JPH0479578B2 - - Google Patents
Info
- Publication number
- JPH0479578B2 JPH0479578B2 JP16268885A JP16268885A JPH0479578B2 JP H0479578 B2 JPH0479578 B2 JP H0479578B2 JP 16268885 A JP16268885 A JP 16268885A JP 16268885 A JP16268885 A JP 16268885A JP H0479578 B2 JPH0479578 B2 JP H0479578B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- gases
- detection agent
- gas
- detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000007789 gas Substances 0.000 claims description 35
- 238000001514 detection method Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 14
- 150000002940 palladium Chemical class 0.000 claims description 10
- -1 diborane Chemical compound 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002845 discoloration Methods 0.000 claims description 5
- 229910000078 germane Inorganic materials 0.000 claims description 5
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000058 selane Inorganic materials 0.000 claims description 5
- 150000004678 hydrides Chemical class 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical class OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は水素化物系ガスの検知剤に関し、さら
に詳細には半導体製造工程などに使用されるアル
シン、ホスフイン、ジボラン、セレン化水素、硫
化水素、ゲルマン、モノシラン、ジジランおよび
ジクロロシランの検知剤に関する。
近年、半導体工業の発展とともにそれに使用さ
れるガスの種類と量が急激に増加している。これ
らのガスの中でも特に水素化物系ガスは毒性が強
いばかりではなく可燃性でもあるので、その取り
扱いには十分な注意が必要とされる。
従つて、これらのガスの取り扱いに際しては絶
えず作業環境の測定を行わなければならず、万
一、これらのガスが漏れた場合には的確に作業者
に知らされるような処置を講ずる必要がある。
また半導体プロセスなどから排出されるガスに
はこれらの水素化物系ガスが含有されているため
除害装置などを用いて浄化した後、外部に放出さ
れるが、放出に先立つてこれらの水素化物系ガス
の有無を確認する必要がある。
〔従来の技術〕
これら水素化物系ガスの検知方法としては、例
えばガラス管に検知剤を充填した検知管が知られ
ており、検知剤と被測定ガスとの反応により検知
剤が変色することを利用している。従来検知剤と
しては例えば第二水銀またはその錯塩を単独に、
あるいはこれに第二鉄塩または第二銅塩を混合し
たものをシリカゲル粒に吸着させたものがホスフ
インの検知用として、また金化合物をシリカゲル
粒に吸着させたものがホスフイン、アルシン、ジ
ボランの検知用として、さらに酢酸鉛あるいは硫
酸銅をシリカゲル粒に吸着させたものが硫化水素
検知用としてそれぞれ知らされている。
しかしながら、これらの検知剤は被測定ガスの
種類によつて適合する検知剤の種類がそれぞれ異
なるため一種類の検知管で測定できるガスが限定
されるという問題点があつた。
さらにモノシラン、ジシランの検知に対しては
未だ実用に供しうる検知剤は知られていないため
半導体製造工程などで使用される水素化物系ガス
のすべてを感度よく検知することはできなかつ
た。
これらの検知管の他に水素化物系ガスを検知す
る検知警報計が設置されることもあるが、これと
ても被測定ガスの種類が限定されており、しかも
測定原理および構造が複雑であるため高価でもあ
つた。
〔発明が解決しようとする問題点〕
従つて多種類の水素化物系ガスの検知に適用す
ることができ、かつ感度の優れた検知剤を得るこ
とが必要である。
〔問題点を解決するための手段〕
本発明者らはこれらの従来技術の問題点を解決
すべく鋭意検討した結果、半導体製造工程などで
使用される水素化物系ガスの検知に第二銅塩とパ
ラジウム塩との混合物が変色成分として極めて優
れていることを見いだし、本発明に到達した。
本発明は第二銅塩とパラジウム塩との混合物を
変色成分とする、アルシン、ホスフイン、ジボラ
ン、セレン化水素、硫化水素、ゲルマン、モノシ
ラン、ジジランおよびジクロロシランの一種以上
（以下、水素化物系ガスと記す）を含有するガス
の検知剤である。
本発明の検知剤は窒素ガス、水素ガス、アルゴ
ンガス、ヘリウムガスおよび空気などに前述の水
素化物系ガスを含有するガスの検知に共通して使
用することができる。本発明の検知剤にこれらの
ガスを接触させると黄褐色の変色成分が黒色へと
敏感に変色する。
本発明は用いられる第二銅塩には、無機酸およ
び有機酸の塩があり無機酸の塩としてはオキソ酸
の塩および／またはハロゲン化物があげられる。
オキソ酸の塩としては例えば炭酸、ケイ酸、硝
酸、硫酸、ヒ酸、ホウ酸、塩素酸、過塩素酸、亜
塩素酸、次亜塩素酸などの第二銅塩があげられ、
ハロゲン化物としては例えば塩化第二銅、臭化第
二銅、ヨウ化第二銅などがあげられる。有機酸と
してはギ酸、酢酸、プロピオン酸、酪酸、オレイ
ン酸、ステアリン酸などの脂肪族モノカルボン酸
やシユウ酸、アジピン酸、セバシン酸などの脂肪
族ジカルボン酸、乳酸や酒石酸のようなオキシ
酸、安息香酸、トルイル酸などの芳香族酸やナフ
テン酸のような構造を特定し難い酸など種々の酸
があげられ、これらの銅塩のいずれを用いても構
造に第二銅イオンを含む限りは有効である。
パラジウム塩としても、無機酸および有機酸の
塩があげられ、その組成については銅について述
べたのと全く同様である。
第二銅塩の中では、硝酸銅、硫酸銅、塩化銅、
酢酸銅などが、水溶液として扱う場合には好まし
く、またパラジウム塩についても硝酸パラジウ
ム、硫酸パラジウム、塩化パラジウム、酢酸パラ
ジウムなどが、水溶性の点から好ましい。
第二銅塩とパラジウム塩の組合せには制限はな
いが、入手のし易さ及び水溶性の点から、硝酸
塩、硫酸塩、塩化物及び／または酢酸塩同士また
はこれらのいずれかの組合せが好ましい。
第二銅塩に対するパラジウム塩の混合割合には
特に制限はないが、第二銅塩中の銅１ｇに対し
て、パラジウム塩中のパラジウムは0.3ｇ〜0.005
ｇの範囲であることが好ましい。パラジウムが
0.3ｇ以上であると検知剤自体の色が褐色を呈し、
変色した様子が見わけ難くなることがあり、また
0.005ｇ以下であると鋭敏な変色が生じ難くなる
ことがある。
本発明においては変色成分である第二銅塩とパ
ラジウム塩との混合物、それ自体を粉末状のま
ま、またはペレツトなどに成型して検知剤として
もよく、また担体、好ましくは多孔質担体、など
に担持させて検知剤としてもよいが、担持体が好
ましく、特に多孔質担体に担持させたものが好ま
しい。担体の種類は広い範囲から選択でき、例え
ばシリカゲル、シリカアルミナ、アルミナなどで
例示される通常の触媒担体があげられる。これら
のうちでもシリカアルミナ、アルミナが好まし
い。担体の比表面積は50m2／ｇ以下、特に２m2／
ｇ以下が好ましい。担体としては通常は淡色のも
のが用いられ、中でも白色乃至無色のものが好適
に用いられる。担体を用いる場合の変色成分の担
持方法としては、たとえば変色成分や各種の有機
溶媒などに溶解または懸濁させた液に担体を浸漬
するかまたは液を担体表面に散布する。なおエタ
ノールなどの有機溶媒を用いた場合には、100℃
以上で空気中で乾燥させると、検知剤が黒化する
ので、このような場合には、80℃程度で不活性な
ガスの雰囲気下で減圧乾燥する。
担体に対する変色成分の担持量は通常担体100
重量部に対し、0.5〜10重量部、好ましくは１〜
８重量部とされる。
本発明の検知剤によつて検知される水素化物系
ガスの濃度は通常はアルシン、ホスフイン、硫化
水素およびセレン化水素については0.1ppm以上、
ジボラン、ゲルマン、モノシラン、ジシランおよ
びジクロロシランについては0.5ppm以上とされ
る。検知剤と接触させるガスの流速は通常、線速
度で0.01〜100cm／secとされる。また接触時のガ
スの温度および圧力は通常、−20〜100℃および
0.001〜20Kg／cm2absとされる。
本発明の検知剤は固形であり通常、透明の容器
（通常は管）に入れて使用され、系内の水素化物
系ガスの存在を検知剤の色変色により知ることが
できる。本発明の検知剤は検知管に入れても使用
し得るが、より簡便な形態でも使用することがで
きる。例えば、ガラス、プラスチツクなどの透明
の容器に入れ、この中にガスを通すことによつて
ガス中の水素化物系ガスの存在を簡易に検知する
ことができる。
この場合、検知剤は水素化物系ガスの除去筒の
筒の除去剤の層の後または複数の層の間に入れた
り、検知筒の中に入れ検知筒を除去筒の後につな
いだりして使用される。
〔作用、効果〕
本発明の検知剤が以下のような優れた効果を有
しており、工業的に極めて有用である。
(1) 半導体製造工程などで使用されるほとんどの
水素化物系ガスの検知に感度よく、且つ共通し
て使用することができる。
(2) ガス吸着筒など除害装置の出口部などに充填
して破過の検知に用いてもよく、また作業場に
おける漏れの検知などに用いてもよく利用範囲
が広い。
〔実施例〕
粉末のシリカゲル100ｇに硫酸銅2.5ｇと塩化パ
ラジウム0.5ｇを溶解させた溶液25mlを含浸させ
たのち、120℃の温度で乾燥させて検知剤を調製
した。この検知剤１ｇを内径13mmφの硬質ポリ塩
化ビニル製カラムに充填し、0.1ppmのアルシン、
ホスフイン、セレン化水素もしくは硫化水素また
は0.5ppmのジボラン、ゲルマン、モノシラン、
ジシランもしくはジクロロシランを含有する窒素
ガスを線速度0.1cm／secでそれぞれ検知剤に接触
させ完全に黒変するまでの時間を測定した。結果
を第１表に示す。
【表】[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a detection agent for hydride-based gases, and more particularly to arsine, phosphine, diborane, hydrogen selenide, and hydrogen sulfide used in semiconductor manufacturing processes. , germane, monosilane, didyrane and dichlorosilane detection agent. In recent years, with the development of the semiconductor industry, the types and amounts of gases used therein have rapidly increased. Among these gases, hydride gases in particular are not only highly toxic but also flammable, so sufficient care must be taken when handling them. Therefore, when handling these gases, it is necessary to constantly measure the working environment, and in the unlikely event that these gases leak, it is necessary to take measures to notify workers accurately. . In addition, gases emitted from semiconductor processes contain these hydride gases, so they are purified using abatement equipment and then released to the outside. It is necessary to check whether there is gas. [Prior Art] As a detection method for these hydride gases, for example, a detection tube in which a glass tube is filled with a detection agent is known. We are using. Conventional detection agents include, for example, mercury or its complex salt alone;
Alternatively, a mixture of ferric salt or cupric salt adsorbed on silica gel particles can be used to detect phosphine, and a gold compound adsorbed on silica gel particles can be used to detect phosphine, arsine, and diborane. In addition, lead acetate or copper sulfate adsorbed onto silica gel particles are known to be used to detect hydrogen sulfide. However, these detection agents have different types of detection agents depending on the type of gas to be measured, so there is a problem that the gases that can be measured with one type of detection tube are limited. Furthermore, since there is still no known detecting agent that can be used practically for detecting monosilane and disilane, it has not been possible to detect all hydride gases used in semiconductor manufacturing processes with high sensitivity. In addition to these detector tubes, detection alarm meters that detect hydride gases are sometimes installed, but these are very limited in the types of gases that can be measured and are expensive due to their complicated measurement principles and structures. But it was hot. [Problems to be Solved by the Invention] Therefore, it is necessary to obtain a detection agent that can be applied to the detection of many types of hydride gases and has excellent sensitivity. [Means for Solving the Problems] As a result of intensive studies to solve the problems of these conventional techniques, the present inventors found that cupric salts can be used to detect hydride gases used in semiconductor manufacturing processes, etc. It has been discovered that a mixture of palladium salt and palladium salt is extremely excellent as a color-changing component, and the present invention has been achieved. The present invention uses a mixture of a cupric salt and a palladium salt as a discoloration component, and one or more of arsine, phosphine, diborane, hydrogen selenide, hydrogen sulfide, germane, monosilane, didyrane, and dichlorosilane (hereinafter referred to as hydride gas). This is a detection agent for gases containing The detection agent of the present invention can be commonly used to detect gases containing the aforementioned hydride gases such as nitrogen gas, hydrogen gas, argon gas, helium gas, and air. When these gases are brought into contact with the detection agent of the present invention, the yellow-brown discoloration component sensitively changes color to black. The cupric salts used in the present invention include salts of inorganic acids and organic acids, and examples of the salts of inorganic acids include oxoacid salts and/or halides. Examples of salts of oxo acids include cupric salts of carbonic acid, silicic acid, nitric acid, sulfuric acid, arsenic acid, boric acid, chloric acid, perchloric acid, chlorous acid, hypochlorous acid, etc.
Examples of the halides include cupric chloride, cupric bromide, and cupric iodide. Organic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oleic acid, and stearic acid; aliphatic dicarboxylic acids such as oxalic acid, adipic acid, and sebacic acid; oxyacids such as lactic acid and tartaric acid; Various acids can be mentioned, such as aromatic acids such as benzoic acid and toluic acid, and acids whose structure is difficult to specify such as naphthenic acid. No matter which of these copper salts is used, as long as the structure contains cupric ions, It is valid. Palladium salts include salts of inorganic acids and organic acids, and their compositions are exactly the same as those described for copper. Among cupric salts, copper nitrate, copper sulfate, copper chloride,
Copper acetate and the like are preferred when treated as an aqueous solution, and as palladium salts, palladium nitrate, palladium sulfate, palladium chloride, palladium acetate and the like are preferred from the viewpoint of water solubility. There are no restrictions on the combination of cupric salts and palladium salts, but from the viewpoint of availability and water solubility, nitrates, sulfates, chlorides and/or acetates or combinations of any of these are preferred. . There is no particular restriction on the mixing ratio of palladium salt to cupric salt, but the amount of palladium in palladium salt is 0.3g to 0.005g for 1g of copper in cupric salt.
It is preferable that it is in the range of g. Palladium is
If the amount is 0.3g or more, the color of the detection agent itself becomes brown,
The discoloration may become difficult to distinguish, and
When the amount is 0.005 g or less, it may be difficult to cause sharp discoloration. In the present invention, a mixture of a cupric salt and a palladium salt, which are discoloring components, may be used as a detection agent in powder form or in the form of a pellet or the like, and a carrier, preferably a porous carrier, etc. The detection agent may be used as a detection agent by being supported on a carrier, but a carrier is preferable, and one supported on a porous carrier is particularly preferable. The type of carrier can be selected from a wide range, and includes common catalyst carriers such as silica gel, silica alumina, and alumina. Among these, silica alumina and alumina are preferred. The specific surface area of the carrier is 50 m 2 /g or less, especially 2 m 2 / g.
g or less is preferable. As the carrier, a light-colored carrier is usually used, and among them, a white to colorless carrier is preferably used. When a carrier is used, the color-changing component can be supported by, for example, immersing the carrier in a liquid in which the color-changing component and various organic solvents are dissolved or suspended, or by spraying the liquid onto the surface of the carrier. In addition, when using an organic solvent such as ethanol, the temperature is 100℃.
If dried in the air above, the detection agent will turn black, so in such a case, dry it under reduced pressure at about 80°C in an inert gas atmosphere. The amount of color-changing component supported on the carrier is usually 100% of the carrier.
0.5 to 10 parts by weight, preferably 1 to 10 parts by weight
It is said to be 8 parts by weight. The concentration of hydride gas detected by the detection agent of the present invention is usually 0.1 ppm or more for arsine, phosphine, hydrogen sulfide, and hydrogen selenide.
For diborane, germane, monosilane, disilane, and dichlorosilane, the limit is 0.5 ppm or more. The flow rate of the gas brought into contact with the detection agent is usually 0.01 to 100 cm/sec in linear velocity. Also, the temperature and pressure of the gas during contact are usually -20 to 100℃ and
It is estimated to be 0.001 to 20Kg/cm 2 abs. The detection agent of the present invention is solid and is usually used in a transparent container (usually a tube), and the presence of hydride gas in the system can be detected by the color change of the detection agent. The detection agent of the present invention can be used even if it is placed in a detection tube, but it can also be used in a simpler form. For example, the presence of hydride gas in the gas can be easily detected by placing it in a transparent container such as glass or plastic and passing the gas through the container. In this case, the detection agent is placed after the removal agent layer in the hydride gas removal tube or between multiple layers, or it is placed inside the detection tube and the detection tube is connected after the removal tube. be done. [Functions and Effects] The detection agent of the present invention has the following excellent effects and is extremely useful industrially. (1) It has good sensitivity and can be commonly used for detecting most hydride gases used in semiconductor manufacturing processes. (2) It can be used to detect breakthroughs by filling the outlet of a gas adsorption tube or other abatement device, and can also be used to detect leaks in workplaces, and has a wide range of applications. [Example] A detection agent was prepared by impregnating 100 g of powdered silica gel with 25 ml of a solution in which 2.5 g of copper sulfate and 0.5 g of palladium chloride were dissolved, and then drying at a temperature of 120°C. 1 g of this detection agent was packed into a hard polyvinyl chloride column with an inner diameter of 13 mmφ, and 0.1 ppm of arsine,
phosphine, hydrogen selenide or hydrogen sulfide or 0.5ppm diborane, germane, monosilane,
Nitrogen gas containing disilane or dichlorosilane was brought into contact with each detecting agent at a linear velocity of 0.1 cm/sec, and the time until it completely turned black was measured. The results are shown in Table 1. 【table】
Claims (1)
分とするアルシン、ホスフイン、ジボラン、セレ
ン化水素、硫化水素、ゲルマン、モノシラン、ジ
ジランおよびジクロロシランの一種以上を含有す
る有害ガスの検知剤。1. A detection agent for harmful gases containing one or more of arsine, phosphine, diborane, hydrogen selenide, hydrogen sulfide, germane, monosilane, didyrane, and dichlorosilane, which contains a mixture of a cupric salt and a palladium salt as a discoloration component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16268885A JPS6222062A (en) | 1985-07-23 | 1985-07-23 | Detecting agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16268885A JPS6222062A (en) | 1985-07-23 | 1985-07-23 | Detecting agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6222062A JPS6222062A (en) | 1987-01-30 |
| JPH0479578B2 true JPH0479578B2 (en) | 1992-12-16 |
Family
ID=15759407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16268885A Granted JPS6222062A (en) | 1985-07-23 | 1985-07-23 | Detecting agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6222062A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4020753A1 (en) * | 1989-09-22 | 1991-04-04 | Draegerwerk Ag | COLORIMETRIC TEST AND MEASURING DEVICE FOR HYDRIDGAS |
| JP3716030B2 (en) * | 1996-02-29 | 2005-11-16 | 日本パイオニクス株式会社 | How to clean harmful gases |
| US6419574B1 (en) | 1999-09-01 | 2002-07-16 | Mitsubishi Materials Corporation | Abrasive tool with metal binder phase |
| JP4747046B2 (en) * | 2006-07-13 | 2011-08-10 | 日本パイオニクス株式会社 | Germanium detection agent |
-
1985
- 1985-07-23 JP JP16268885A patent/JPS6222062A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6222062A (en) | 1987-01-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |