less than the lower limit of quantification.
실시예 2Example 2
유리병에 실온에서 2년간 보관한 HCD(이하, 「HCD 시료」라고 약칭함)를 사용한 것 이외에는, 실시예 1과 마찬가지의 방법으로 탄소 분석을 행하였다. 얻어진 가수분해물인 백색 고체의 탄소량을 연소 적외선 흡수법으로 구한바, 0.054질량％였다. 가수분해 조작으로 탄소량은 0.001 내지 0.002질량％ 늘었음을 알 수 있기 때문에, 0.054질량％에서 0.002질량％를 뺀 0.052질량％를 백색 고체의 탄소량으로 하였다. 그리고, 상기 식 (1)에 의해, 가수분해 전의 HCD 시료에 포함된 탄소량을 구한바, 226질량ppm이었다.Carbon analysis was performed in the same manner as in Example 1, except that HCD (hereinafter abbreviated as “HCD sample”) stored in a glass bottle at room temperature for 2 years was used. The carbon content of the white solid that was the obtained hydrolyzate was determined by combustion infrared absorption method and was found to be 0.054% by mass. Since it can be seen that the carbon content increased by 0.001 to 0.002 mass% through the hydrolysis operation, 0.052 mass%, obtained by subtracting 0.002 mass% from 0.054 mass%, was taken as the carbon content of the white solid. Then, the amount of carbon contained in the HCD sample before hydrolysis was calculated using the above equation (1), and was found to be 226 ppm by mass.
또한, HCD를 보관하고 있던 유리병에는 폴리에틸렌제의 내부 덮개가 있었지만, 흑갈색으로 변색되어 단단하게 되었고, 전혀 유연성은 없어져 있었다. 또한, 내부 덮개는, 유리병의 개구부 내벽에 단단히 고착되어 있고, 내부 덮개와 유리의 계면에는 흰 부착물이 있었다. 그리고, 채취한 HCD 시료는 얇고 황색으로 착색되어 있었다.In addition, the glass bottle storing the HCD had an inner cover made of polyethylene, but it was discolored to dark brown, became hard, and had no flexibility at all. Additionally, the inner cover was firmly adhered to the inner wall of the opening of the glass bottle, and there was a white deposit at the interface between the inner cover and the glass. And, the collected HCD sample was thin and colored yellow.
이 실시예 2에서 226질량ppm의 탄소가 검출된 것은, 폴리에틸렌제의 내부 덮개의 열화나 변질에 수반하여 유기물이 HCD 중에 혼입되었기 때문이라고 추정된다.It is presumed that the reason that 226 mass ppm of carbon was detected in Example 2 was because organic matter was mixed into the HCD due to deterioration or deterioration of the polyethylene inner cover.
실시예 3Example 3
청정한 유리 용기에 5.15질량부의 초순수(전체 유기 탄소의 함유량: 18질량ppb)를 넣었다. 그리고, 유리 용기에 빙수를 접촉시켜 초순수를 냉각하면서, 1.93질량부의 증류 정제한 HCD에 0.02질량부의 트리클로로메틸실란(이하, 「TCMS」라고 약칭함)을 첨가한 혼합액을 초순수에 조금씩 첨가하고, 모두 첨가한 후 5시간 방치하였다. HCD 및 TCMS는 가수분해되고, 백탁된 슬러리를 얻었다. 이하, 실시예 1과 마찬가지의 조작을 행하여, 0.83질량부의 백색 고체를 얻었다. 얻어진 백색 고체의 탄소량을 연소 적외선 흡수법으로 구한바, 0.161질량％였다. 이 분석값을 기초로, HCD 및 TCMS의 혼합액에 포함되는 탄소량(E)은, 하기 식 (2)로부터 690질량ppm이 되었다.5.15 parts by mass of ultrapure water (content of total organic carbon: 18 ppb by mass) was placed in a clean glass container. Then, while cooling the ultrapure water by bringing ice water into contact with a glass container, a mixed solution of 1.93 parts by mass of distillation-purified HCD and 0.02 parts by mass of trichloromethylsilane (hereinafter abbreviated as "TCMS") was added little by little to the ultrapure water, After everything was added, it was left for 5 hours. HCD and TCMS were hydrolyzed, giving a cloudy slurry. Hereinafter, 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 combustion infrared absorption method and was found to be 0.161% by mass. Based on this analysis value, the amount of carbon (E) contained in the mixed liquid of HCD and TCMS was 690 ppm by mass from the following formula (2).
E=[(B×C/100)/(D+F)]×1000000 (2)E=[(B×C/100)/(D+F)]×1000000 (2)
여기서, E는 HCD 및 TCMS의 혼합액에 포함되는 탄소량(질량ppm), B는 가수분해물을 가열 건조시킨 후의 백색 고체의 질량, C는 연소 적외선 흡수법으로 구한 탄소량(질량％), D와 F는 각각 가수분해에 제공한 HCD 및 TCMS의 질량이다.Here, E is the amount of carbon contained in the mixed solution of HCD and TCMS (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 combustion infrared absorption method, D and F is the mass of HCD and TCMS contributed to hydrolysis, respectively.
실시예 4Example 4
2.04질량부의 담체 X 및 0.65질량부의 디클로로디메틸실란(DCDMS)을 청정한 유리 용기에 넣고, 추가로 5.09질량부의 초순수(전체 유기 탄소의 함유량: 18질량ppb)를 넣어, 이들을 30분간 교반하였다. 그 후, 유리 용기를 밀봉하여 약 25℃에서 24시간 방치하였다. 이어서, 개봉한 유리 용기마다 질소 기류 하, 90℃에서 8시간, 추가로 120℃에서 19시간 가열하였다. 이에 의해 건조물 2.27질량부를 얻었다. 이 건조물의 탄소량을 연소 적외선 흡수법으로 구한바, 4.32질량％였다.2.04 parts by mass of carrier After that, the glass container was sealed and left at about 25°C for 24 hours. Next, each 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 dried material was obtained. The carbon content of this dried product was determined by combustion infrared absorption method and was found to be 4.32% by mass.
이상으로부터, 담체 X와 DCDMS의 혼합물에 포함되는 탄소량은, 식 (2)로부터 3.65질량％로 구해졌다. 담체 X의 탄소량은 0.001질량％로 미량이므로 무시하면, DCDMS에 포함되는 탄소량은 15.1질량％로 구할 수 있었다.From the above, the amount of carbon contained in the mixture of carrier If the carbon content of carrier
본 발명에 있어서의 탄소 분석 방법은, 안전하면서도 간이한 방법으로, 반도체의 제조에 있어서 관리되는 탄소의 양을 정확하게 정량할 수 있는 방법이기 때문에, 반도체 등의 전자 재료 분야에서 유용한 분석 방법이다.The carbon analysis method in the present invention is a safe and simple method that can accurately quantify the amount of carbon controlled in the manufacture of semiconductors, and is therefore a useful analysis method in the field of electronic materials such as semiconductors.
Claims (10)
상기 가수분해물을 얻었을 때 부생된 할로겐화수소를, 불활성 분위기 하에서 30 내지 180℃의 가열에 의해 제거하는 공정을 구비하는 것을 특징으로 하는 탄소 분석 방법.A raw material containing a hydrolyzable halogenated metal compound and an organic component is mixed with water, the halogenated metal compound is hydrolyzed to form a hydrolyzate, and then the mixture of the hydrolyzate and the organic component is recovered, It is a carbon analysis method to obtain the amount of carbon by analyzing the carbon of the mixture,
A carbon analysis method comprising a step of removing hydrogen halide by-produced when the hydrolyzate is obtained by heating at 30 to 180° C. in an inert atmosphere.
상기 가수분해물을 얻었을 때 부생된 할로겐화수소를, 불활성 분위기 하에서 30 내지 180℃의 가열에 의해 제거하는 공정을 구비하는 것을 특징으로 하는 탄소 분석 방법.Carbon analysis to obtain the amount of carbon by hydrolyzing a metal compound that has hydrolyzability and contains a halogen atom and a carbon atom with water to form a hydrolyzate containing the carbon atom, and then analyzing the hydrolyzate for carbon. It is a method,
A carbon analysis method comprising a step of removing hydrogen halide by-produced when the hydrolyzate is obtained by heating at 30 to 180° C. in an inert atmosphere.
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