JP2008020343A - Agent for detecting germane and organic silicon compound - Google Patents
Agent for detecting germane and organic silicon compound Download PDFInfo
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- JP2008020343A JP2008020343A JP2006192842A JP2006192842A JP2008020343A JP 2008020343 A JP2008020343 A JP 2008020343A JP 2006192842 A JP2006192842 A JP 2006192842A JP 2006192842 A JP2006192842 A JP 2006192842A JP 2008020343 A JP2008020343 A JP 2008020343A
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- dichromate
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 229910000078 germane Inorganic materials 0.000 title claims abstract description 46
- 150000003377 silicon compounds Chemical class 0.000 title abstract description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims abstract description 8
- -1 vinyltrimethylsilane Chemical class 0.000 claims abstract description 7
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims description 103
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 41
- 238000000746 purification Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 7
- 101150065749 Churc1 gene Proteins 0.000 claims description 7
- 102100038239 Protein Churchill Human genes 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 4
- DXJZZRSMGLGFPW-UHFFFAOYSA-N triphenyl(prop-2-enyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 DXJZZRSMGLGFPW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 32
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OCXZUOIMVATIKY-UHFFFAOYSA-N [Cu].C[Si](C)(C)C=C Chemical compound [Cu].C[Si](C)(C)C=C OCXZUOIMVATIKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 1
- 229910052986 germanium hydride Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
本発明は、ゲルマン及び有機ケイ素化合物の検知剤に関する。さらに詳細には、半導体製造工程等から排出される排ガスに含まれるゲルマン及び有機ケイ素化合物を高感度で検知できる検知剤に関する。 The present invention relates to a detection agent for germane and organosilicon compounds. More specifically, the present invention relates to a detection agent that can detect germane and organosilicon compounds contained in exhaust gas discharged from a semiconductor manufacturing process or the like with high sensitivity.
半導体製造工業においては、アルシン、ホスフィン、ジボラン、セレン化水素等とともにゲルマンが原料ガスとして使用されている。ゲルマンを使用した際には、半導体製造工程からは、窒素、水素、ヘリウム等のガスで希釈された状態で、未反応のゲルマンが排出されるが、ゲルマンは毒性が高く、大気にそのまま放出した場合は人体及び環境に悪影響を与えるので、大気に放出するに先立ってゲルマンを含有する排ガスを浄化し、これが含まれていないことを確認する必要がある。 In the semiconductor manufacturing industry, germane is used as a source gas together with arsine, phosphine, diborane, hydrogen selenide and the like. When germane is used, unreacted germane is discharged from the semiconductor manufacturing process in a state diluted with a gas such as nitrogen, hydrogen, or helium, but germane is highly toxic and released directly into the atmosphere. In this case, since it adversely affects the human body and the environment, it is necessary to purify the exhaust gas containing germane and confirm that it is not contained before releasing it into the atmosphere.
また、ＣＶＤ法による銅の成膜として、ヘキサフルオロアセチルアセトン銅ビニルトリメチルシラン（（ＣＦ3ＣＯ）2ＣＨＣｕ・ＣＨ2ＣＨＳｉ（ＣＨ3）3）、ヘキサフルオロアセチルアセトン銅アリルトリメチルシラン（（ＣＦ3ＣＯ）2ＣＨＣｕ・ＣＨ2ＣＨＣＨ2Ｓｉ（ＣＨ3）3）等がＣＶＤ原料として使用されている。これらのＣＶＤ原料を使用した際には、半導体製造工程からは、窒素、水素、ヘリウム等のガスで希釈された状態で、分解物であるビニルトリメチルシラン、アリルトリメチルシラン等の有機ケイ素化合物が排出されるが、これらの有機ケイ素化合物も毒性が高く、大気にそのまま放出した場合は人体及び環境に悪影響を与えるので、大気に放出するに先立って有機ケイ素化合物を含有する排ガスを浄化し、これらが含まれていないことを確認する必要がある。 In addition, as a copper film formed by CVD, hexafluoroacetylacetone copper vinyltrimethylsilane ((CF 3 CO) 2 CHCu · CH 2 CHSi (CH 3 ) 3 ), hexafluoroacetylacetone copper allyltrimethylsilane ((CF 3 CO) 2 CHCu · CH 2 CHCH 2 Si (CH 3 ) 3 ) or the like is used as a CVD raw material. When these CVD raw materials are used, organic silicon compounds such as vinyltrimethylsilane and allyltrimethylsilane, which are decomposition products, are discharged from the semiconductor manufacturing process in a state diluted with a gas such as nitrogen, hydrogen, or helium. However, these organosilicon compounds are also highly toxic and, if released into the atmosphere as they are, will adversely affect the human body and the environment. Prior to release into the atmosphere, the exhaust gases containing the organosilicon compounds are purified, It is necessary to confirm that it is not included.
そのため、半導体製造工程から排出されるゲルマンあるいは有機ケイ素化合物を含む排ガスを、例えば乾式浄化法により浄化する場合は、浄化筒の破過を検知してこれらの有害成分が外部に放出されないようにしてきた。このような状況下、取り扱いが容易で感度が高いゲルマンあるいは有機ケイ素化合物を検知するための検知剤が開発されている。このような検知剤の多くは、有害成分と接触すると変色する成分を無機質担体に担持させてなる検知剤である。 For this reason, when exhaust gas containing germane or organosilicon compounds discharged from the semiconductor manufacturing process is purified by, for example, the dry cleaning method, it detects the breakthrough of the cleaning cylinder so that these harmful components are not released to the outside. It was. Under such circumstances, detection agents for detecting germane or organosilicon compounds that are easy to handle and have high sensitivity have been developed. Many of such detection agents are detection agents in which a component that changes color when in contact with harmful components is supported on an inorganic carrier.
従来から、ゲルマン等の水素化物ガスを検知するための検知剤としては、例えば、第二銅塩とパラジウム塩との混合物を変色成分とする検知剤（特開昭６２−２２０６２号公報）、第二銅塩と金塩との混合物を変色成分とする検知剤（特開平２−３２２５４号公報）、モリブデン酸及びモリブデン酸塩の少なくとも一種を変色成分とする検知剤（特開平８−１２９００９号公報）、アルカリ金属の過マンガン酸塩を変色成分とする検知剤（特開２００３−２０７５００号公報）が知られている。また、有機ケイ素化合物を検知するための検知剤としても、アルカリ金属の過マンガン酸塩を変色成分とする検知剤（特開２００３−２０７４９９号公報）が知られている。 Conventionally, as a detection agent for detecting hydride gas such as germane, for example, a detection agent having a color-changing component of a mixture of cupric salt and palladium salt (JP-A-62-22062), No. 1 A detector using a mixture of a dicopper salt and a gold salt as a color-changing component (JP-A-2-32254), a detection agent using at least one of molybdic acid and molybdate as a color-changing component (JP-A-8-129209) ), A detection agent (Japanese Patent Application Laid-Open No. 2003-207500) using an alkali metal permanganate as a discoloring component is known. Further, as a detection agent for detecting an organosilicon compound, a detection agent (Japanese Patent Laid-Open No. 2003-207499) using an alkali metal permanganate as a color changing component is known.
これらの検知剤を用いた検知方法としては、前記のような変色成分を含む検知剤をガラス管に充填して検知管を製作した後、サンプリングした検査対象ガスを検知管に通して、その変色によりゲルマンあるいは有機ケイ素化合物の有無を検知する方法、排ガスの浄化筒の浄化剤の下流側の覗き窓部に検知剤を充填した後、ゲルマンあるいは有機ケイ素化合物を含む排ガスを流通し、その変色によって浄化筒の破過を検知する方法等が一般的に用いられている。
しかしながら、第二銅塩とパラジウム塩との混合物を変色成分とする検知剤は、水素の存在下では水素により変色するので、水素を含むガス中のゲルマンを選択的に検知することができないほか、ゲルマンまたは有機ケイ素化合物と、浄化剤が反応して水素を発生するような浄化筒の破過を検知することができないという不都合があった。また、第二銅塩と金塩との混合物を変色成分とする検知剤、モリブデン酸及びモリブデン酸塩の少なくとも一種を変色成分とする検知剤は、アルシン、ホスフィンを高感度で検知することができるが、ゲルマン、有機ケイ素化合物の検知については充分な感度が得られなかった。さらに、アルカリ金属の過マンガン酸塩を変色成分とする検知剤は、光により感度が低下するので、使用するまでの期間、光に当たらないように保存に注意が必要であるという欠点があった。 However, the detection agent that uses a mixture of cupric salt and palladium salt as a color-changing component is discolored by hydrogen in the presence of hydrogen, so it cannot selectively detect germane in a gas containing hydrogen, There has been a disadvantage that it is not possible to detect breakthrough of the purification cylinder in which germanium or an organosilicon compound reacts with the purification agent to generate hydrogen. Moreover, the detection agent which uses a mixture of cupric salt and gold salt as a color-changing component, and the detection agent which uses at least one of molybdic acid and molybdate as a color-changing component can detect arsine and phosphine with high sensitivity. However, sufficient sensitivity could not be obtained for detection of germane and organosilicon compounds. Furthermore, the detection agent having a discoloration component of an alkali metal permanganate has a drawback in that the sensitivity is lowered by light, so that care must be taken for storage so that it is not exposed to light until it is used. .
従って、本発明が解決しようとする課題は、半導体製造工程等から排出されるゲルマン及び有機ケイ素化合物を、雰囲気ガスに影響されることなく高感度で検知でき、しかも使用するまでの期間中、光等により容易に感度が低下しない検知剤を提供することである。 Therefore, the problem to be solved by the present invention is that germane and organosilicon compounds discharged from the semiconductor manufacturing process and the like can be detected with high sensitivity without being affected by atmospheric gas, and light is used during the period until use. It is an object of the present invention to provide a detection agent whose sensitivity is not easily lowered by such as.
本発明者らは、これらの課題を解決すべく鋭意検討した結果、変色成分として重クロム酸塩を用いることにより、ゲルマン及び有機ケイ素化合物を、雰囲気ガスに影響されることなく高感度で検知でき、しかも使用するまでの期間中、光等により容易に感度が低下しないことを見出し、本発明のゲルマン及び有機ケイ素化合物の検知剤に到達した。
すなわち本発明は無機質担体に変色成分として重クロム酸塩を担持させてなることを特徴とするゲルマンの検知剤である。
また、本発明は、無機質担体に変色成分として重クロム酸塩を担持させてなることを特徴とする一般式ＣＨ２ＣＨ-ＳｉＲ３、ＣＨ２ＣＨ-Ｓｉ(ＯＲ)３、ＣＨ２ＣＨＣＨ２-ＳｉＲ３、またはＣＨ２ＣＨＣＨ２-Ｓｉ(ＯＲ)３（Ｒは飽和炭化水素または芳香族化合物）で表される有機ケイ素化合物の検知剤である。
As a result of diligent studies to solve these problems, the present inventors can detect germane and organosilicon compounds with high sensitivity without being affected by atmospheric gas by using dichromate as a color-changing component. In addition, during the period until use, the inventors found that the sensitivity was not easily lowered by light or the like, and reached the germane and organosilicon compound detectors of the present invention.
That is, the present invention is a germane detection agent comprising a dichromate supported on an inorganic carrier as a discoloring component.
Further, the present invention provides a general formula CH 2 CH—SiR 3 , CH 2 CH—Si (OR) 3 , CH 2 CHCH 2 −, wherein a dichromate is supported as a discoloring component on an inorganic carrier. It is a detector for an organosilicon compound represented by SiR 3 or CH 2 CHCH 2 —Si (OR) 3 (R is a saturated hydrocarbon or aromatic compound).
本発明のゲルマン及び有機ケイ素化合物の検知剤により、半導体製造工程等から排出されるゲルマン及び有機ケイ素化合物を、雰囲気ガスに影響されることなく高感度で検知することが可能となった。また、本発明の検知剤は、光等により容易に感度が低下しないので、使用するまでの保存が容易である。 The germane and organosilicon compound detectors of the present invention make it possible to detect germane and organosilicon compounds discharged from semiconductor manufacturing processes and the like with high sensitivity without being affected by the atmospheric gas. Moreover, since the sensitivity of the detection agent of the present invention is not easily lowered by light or the like, it can be easily stored until it is used.
本発明は、窒素、水素、アルゴン、ヘリウム等をベースガスとして含むガス中に存在するゲルマン及び有機ケイ素化合物を検知する検知剤に適用されるが、特に水素を含むガス中のゲルマン及び有機ケイ素化合物の検知に効果が発揮される。尚、本発明におけるゲルマンは、モノゲルマン（ＧｅＨ４）のほか、ジゲルマン（Ｇｅ２Ｈ６）、トリゲルマン（Ｇｅ３Ｈ８）を含むものである。また、本発明における有機ケイ素化合物は、一般式ＣＨ２ＣＨ-ＳｉＲ３、ＣＨ２ＣＨ-Ｓｉ(ＯＲ)３、ＣＨ２ＣＨＣＨ２-ＳｉＲ３、またはＣＨ２ＣＨＣＨ２-Ｓｉ(ＯＲ)３（Ｒは飽和炭化水素または芳香族化合物）で表される有機ケイ素化合物であり、例えば、ビニルトリメチルシラン、ビニルトリメトキシシラン、アリルトリメチルシラン、アリルトリメトキシシラン、アリルトリフェニルシラン等である。 The present invention is applied to a detection agent for detecting germane and an organosilicon compound present in a gas containing nitrogen, hydrogen, argon, helium or the like as a base gas, and in particular, germane and an organosilicon compound in a gas containing hydrogen. Effective in detecting The germane in the present invention includes digermane (Ge 2 H 6 ) and trigermane (Ge 3 H 8 ) in addition to monogermane (GeH 4 ). The organosilicon compound in the present invention has a general formula of CH 2 CH—SiR 3 , CH 2 CH—Si (OR) 3 , CH 2 CHCH 2 —SiR 3 , or CH 2 CHCH 2 —Si (OR) 3 (R). Is an organosilicon compound represented by a saturated hydrocarbon or aromatic compound), such as vinyltrimethylsilane, vinyltrimethoxysilane, allyltrimethylsilane, allyltrimethoxysilane, allyltriphenylsilane, and the like.
以下、本発明の検知剤について詳細に説明する。
本発明のゲルマン及び有機ケイ素化合物の検知剤においては、重クロム酸塩が無機質担体に担持せしめられて検知剤とされる。無機質担体としては、シリカゲル、アルミナ、ジルコニア、チタニア、シリカアルミナ、シリカチタニア等を例示することができる。しかし、これらの無機質担体の中で、高比表面積の無機質担体として使用でき高感度の検知剤が得られる点からシリカゲルを用いることが好ましい。無機質担体の形態には特に制限はないが、シリカゲルの場合は、通常は比表面積が０．１〜４００ｍ２／ｇの範囲のものが使用可能である。
Hereinafter, the detection agent of the present invention will be described in detail.
In the germanium and organosilicon compound detection agents of the present invention, dichromate is supported on an inorganic carrier to form a detection agent. Examples of the inorganic carrier include silica gel, alumina, zirconia, titania, silica alumina, silica titania and the like. However, among these inorganic carriers, silica gel is preferably used because it can be used as an inorganic carrier having a high specific surface area and a highly sensitive detection agent can be obtained. The form of the inorganic carrier is not particularly limited, but in the case of silica gel, those having a specific surface area in the range of 0.1 to 400 m 2 / g can be used.
本発明の検知剤における重クロム酸塩としては、重クロム酸アンモニウム、または重クロム酸カリウム等のアルカリ金属の重クロム酸塩を挙げることができる。重クロム酸塩の含有量は、無機質担体に対して、通常は０．０５〜１０ｗｔ％、好ましくは０．１〜５．０ｗｔ％である。重クロム酸塩の含有量が無機質担体に対して０．０５ｗｔ％未満の場合は、検知剤の変色成分の色が薄すぎて検知しにくくなる不都合を生じる。また、重クロム酸塩の含有量が無機質担体に対して１０ｗｔ％を超える場合は、水素に対して変色しやすくなる不都合、検知剤の色が濃くなりすぎて検出感度が悪くなる不都合を生じる。 Examples of the dichromate in the detection agent of the present invention include an alkali metal dichromate such as ammonium dichromate or potassium dichromate. The content of the dichromate is usually 0.05 to 10 wt%, preferably 0.1 to 5.0 wt% with respect to the inorganic carrier. When the content of the dichromate is less than 0.05 wt% with respect to the inorganic carrier, the color of the discoloration component of the detection agent is too light and is difficult to detect. In addition, when the content of dichromate exceeds 10 wt% with respect to the inorganic carrier, there arises a problem that the discoloration is likely to occur with respect to hydrogen and a problem that the detection sensitivity is deteriorated because the color of the detection agent becomes too dark.
本発明のゲルマン及び有機ケイ素化合物の検知剤においては、変色成分である重クロム酸塩のほか、さらに貴金属塩を無機質担体に担持させることが好ましい。本発明に使用できる貴金属塩としては、貴金属のハロゲン化物、炭酸塩、硫酸塩、硝酸塩、有機酸塩等を例示することができるが、これらの中では、パラジウムのハロゲン化物、炭酸塩、硫酸塩、または硝酸塩が好ましい。また、貴金属塩の担持量は、無機質担体に対して、通常は０．５ｗｔ％以下であり、好ましくは０．００１〜０．２ｗｔ％である。貴金属塩の含有量が無機質担体に対して０．５ｗｔ％を超える場合は水素の存在下で変色してしまう。本発明においては、パラジウム等の貴金属の塩を重クロム酸塩と併せて無機質担体に担持させることにより、検知剤の検出感度が良好になる。
本発明の検知剤の製造方法としては、重クロム酸塩を含む水溶液、または重クロム酸塩と貴金属塩を含む水溶液を、無機質担体に含浸させた後乾燥する方法、あるいは無機質担体をかき混ぜながら前記水溶液を振りかけた後乾燥させる方法を例示することができる。
In the germane and organosilicon compound detectors of the present invention, it is preferable to support a noble metal salt on an inorganic carrier in addition to the dichromate which is a discoloring component. Examples of noble metal salts that can be used in the present invention include noble metal halides, carbonates, sulfates, nitrates, organic acid salts, and the like. Among these, palladium halides, carbonates, sulfates, etc. Or nitrate is preferred. Further, the amount of the noble metal salt supported is usually 0.5 wt% or less, preferably 0.001 to 0.2 wt% with respect to the inorganic carrier. When the content of the noble metal salt exceeds 0.5 wt% with respect to the inorganic support, the color changes in the presence of hydrogen. In the present invention, the detection sensitivity of the detection agent is improved by supporting a salt of a noble metal such as palladium together with a dichromate on an inorganic carrier.
As a method for producing the detection agent of the present invention, an aqueous solution containing dichromate, or an aqueous solution containing dichromate and a noble metal salt is impregnated into an inorganic carrier and then dried, or while stirring the inorganic carrier, The method of drying after sprinkling aqueous solution can be illustrated.
次に本発明の検知剤の使用方法について詳細に説明する。
本発明のゲルマン及び有機ケイ素化合物の検知剤は、例えば半導体製造工程等から排出されるゲルマンまたは有機ケイ素化合物を含有するガスと接触させることにより、ガスに含まれるゲルマンまたは有機ケイ素化合物が検知される。
本発明において、重クロム酸塩がゲルマンまたは有機ケイ素化合物と接触すると分解し変色するので、この間の検知剤の変色を検知することによりガス中のゲルマンまたは有機ケイ素化合物を検知することができる。例えば、ゲルマンまたは有機ケイ素化合物が、白色の無機質担体に重クロム酸塩（重クロム酸アンモニウム、重クロム酸カリウム、重クロム酸ナトリウム）を担持させた検知剤と接触した場合、検知剤は黄色ないし橙色から焦茶色に鋭敏に変色する。
Next, the method for using the detection agent of the present invention will be described in detail.
The germane and organosilicon compound detectors of the present invention detect germane or organosilicon compounds contained in a gas, for example, by contacting them with a gas containing germane or organosilicon compounds discharged from a semiconductor manufacturing process or the like. .
In the present invention, when dichromate contacts with germane or an organosilicon compound, it decomposes and discolors, so that the germane or organosilicon compound in the gas can be detected by detecting the discoloration of the detection agent during this period. For example, when germane or an organosilicon compound is contacted with a detection agent in which a dichromate (ammonium dichromate, potassium dichromate, sodium dichromate) is supported on a white inorganic carrier, the detection agent is yellow or The color changes sharply from orange to dark brown.
本発明のゲルマン及び有機ケイ素化合物の検知剤は、通常は固体であり、例えば本発明の検知剤をガラス製の透明管に充填して検知管とし、検知対象ガスを配管等のガス採取口より検知管に吸引することにより目的のゲルマンまたは有機ケイ素化合物を検知することができる。また、本発明の検知剤をガラス製あるいはプラスチック製の透明管に充填し、これを検知対象ガスが流通する配管のバイパス管として設置し、透明管の中に検知対象ガスを通すことにより目的のゲルマンまたは有機ケイ素化合物を検知することができる。また、本発明の検知剤を、浄化筒の破過を検知するために使用する場合には、検知剤を浄化筒内の浄化剤層の下流側、浄化筒の後、または複数の浄化剤層の間などに設けられた透明な覗き窓部に充填して使用される。 The detection agent of the germane and organosilicon compound of the present invention is usually solid, for example, the detection agent of the present invention is filled in a transparent tube made of glass to form a detection tube, and the detection target gas is from a gas sampling port such as a pipe. The target germane or organosilicon compound can be detected by suction into the detector tube. In addition, the detection agent of the present invention is filled in a transparent tube made of glass or plastic, installed as a bypass pipe of a pipe through which the detection target gas flows, and the target gas is passed through the transparent pipe. Germane or organosilicon compounds can be detected. Further, when the detection agent of the present invention is used for detecting breakthrough of the purification cylinder, the detection agent is disposed downstream of the purification agent layer in the purification cylinder, after the purification cylinder, or a plurality of purification agent layers. It is used by filling a transparent viewing window provided in between.
本発明の検知剤を透明管に充填し、これをバイパス管に設置して使用する場合、あるいは本発明の検知剤を浄化剤等とともに使用する場合等において、検知剤と接触させる検知対象ガスの速度に特に制限はないが、通常は空筒線速度で０．０１〜１００ｃｍ／ｓｅｃ程度とされる。空筒線速度が０．０１ｃｍ／ｓｅｃより低い場合は検知が遅くなり、１００ｃｍ／ｓｅｃより高い場合は圧力損失が大きくなる虞がある。接触時の検知対象ガスの温度は通常は−２０〜１００℃、また、圧力は通常は常圧であるが１ｋＰａ（ａｂｓ）の減圧から１ＭＰａ（ａｂｓ）の加圧下においても使用可能である。 When the detection agent of the present invention is filled in a transparent tube and used in a bypass tube, or when the detection agent of the present invention is used together with a purifying agent, etc., the detection target gas to be brought into contact with the detection agent Although there is no restriction | limiting in particular in speed, Usually, it is set as about 0.01-100 cm / sec by a blank tube linear speed. When the empty tube linear velocity is lower than 0.01 cm / sec, the detection is slow, and when it is higher than 100 cm / sec, the pressure loss may increase. The temperature of the gas to be detected at the time of contact is usually -20 to 100 ° C., and the pressure is usually normal pressure, but it can be used even under reduced pressure of 1 kPa (abs) to 1 MPa (abs).
本発明の検知剤は、水素の存在下でも水素により変色しないので、水素を含むガス中のゲルマンまたは有機ケイ素化合物を選択的に高感度で検知することができる。また、半導体製造工程から排出されるゲルマンまたは有機ケイ素化合物を乾式浄化法により浄化する場合、ゲルマンまたは有機ケイ素化合物と浄化剤が反応して水素を発生するような浄化筒の破過も高感度で検知することができる。さらに、本発明の検知剤は、日光が入る室内においても日光が直接当たらなければ変質しないので保存が容易である。 Since the detection agent of the present invention is not discolored by hydrogen even in the presence of hydrogen, it is possible to selectively detect germane or an organosilicon compound in a gas containing hydrogen with high sensitivity. In addition, when the germane or organosilicon compound discharged from the semiconductor manufacturing process is purified by the dry purification method, breakthrough of the purification cylinder where the germane or organosilicon compound reacts with the cleaning agent to generate hydrogen is also highly sensitive. Can be detected. Furthermore, the detection agent of the present invention is easy to preserve because it does not change even in a room where sunlight enters, unless it is directly exposed to sunlight.
次に、本発明を実施例により具体的に説明するが、本発明がこれらにより限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
（検知剤の調製）
変色成分として１０ｇの重クロム酸アンモニウムを１０００ｍｌの水に溶解した溶液と、貴金属塩として０．２５ｇの硫酸パラジウムを５０ｍｌの硫酸に溶解した溶液を混合し、径１．５〜４ｍｍ、比表面積３００ｍ２／ｇの球状シリカゲル５００ｇに含浸させた後、ロータリーエバポレーターを用いて８０℃の温度で減圧乾燥させて検知剤（重クロム酸アンモニウムと、硫酸パラジウムと、シリカゲルの含有重量比は、２：０．０５：１００）を調製した。このように調製した検知剤を透明密閉容器に入れ、温度２５℃、湿度５０％の空気で満たされた実験室の日光が直接当たらない明るい場所に３０日間放置したが、変色、変質等は見られなかった。次に、この検知剤を用いて、検知能力の測定を行なった。
(Preparation of detection agent)
A solution in which 10 g of ammonium dichromate was dissolved in 1000 ml of water as a discoloring component and a solution in which 0.25 g of palladium sulfate was dissolved in 50 ml of sulfuric acid as a noble metal salt were mixed, and the diameter was 1.5 to 4 mm and the specific surface area was 300 m. After impregnating 500 g of 2 / g spherical silica gel, it was dried under reduced pressure at a temperature of 80 ° C. using a rotary evaporator, and the content ratio of the detection agent (ammonium dichromate, palladium sulfate, and silica gel was 2: 0) .05: 100). The detection agent thus prepared was placed in a transparent sealed container and left for 30 days in a laboratory filled with air at a temperature of 25 ° C. and a humidity of 50% where it was not directly exposed to sunlight. I couldn't. Next, the detection ability was measured using this detection agent.
（検知能力の測定）
この検知剤２０ｇを内径２０ｍｍのガラス管に充填した検知管を製作した。この検知管に、１０％の水素を含有する窒素ガスを、２５℃、常圧、空筒線速度５ｃｍ／ｓｅｃの条件で１００時間流通し検知剤に接触させた結果、検知剤は橙色を維持し変色しないことが確認された。次に５０ｐｐｍのゲルマン及び１０％の水素を含有する窒素ガスを、２５℃、常圧、空筒線速度５ｃｍ／ｓｅｃの条件で流通し検知剤に接触させた結果、検知剤が橙色から焦茶色に変色した。検知剤が変色し始めるまでの時間を測定した結果を表１に示す。
(Measurement of detection ability)
A detection tube in which 20 g of this detection agent was filled in a glass tube having an inner diameter of 20 mm was manufactured. As a result of flowing nitrogen gas containing 10% hydrogen through this detection tube for 100 hours under conditions of 25 ° C., normal pressure, and an empty cylinder linear velocity of 5 cm / sec, the detection agent remains orange. It was confirmed that the color did not change. Next, as a result of flowing nitrogen gas containing 50 ppm germane and 10% hydrogen under the conditions of 25 ° C., normal pressure, and an empty cylinder linear velocity of 5 cm / sec, the detection agent was changed from orange to dark brown. Discolored. Table 1 shows the results of measuring the time until the detection agent starts to change color.
［実施例２］
実施例１の検知能力の測定におけるゲルマンの濃度を１０ｐｐｍに変えたほかは実施例１と同様にして検知能力の測定を行なった。その結果を表１に示す。
[Example 2]
The detection ability was measured in the same manner as in Example 1 except that the germane concentration in the measurement of the detection ability in Example 1 was changed to 10 ppm. The results are shown in Table 1.
［実施例３、４］
実施例１の検知剤の調製における重クロム酸アンモニウムの含有量を、各々シリカゲルに対して０．６ｗｔ％、６ｗｔ％に変えたほかは実施例１と同様にして検知剤を調製した。この検知剤を用いたほかは実施例１と同様にして検知能力の測定を行なった。その結果を表１に示す。
[Examples 3 and 4]
A detection agent was prepared in the same manner as in Example 1 except that the content of ammonium dichromate in the preparation of the detection agent of Example 1 was changed to 0.6 wt% and 6 wt%, respectively, with respect to the silica gel. The detection ability was measured in the same manner as in Example 1 except that this detection agent was used. The results are shown in Table 1.
［実施例５、６］
実施例１の検知剤の調製における変色成分を、各々重クロム酸カリウム、重クロム酸ナトリウムに替えたほかは実施例１と同様にして検知剤を調製した。この検知剤を用いたほかは実施例１と同様にして検知能力の測定を行なった。その結果を表１に示す。
[Examples 5 and 6]
A detection agent was prepared in the same manner as in Example 1 except that the discoloration component in the preparation of the detection agent of Example 1 was replaced with potassium dichromate and sodium dichromate, respectively. The detection ability was measured in the same manner as in Example 1 except that this detection agent was used. The results are shown in Table 1.
［実施例７、８］
実施例１の検知剤の調製における貴金属塩を、各々塩化パラジウム、塩化白金酸に替えたほかは実施例１と同様にして検知剤を調製した。この検知剤を用いたほかは実施例１と同様にして検知能力の測定を行なった。その結果を表１に示す。
[Examples 7 and 8]
A detection agent was prepared in the same manner as in Example 1 except that the noble metal salt in the preparation of the detection agent of Example 1 was replaced with palladium chloride and chloroplatinic acid, respectively. The detection ability was measured in the same manner as in Example 1 except that this detection agent was used. The results are shown in Table 1.
［実施例９〜１３］
実施例１の検知能力の測定における検知対象ガス（ゲルマン）を、各々ビニルトリメチルシラン、ビニルトリメトキシシラン、アリルトリメチルシラン、アリルトリメトキシシラン、アリルトリフェニルシランに替えたほかは実施例１と同様にして検知能力の測定を行なった。その結果を表１に示す。
[Examples 9 to 13]
The detection target gas (german) in measurement of the detection capability of Example 1 is the same as that of Example 1 except that vinyltrimethylsilane, vinyltrimethoxysilane, allyltrimethylsilane, allyltrimethoxysilane, and allyltriphenylsilane are used. Thus, the detection ability was measured. The results are shown in Table 1.
［比較例１］
（検知剤の調製）
変色成分として５．０ｇのリンモリブデン酸と１．０ｇの硫酸銅を１０００ｍｌの水に溶解させた溶液を、径１．５〜４ｍｍ、比表面積３００ｍ２／ｇの球状シリカゲル５００ｇに含浸させた後、ロータリーエバポレーターを用いて８０℃の温度で減圧乾燥させて検知剤を調製した。
[Comparative Example 1]
(Preparation of detection agent)
After impregnating 500 g of spherical silica gel having a diameter of 1.5 to 4 mm and a specific surface area of 300 m 2 / g, a solution prepared by dissolving 5.0 g of phosphomolybdic acid and 1.0 g of copper sulfate as a discoloring component in 1000 ml of water. The detector was prepared by drying under reduced pressure at a temperature of 80 ° C. using a rotary evaporator.
（検知能力の測定）
この検知剤２０ｇを内径２０ｍｍのガラス管に充填した検知管を製作した。この検知管に、１０％の水素を含有する窒素ガスを、２５℃、常圧、空筒線速度５ｃｍ／ｓｅｃの条件で流通し検知剤に接触させた結果、検知剤は黄褐色を維持し変色しないことが確認された。次に５０ｐｐｍのゲルマン及び１０％の水素を含有する窒素ガスを、２５℃、常圧、空筒線速度５ｃｍ／ｓｅｃの条件で流通し検知剤に接触させた結果、検知剤は６０分経過後も変色しなかった。
(Measurement of detection ability)
A detection tube in which 20 g of this detection agent was filled in a glass tube having an inner diameter of 20 mm was manufactured. Nitrogen gas containing 10% hydrogen was circulated through this detector tube under the conditions of 25 ° C., normal pressure, and an empty cylinder linear velocity of 5 cm / sec. As a result, the detector kept yellowish brown. It was confirmed that there was no discoloration. Next, as a result of flowing nitrogen gas containing 50 ppm germane and 10% hydrogen under the conditions of 25 ° C., normal pressure, and an empty cylinder linear velocity of 5 cm / sec, the detection agent was brought into contact after 60 minutes. Also did not change color.
［比較例２〜６］
比較例１の検知能力の測定における検知対象ガス（ゲルマン）を、各々ビニルトリメチルシラン、ビニルトリメトキシシラン、アリルトリメチルシラン、アリルトリメトキシシラン、アリルトリフェニルシランに替えたほかは実施例１と同様にして検知能力の測定を行なった。その結果を表１に示す。
[Comparative Examples 2 to 6]
The detection target gas (german) in the measurement of the detection ability of Comparative Example 1 is the same as that of Example 1 except that vinyltrimethylsilane, vinyltrimethoxysilane, allyltrimethylsilane, allyltrimethoxysilane, and allyltriphenylsilane are used. Thus, the detection ability was measured. The results are shown in Table 1.
［比較例７］
（検知剤の調製）
変色成分として１２．５ｇの硫酸銅と２．５ｇの塩化パラジウムを１０００ｍｌの水に溶解させた溶液を、径１．５〜４ｍｍ、比表面積３００ｍ２／ｇの球状シリカゲル５００ｇに含浸させた後、ロータリーエバポレーターを用いて８０℃の温度で減圧乾燥させて検知剤を調製した。
[Comparative Example 7]
(Preparation of detection agent)
After impregnating 500 g of spherical silica gel having a diameter of 1.5 to 4 mm and a specific surface area of 300 m 2 / g, a solution prepared by dissolving 12.5 g of copper sulfate and 2.5 g of palladium chloride in 1000 ml of water as a discoloring component, A detection agent was prepared by drying under reduced pressure at a temperature of 80 ° C. using a rotary evaporator.
（検知能力の測定）
この検知剤２０ｇを内径２０ｍｍのガラス管に充填した検知管を製作した。この検知管に、１０％の水素を含有する窒素ガスを、２５℃、常圧、空筒線速度５ｃｍ／ｓｅｃの条件で流通し検知剤に接触させた結果、検知剤が黄褐色から黒色に変色してしまった。
(Measurement of detection ability)
A detection tube in which 20 g of this detection agent was filled in a glass tube having an inner diameter of 20 mm was manufactured. Nitrogen gas containing 10% hydrogen was circulated through this detector tube under the conditions of 25 ° C., normal pressure, and an empty cylinder linear velocity of 5 cm / sec. As a result, the detector agent changed from tan to black. Discolored.
以上のように、本発明の実施例の検知剤は、雰囲気ガスに影響されることなくゲルマン及び有機ケイ素化合物を高感度で検知でき、しかも使用するまでの期間中、光等により容易に感度が低下しないことが確認された。
As described above, the detection agents of the examples of the present invention can detect germane and organosilicon compounds with high sensitivity without being affected by the atmospheric gas, and are easily sensitive to light during the period until use. It was confirmed that it did not decrease.
Claims (9)
The organosilicon compound detector according to claim 8, wherein the noble metal is palladium.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222062A (en) * | 1985-07-23 | 1987-01-30 | Nippon Paionikusu Kk | Detecting agent |
| JPH02139033A (en) * | 1988-11-18 | 1990-05-29 | Chiyoda Corp | Poisonous gas adsorbent, its manufacture and purification of exhaust gas using it |
| JPH03135419A (en) * | 1989-09-22 | 1991-06-10 | L'air Liquide | Method of removing gaseous hydrogenation product |
| JPH03137917A (en) * | 1989-10-24 | 1991-06-12 | Iwatani Internatl Corp | Dry treatment of hydride type waste gas |
| JP2003207500A (en) * | 2002-01-17 | 2003-07-25 | Japan Pionics Co Ltd | Agent and method for detecting germane |
| JP2003207499A (en) * | 2002-01-17 | 2003-07-25 | Japan Pionics Co Ltd | Agent and method for detecting compound including vinyl group |
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2006
- 2006-07-13 JP JP2006192842A patent/JP4747046B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222062A (en) * | 1985-07-23 | 1987-01-30 | Nippon Paionikusu Kk | Detecting agent |
| JPH02139033A (en) * | 1988-11-18 | 1990-05-29 | Chiyoda Corp | Poisonous gas adsorbent, its manufacture and purification of exhaust gas using it |
| JPH03135419A (en) * | 1989-09-22 | 1991-06-10 | L'air Liquide | Method of removing gaseous hydrogenation product |
| JPH03137917A (en) * | 1989-10-24 | 1991-06-12 | Iwatani Internatl Corp | Dry treatment of hydride type waste gas |
| JP2003207500A (en) * | 2002-01-17 | 2003-07-25 | Japan Pionics Co Ltd | Agent and method for detecting germane |
| JP2003207499A (en) * | 2002-01-17 | 2003-07-25 | Japan Pionics Co Ltd | Agent and method for detecting compound including vinyl group |
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