JP3051231B2 - Method and apparatus for analyzing oxygen in hydride gas-containing gas - Google Patents
Method and apparatus for analyzing oxygen in hydride gas-containing gasInfo
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- JP3051231B2 JP3051231B2 JP3316282A JP31628291A JP3051231B2 JP 3051231 B2 JP3051231 B2 JP 3051231B2 JP 3316282 A JP3316282 A JP 3316282A JP 31628291 A JP31628291 A JP 31628291A JP 3051231 B2 JP3051231 B2 JP 3051231B2
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- gas
- oxygen
- hydride
- cylinder
- analyzer
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は水素化物ガスを含有する
ガス中に含まれる酸素の分析方法および装置に関し、さ
らに詳細には試料ガス中の水素化物ガスを吸着剤によっ
て除去する前処理工程を伴う酸素分析方法および装置に
関する。電子産業、特に半導体製造工業などにおいて、
アルシン（ＡｓＨ3 ）、ホスフィン（ＰＨ3 ）、シラン
（ＳｉＨ4 ）などの水素化物ガスはガリウム−砒素（Ｇ
ａＡｓ）、インジウム−燐（ＩｎＰ）およびシリコン半
導体の材料ガスとして多量に使用されている。これらの
ガスは、通常はボンベに単独で充填されるか、または窒
素、アルゴンなどの不活性ガスあるいは水素などで希釈
して充填された状態で用いられる。そしてこれらのガス
はボンベより半導体結晶を成長させる反応炉などへ供給
される。良質の半導体結晶を得るためにはこれらの水素
化物ガスを含有するガス中の不純物を除去する必要があ
り、特に酸素は結晶欠陥を引き起しやすいため、ガス中
の酸素は極低濃度に管理されていなければならない。従
って、その分析についても極低濃度まで高感度で分析で
きる方法および装置が望まれている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for analyzing oxygen contained in a gas containing a hydride gas, and more particularly, to a pretreatment step for removing a hydride gas in a sample gas by an adsorbent. The present invention relates to a method and an apparatus for analyzing oxygen. In the electronics industry, especially in the semiconductor manufacturing industry,
Hydride gas such as arsine (AsH 3 ), phosphine (PH 3 ), silane (SiH 4 ) is gallium-arsenic (G
aAs), indium-phosphorus (InP), and a large amount of material gas for silicon semiconductor. These gases are usually used alone in a cylinder or diluted with an inert gas such as nitrogen or argon or hydrogen. These gases are supplied from a cylinder to a reactor for growing semiconductor crystals. In order to obtain high-quality semiconductor crystals, it is necessary to remove impurities in the gas containing these hydride gases. Particularly, oxygen tends to cause crystal defects, so oxygen in the gas is controlled to an extremely low concentration. Must have been. Therefore, a method and an apparatus which can analyze even very low concentrations with high sensitivity are desired.
【０００２】[0002]
【従来の技術】水素化物ガスを含有するガスに含まれる
酸素濃度の分析方法としては、ガスクロマトグラフ法が
挙げられるが、酸素濃度の測定下限界が１ｐｐｍ程度と
感度が低く、半導体工業において要求される極低濃度酸
素の分析には対処できない。一方、窒素、アルゴンなど
の不活性ガスまたは水素中の酸素濃度分析方法としては
陽極に銀、陰極に鉛を使用し、電解液に水酸化カリウム
を用いたガルバニックセル法や黄リンと酸素が反応する
ときに発する光を光電子倍増管で検出する黄リン発光式
などがあり、これらの分析方法を用いることにより、
０．０１ｐｐｍレベルの低濃度まで測定が可能である。2. Description of the Related Art As a method for analyzing the concentration of oxygen contained in a gas containing a hydride gas, a gas chromatographic method can be cited. However, the lower limit of the measurement of the oxygen concentration is as low as about 1 ppm, and the sensitivity is low. Analysis of very low oxygen concentrations cannot be handled. On the other hand, as a method for analyzing the concentration of oxygen in an inert gas such as nitrogen or argon or hydrogen, silver is used for the anode, lead is used for the cathode, and a galvanic cell method using potassium hydroxide for the electrolyte or a reaction between yellow phosphorus and oxygen is used. There is a yellow phosphorus emission type and the like that detects the light emitted when the photomultiplier tube, by using these analysis methods,
Measurement is possible down to a low concentration of 0.01 ppm.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
の分析計をそのまま用いて水素化物ガスを含有するガス
の酸素濃度分析をおこなった場合には、ガルバニックセ
ル法においては水素化物ガスが電極や電解液に悪影響を
与えるため、感度が著しく低下し、また、黄燐発光式に
おいては黄リンの発光を消失させるなどの問題があり、
いずれも分析が不可能である。このように従来技術では
水素化物ガスを含有するガス中に不純物として含まれる
酸素の濃度を極低濃度まで精度よく分析しうる方法は知
られていない。However, when the oxygen concentration analysis of a gas containing a hydride gas is performed by using these analyzers as they are, the hydride gas is not used in the galvanic cell method. In order to adversely affect the sensitivity, the sensitivity is significantly reduced, and in the yellow phosphorus emission method, there is a problem such as disappearance of yellow phosphorus emission,
Neither can be analyzed. Thus, in the prior art, there is no known method capable of accurately analyzing the concentration of oxygen contained as an impurity in a gas containing a hydride gas to an extremely low concentration.
【０００４】[0004]
【課題を解決するための手段】本発明者らはこれらの課
題を解決するべく鋭意検討を重ねた結果、アルシン、ホ
スフィン、モノシランなどの水素化物ガスを吸着剤によ
る０℃以下の温度での前処理によって除去することによ
り、酸素分析計への悪影響および感度低下を生ずること
なく酸素濃度を高精度で分析しうることを見いだし、本
発明を完成した。すなわち本発明は、（１）水素化物ガ
スを含有するガス中に含まれる酸素の分析方法におい
て、試料ガスを水素化物ガスに対して吸着能力を有する
吸着剤と０℃以下の温度で接触させた後、酸素分析計に
導くことを特徴とする水素化物ガス含有ガス中の酸素分
析方法および、（２）水素化物ガスを含有するガス中に
含まれる酸素の分析装置において、試料ガスの導入管
と、該導入管に接続された吸着筒であってガスの入口お
よび出口を有し、かつ内部に水素化物ガスの吸着剤が充
填された吸着筒と、該吸着筒を収容し、内部に０℃以下
の温度の冷媒を満たすための冷却槽と、該吸着筒の出口
と導管によって接続された酸素分析計、とを備えてなる
ことを特徴とする水素化物含有ガス中の酸素分析装置で
ある。本発明において、水素化物ガスを含有するガスと
はアルシン、ホスフィン、シラン、ジシラン、ジボラ
ン、セレン化水素、ゲルマン、硫化水素など水素化物ガ
ス単独および窒素、アルゴンなどの不活性ガスまたは水
素などで希釈された水素化物ガスに適用されるが、水素
化物ガス単独または濃度が高い場合には、これらのガス
を酸素を含有しない窒素、アルゴンまたは水素などの精
製ガスで希釈した状態で分析される。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, a hydride gas such as arsine, phosphine, monosilane, etc. was cooled by an adsorbent at a temperature of 0 ° C. or less. The inventors have found that the oxygen concentration can be analyzed with high accuracy without removing the oxygen concentration by the treatment without adversely affecting the oxygen analyzer and lowering the sensitivity, thereby completing the present invention. That is, in the present invention, in the (1) method for analyzing oxygen contained in a gas containing a hydride gas, the sample gas was brought into contact with an adsorbent having an adsorption ability to the hydride gas at a temperature of 0 ° C. or lower . Then, the method for analyzing oxygen in a hydride gas-containing gas, which is led to an oxygen analyzer, and (2) an apparatus for analyzing oxygen contained in a gas containing a hydride gas, includes a sample gas introduction pipe, , a adsorption column which is connected to the introduction pipe has an inlet and an outlet of the gas, and the adsorption column adsorbent hydride gas is filled therein, to accommodate the adsorption tube, inside 0 ℃ Less than
And cooling bath order to satisfy the refrigerant temperature of an oxygen analyzer hydride-containing gas, wherein the oxygen analyzer connected by an outlet conduit of the adsorber cylinder to become equipped and. In the present invention, the gas containing a hydride gas is a hydride gas alone such as arsine, phosphine, silane, disilane, diborane, hydrogen selenide, germane, and hydrogen sulfide, and diluted with an inert gas such as nitrogen or argon or hydrogen. When the hydride gas alone or at a high concentration is used, the analysis is performed in a state where these gases are diluted with a purified gas such as nitrogen, argon, or hydrogen not containing oxygen.
【０００５】本発明で使用される吸着剤は、酸素は吸着
せず、水素化物ガスに対して吸着能を有するものであ
り、例えば合成ゼオライト、天然ゼオライト、シリカゲ
ル、活性アルミナなどである。これらの吸着剤の吸着能
力は、分析する水素化物ガスの種類によって若干異なる
ので、それぞれの条件に応じてその種類、充填量などが
適宜選択されるが、通常、分析に要する時間は３０分か
ら１時間程度であるので、少なくともこの間は水素化物
ガスを除去しうる容量が必要である。[0005] The adsorbent used in the present invention does not adsorb oxygen and has an adsorbing ability to hydride gas, and examples thereof include synthetic zeolite, natural zeolite, silica gel, and activated alumina. Since the adsorption capacity of these adsorbents slightly varies depending on the type of hydride gas to be analyzed, the type, filling amount, and the like are appropriately selected according to each condition, but usually, the time required for the analysis is 30 minutes to 1 minute. Since it is about time, at least during this time, a capacity capable of removing the hydride gas is required.
【０００６】水素化物ガスを吸着剤に吸着させるための
温度条件としては、吸着効率の点からガスが液化しない
温度範囲であれば極力低い方が望ましいが、通常は０℃
以下であり、好ましくは−１０℃〜−８０℃程度の範囲
でガスの種類などによって選択される。吸着温度が０℃
よりも高くなると吸着能力が低下して飽和状態に達する
までの時間が短くなり、分析の途中で水素化物ガスが漏
れ出す虞を生ずるので吸着筒の容積を大きくしなければ
ならず、また、ガスの滞留時間が増加するため分析計の
応答時間も長くなる。The temperature condition for allowing the hydride gas to be adsorbed by the adsorbent is preferably as low as possible within a temperature range in which the gas is not liquefied from the viewpoint of adsorption efficiency.
Or less, preferably in the range of about −10 ° C. to −80 ° C. depending on the type of gas. Adsorption temperature is 0 ℃
If it is higher than this, the adsorption capacity decreases and the time required to reach a saturated state is shortened, and the hydride gas may leak during the analysis, so that the volume of the adsorption column must be increased, and The response time of the analyzer also increases because the residence time of the analyzer increases.
【０００７】本発明に用いる酸素分析計としては酸素濃
度をを高精度で分析しうるものであればよく、その種類
には特に制限はないが、具体的例としては前記のガルバ
ニックセル式、黄燐発光式および大気圧イオン化質量分
析計などが挙げられる。The oxygen analyzer used in the present invention is not particularly limited as long as it can analyze the oxygen concentration with high accuracy. The type of the oxygen analyzer is not particularly limited. Luminescent and atmospheric pressure ionization mass spectrometers are included.
【０００８】本発明において、水素化物ガスを吸着した
吸着筒は分析の終了後、新しいものと交換してもよい
が、吸着筒を１００℃以上のような高温に加熱しながら
窒素、アルゴンなどの不活性吸着筒内をパージすること
により、吸着剤の再生をおこなうこともできる。この場
合には、吸着剤から脱着した水素化物ガスは毒性が高い
ため、取扱いには充分な注意を払う必要があり、パージ
ガスは水素化物ガスの除害筒などに導入し、そこで無害
化処理することが好ましい。除害筒としてはパージガス
に同伴する水素化物ガスを確実に除去しうるものであれ
ば乾式、湿式のいずれでも使用できるが、例えば、酸化
銅、二酸化マンガンなどの重金属酸化物を有効成分とす
る水素化物ガスの除去剤（特開昭６０−６８０３４号）
が充填された除害筒などが優れた除去性能を有するとと
もに乾式で、装置全体もコンパクトにできる点で好適で
ある。In the present invention, the adsorption column adsorbing the hydride gas may be replaced with a new one after the completion of the analysis. However, while the adsorption column is heated to a high temperature such as 100 ° C. or more, nitrogen, argon, etc. Regeneration of the adsorbent can be performed by purging the inert adsorption cylinder. In this case, since the hydride gas desorbed from the adsorbent is highly toxic, it is necessary to pay sufficient attention to its handling, and the purge gas is introduced into a hydride gas abatement cylinder or the like, where it is detoxified. Is preferred. As the abatement cylinder, any of a dry type and a wet type can be used as long as the hydride gas accompanying the purge gas can be reliably removed.For example, hydrogen containing a heavy metal oxide such as copper oxide or manganese dioxide as an active ingredient can be used. Compound remover (JP-A-60-68034)
It is preferable in that a detoxification cylinder filled with, etc. has excellent removal performance, is dry, and can be made compact as a whole.
【０００９】次に、本発明を図面によって例示し、さら
に具体的に説明する。図１は本発明の酸素分析装置のフ
ローシートである。図１において、一端が水素化物ガス
のボンベ１に接続され、減圧弁２、微小流量計３を介在
させ、流量計３の下流側に標準窒素ガスまたは精製窒素
ガスの供給管４が微小流量計３’を介して接続された試
料ガスの導入管５の他端が吸着筒６の入口に接続されて
いる。吸着筒６には水素化物ガスの吸着剤７が充填さ
れ、外部に吸着筒加熱用のヒーター８が配設されてい
る。吸着筒６は冷媒槽９に収容され、冷媒槽９には冷媒
１０が満たされている。吸着筒６の出口は導管１１によ
って酸素分析計１２と接続されている。また、吸着筒の
導入管５から分岐した配管には弁を介して水素化物ガス
の除害筒１３が接続され、一方、吸着筒の出口側の導管
１１にはパージ用窒素ガスの供給管１４が接続されてい
る。Next, the present invention will be described more specifically with reference to the drawings. FIG. 1 is a flow sheet of the oxygen analyzer of the present invention. In FIG. 1, one end is connected to a hydride gas cylinder 1, a pressure reducing valve 2 and a minute flow meter 3 are interposed, and a supply pipe 4 for a standard nitrogen gas or a purified nitrogen gas is provided downstream of the flow meter 3. The other end of the sample gas introduction pipe 5 connected via 3 ′ is connected to the inlet of the adsorption cylinder 6. The adsorption column 6 is filled with a hydride gas adsorbent 7, and a heater 8 for heating the adsorption column is provided outside. The adsorption cylinder 6 is accommodated in a refrigerant tank 9, and the refrigerant tank 9 is filled with a refrigerant 10. The outlet of the adsorption column 6 is connected to an oxygen analyzer 12 by a conduit 11. A hydride gas abatement cylinder 13 is connected via a valve to a pipe branched from the introduction pipe 5 of the adsorption cylinder, while a supply pipe 14 for purging nitrogen gas is connected to a conduit 11 on the outlet side of the adsorption cylinder. Is connected.
【００１０】水素化物ガス中の酸素の分析に際しては、
先ず、供給管４より酸素濃度の定まった標準窒素を流し
て酸素分析計の校正をおこなう。次に、ボンベ１から減
圧弁２を経た水素化物ガスを供給管４からの精製窒素ガ
スで微小流量計３および３’を見ながら所定の濃度に希
釈し、冷媒槽９で冷却された吸着筒６に供給する。吸着
筒６に入ったガスは吸着剤７と接触し、ガス中の水素化
物ガスが吸着除去される。吸着筒６から出たガスは導管
１１を経て酸素分析計１２に導かれ、ここで水素化物ガ
スが除去された試料ガス中の酸素濃度が分析される。分
析後に吸着剤７の再生がおこなわれる。冷媒槽９から冷
媒を抜き出した後、ヒーター８によって吸着筒６を加熱
しながら供給管１４よりパージ用窒素ガスを供給する。
パージガスはの導管１１から吸着筒６、導入管５、除害
筒１３を流れて外部に出るが、これによって吸着剤に吸
着されていた水素化物ガスは脱着し、パージガスととも
に除害筒に入り、水素化物ガスの除去剤と接触して捕捉
され、パージガスは無害化されて外部に放出される。In the analysis of oxygen in a hydride gas,
First, the oxygen analyzer is calibrated by flowing standard nitrogen having a fixed oxygen concentration from the supply pipe 4. Next, the hydride gas having passed through the pressure reducing valve 2 from the cylinder 1 was diluted with the purified nitrogen gas from the supply pipe 4 to a predetermined concentration while observing the minute flow meters 3 and 3 ′. 6 The gas that has entered the adsorption column 6 comes into contact with the adsorbent 7, and the hydride gas in the gas is adsorbed and removed. The gas discharged from the adsorption column 6 is led to an oxygen analyzer 12 through a conduit 11, where the oxygen concentration in the sample gas from which the hydride gas has been removed is analyzed. After the analysis, the adsorbent 7 is regenerated. After the refrigerant is extracted from the refrigerant tank 9, a nitrogen gas for purging is supplied from the supply pipe 14 while the adsorption tube 6 is heated by the heater 8.
The purge gas flows from the conduit 11 through the adsorption cylinder 6, the introduction pipe 5, and the detoxification cylinder 13 to the outside, whereby the hydride gas adsorbed by the adsorbent is desorbed and enters the detoxification cylinder together with the purge gas. The purge gas is trapped in contact with the hydride gas remover, and the purge gas is rendered harmless and discharged to the outside.
【００１１】[0011]
実施例１ 図１で示したと同様な構成の装置を用いて水素化物ガス
中の酸素の分析をおこなった。吸着剤としてシリカゲル
（富士ディビィソン（株）製、Ａ型粒度６ｕｐ）４５０
ｇを内径５７．２ｍｍ、長さ５２０ｍｍのステンレス製
の吸着筒に充填し、あらかじめ酸素が除去された精製窒
素ガス気流中１００〜１２０℃で２時間加熱賦活させた
後、精製窒素をそのまま流しながら室温まで冷却した。
この吸着筒をドライアイス＋エタノール系の冷媒によっ
て−４０〜−５０℃に保冷した。この吸着筒に精製窒素
を通して黄リン発光式酸素分析計（富士電機（株）製、
ＺＡＶ−２型）により、吸着筒のシリカゲルから酸素の
発生などがないことを確認した。引き続き、この吸着筒
に１０ｖｏｌ％のアルシンを含有する水素ガスを１．２
Ｌ／ｍｉｎで流し、酸素濃度を測定したところ０．５０
ｐｐｍの酸素が検出された。Example 1 The oxygen in the hydride gas was analyzed using an apparatus having the same configuration as that shown in FIG. 450 silica gel (A-type particle size 6up, manufactured by Fuji Divison Co., Ltd.) as an adsorbent
g was packed in a stainless steel adsorption cylinder having an inner diameter of 57.2 mm and a length of 520 mm, and heated and activated at 100 to 120 ° C. for 2 hours in a purified nitrogen gas stream from which oxygen had been previously removed. Cooled to room temperature.
This adsorption cylinder was kept cool at -40 to -50 ° C by a dry ice + ethanol type refrigerant. Purified nitrogen is passed through this adsorption column, and a yellow phosphorus emission type oxygen analyzer (Fuji Electric Co., Ltd.)
ZAV-2 type), it was confirmed that there was no generation of oxygen from the silica gel of the adsorption column. Subsequently, hydrogen gas containing 10 vol% of arsine was added to the adsorption column for 1.2 hours.
L / min and the oxygen concentration was measured.
ppm of oxygen was detected.
【００１２】実施例２ 実施例１で用いた１０ｖｏｌ％アルシンを含有する水素
ガスに、酸素濃度が、１．２ｐｐｍになるように２．４
ｐｐｍの酸素を含有する標準窒素を微小流量計（マスフ
ローコントローラー）を見ながら添加し、実施例１で用
いたと同様の吸着筒に通した後、黄リン発光式酸素分析
計で測定したところ、吸着筒の手前で調整した濃度と同
じ１．２ｐｐｍの酸素が検出された。Example 2 2.4 hydrogen gas containing 10 vol% arsine used in Example 1 was adjusted to an oxygen concentration of 1.2 ppm.
Standard nitrogen containing ppm of oxygen was added while looking at a micro flow meter (mass flow controller), passed through the same adsorption column as used in Example 1, and measured with a yellow phosphorus emission type oxygen analyzer. 1.2 ppm of oxygen, the same as the concentration adjusted before the cylinder, was detected.
【００１３】比較例１ 実施例２でおこなったと同様にして調整した１．２ｐｐ
ｍの酸素濃度を有するアルシン含有ガスをを吸着筒を通
さずに、直接黄リン発光式酸素分析計に通して酸素濃度
を測定したところ、分析計の指示は０ｐｐｍのままであ
り、酸素濃度の測定はできなかった。Comparative Example 1 1.2 pp adjusted in the same manner as in Example 2.
When the oxygen concentration was measured by passing an arsine-containing gas having an oxygen concentration of m directly through a yellow phosphorus emission type oxygen analyzer without passing through an adsorption column, the indication of the analyzer remained at 0 ppm, and the oxygen concentration was measured. The measurement could not be performed.
【００１４】実施例３ 実施例１〜２で用いた吸着筒をヒーターで１２０℃に加
熱しながら窒素を２Ｌ／ｍｉｎで４時間流して吸着した
アルシンを脱着させ、酸化銅を用いた除去剤を充填した
除害筒を通して水素化物ガスを除去しながら、パージを
おこなった後、再度、吸着筒をドライアイス＋エタノー
ル系の冷媒によって−４０〜−５０℃に保冷した。この
吸着筒に精製窒素を通しながら、黄リン発光式酸素分析
計によりシリカゲルから酸素などの発生がないことを確
認した後、２０ｖｏｌ％のモノシランを含有する窒素ガ
スを１．２Ｌ／ｍｉｎで吸着筒に通し、黄リン発光式酸
素分析計によって濃度を測定したところ、０．０８ｐｐ
ｍの酸素が検出された。Example 3 While adsorbing cylinders used in Examples 1 and 2 were heated to 120 ° C. with a heater, nitrogen was flowed at 2 L / min for 4 hours to desorb the adsorbed arsine, and a removing agent using copper oxide was removed. After purging while removing the hydride gas through the filled detoxification cylinder, the adsorption cylinder was again cooled to -40 to -50 C with a dry ice + ethanol-based refrigerant. After passing purified nitrogen through this adsorption column and confirming that there is no generation of oxygen or the like from the silica gel by a yellow phosphorus emission type oxygen analyzer, nitrogen gas containing 20 vol% of monosilane was adsorbed at 1.2 L / min. , And the concentration was measured by a yellow phosphorus emission type oxygen analyzer.
m of oxygen were detected.
【００１５】実施例４ 実施例３で用いた同様の２０ｖｏｌ％モノシランを含有
する窒素ガスに酸素濃度が１．２ｐｐｍになるように
２．４ｐｐｍの酸素濃度を有する標準窒素を添加したガ
スを吸着筒に通し、黄リン発光式酸素分析計で測定した
ところ、調整した濃度と同じ１．２ｐｐｍの酸素が検出
された。Example 4 A gas obtained by adding standard nitrogen having an oxygen concentration of 2.4 ppm to the same nitrogen gas containing 20 vol% monosilane used in Example 3 so that the oxygen concentration becomes 1.2 ppm was used as an adsorption column. , And measured with a yellow phosphorus emission type oxygen analyzer. As a result, 1.2 ppm of oxygen, which was the same as the adjusted concentration, was detected.
【００１６】比較例２ 実施例４で用いた１．２ｐｐｍの酸素濃度を有するモノ
シラン含有窒素ガスを吸着筒を通さずに直接黄リン発光
式酸素分析計に通して酸素濃度を測定したところ、分析
計の指示は０ｐｐｍのままであり、酸素濃度は測定でき
なかった。COMPARATIVE EXAMPLE 2 The monosilane-containing nitrogen gas having an oxygen concentration of 1.2 ppm used in Example 4 was directly passed through a yellow phosphorus emission type oxygen analyzer without passing through an adsorption column to measure the oxygen concentration. The indication on the meter remained at 0 ppm, and the oxygen concentration could not be measured.
【００１７】実施例５ 黄リン発光式酸素分析計の代わりにガルバニックセル式
酸素分析計（大阪酸素工業（株）製、ＭＫ３／Ｙ型）を
用いて酸素濃度の測定をおこなった。実施例１と同様の
吸着筒をドライアイス＋エタノール系の冷媒で−４０〜
−５０℃に保冷し、１０％アルシン含有する水素ガスを
０．１Ｌ／ｍｉｎで通し、ガルバニックセル式酸素分析
計で酸素濃度を測定したところ、０．５２ｐｐｍの酸素
が検出された。Example 5 The oxygen concentration was measured using a galvanic cell type oxygen analyzer (MK3 / Y type, manufactured by Osaka Oxygen Industry Co., Ltd.) instead of the yellow phosphorus emission type oxygen analyzer. The same adsorption cylinder as in Example 1 was dried at +40 to 40 with a dry ice + ethanol type refrigerant.
After cooling at -50 ° C and passing hydrogen gas containing 10% arsine at 0.1 L / min and measuring the oxygen concentration with a galvanic cell type oxygen analyzer, 0.52 ppm of oxygen was detected.
【００１８】実施例６ 実施例５で用いたと同様の１０ｖｏｌ％アルシンを含有
する水素ガスに、酸素濃度が１．２ｐｐｍになるように
２．４ｐｐｍの酸素濃度を有する標準窒素を流量計を見
ながら添加し、実施例１で用いたと同様の吸着筒に通し
たガスをガルバニックセル式酸素分析計で測定したとこ
ろ、吸着筒の手前で調整した濃度とほぼ同じ１．２１ｐ
ｐｍの酸素が検出された。 比較例３ 実施例６で用いた１．２１ｐｐｍの酸素濃度を有するア
ルシンを、吸着筒を通さずに直接カルバニックセル式酸
素分析計に通して酸素濃度を測定したところ、分析計の
指示は０ｐｐｍのままであり、酸素濃度の測定はできな
かった。Example 6 A standard nitrogen gas having an oxygen concentration of 2.4 ppm was added to a hydrogen gas containing 10 vol% arsine, which was the same as that used in Example 5, so that the oxygen concentration became 1.2 ppm while observing a flow meter. The gas added and passed through the same adsorption cylinder as used in Example 1 was measured by a galvanic cell type oxygen analyzer. The concentration was 1.21 p, which was almost the same as the concentration adjusted before the adsorption cylinder.
pm of oxygen was detected. Comparative Example 3 Arsine having an oxygen concentration of 1.21 ppm used in Example 6 was directly passed through a carbanic cell oxygen analyzer without passing through an adsorption column to measure the oxygen concentration. The oxygen concentration could not be measured.
【００１９】[0019]
【発明の効果】本発明によって、従来技術では測定でき
なかった水素化物ガス含有ガス中の酸素濃度を高感度
で、しかも、分析計に支障を生ずること無く安全に測定
できるようになった。According to the present invention, the oxygen concentration in the hydride gas-containing gas, which could not be measured by the prior art, can be measured with high sensitivity and without any trouble in the analyzer.
【００２０】[0020]
【図１】酸素分析装置のフローシートである。FIG. 1 is a flow sheet of an oxygen analyzer.
１ ボンベ ２ 減圧弁 ３ 微小流量計 ３’微小流量計 ４ 供給管 ５ 試料ガスの導入管 ６ 吸着筒 ７ 吸着剤 ８ ヒーター ９ 冷媒槽 １０ 冷媒 １１ 導管 １２ 酸素分析計 １３ 除害筒 １４ 供給管 DESCRIPTION OF SYMBOLS 1 Cylinder 2 Pressure reducing valve 3 Micro flow meter 3 'Micro flow meter 4 Supply pipe 5 Sample gas introduction pipe 6 Adsorption cylinder 7 Adsorbent 8 Heater 9 Refrigerant tank 10 Refrigerant 11 Conduit 12 Oxygen analyzer 13 Detoxification cylinder 14 Supply pipe
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｇ０１Ｎ 31/00 Ｇ０１Ｎ 27/46 ３２３ (56)参考文献 特開 昭61−172045（ＪＰ，Ａ) 実開 昭62−15551（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 1/22 G01N 21/64 G01N 21/76 G01N 27/28 G01N 27/404 G01N 31/00 ────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. 7 identifications FI G01N 31/00 G01N 27/46 323 (56 ) reference JP Akira 61-172045 (JP, a) JitsuHiraku Akira 62-15551 ( (JP, U) (58) Fields investigated (Int. Cl. 7 , DB name) G01N 1/22 G01N 21/64 G01N 21/76 G01N 27/28 G01N 27/404 G01N 31/00
Claims (6)
る酸素の分析方法において、試料ガスを水素化物ガスに
対して吸着能力を有する吸着剤と０℃以下の温度で接触
させた後、酸素分析計に導くことを特徴とする水素化物
ガス含有ガス中の酸素分析方法。1. A method for analyzing oxygen contained in a gas containing a hydride gas, comprising: bringing a sample gas into contact with an adsorbent capable of adsorbing hydride gas at a temperature of 0 ° C. or lower ; A method for analyzing oxygen in a hydride gas-containing gas, which is led to an analyzer.
シラン、ジシラン、ジボラン、セレン化水素、ゲルマ
ン、及び硫化水素から選ばれる１種または２種以上であ
る請求項１に記載の酸素分析方法。2. The method of claim 1, wherein the hydride gas is arsine, phosphine,
Silane, disilane, diborane, hydrogen selenide, germanium
The oxygen analysis method according to claim 1, wherein the oxygen analysis method is one or more selected from oxygen and hydrogen sulfide .
ト、シリカゲルまたは活性アルミナである請求項１に記
載の酸素分析方法。3. The method according to claim 1, wherein the adsorbent is a synthetic zeolite, a natural zeolite, silica gel or activated alumina.
る酸素の分析装置において、試料ガスの導入管と、該導
入管に接続された吸着筒であってガスの入口および出口
を有し、かつ内部に水素化物ガスの吸着剤が充填された
吸着筒と、該吸着筒を収容し、内部に０℃以下の温度の
冷媒を満たすための冷却槽と、該吸着筒の出口と導管に
よって接続された酸素分析計、とを備えてなることを特
徴とする水素化物ガス含有ガス中の酸素分析装置。4. An analyzer for oxygen contained in a gas containing a hydride gas, comprising: an inlet pipe for a sample gas; and an adsorption cylinder connected to the inlet pipe, the inlet and outlet for the gas being provided. and a suction cylinder adsorbent hydride gas is filled therein, to accommodate the adsorption cylinder, the cooling bath order to satisfy the 0 ℃ temperature below <br/> refrigerant therein, the adsorption cylinder An oxygen analyzer in a hydride gas-containing gas, comprising: an outlet and an oxygen analyzer connected by a conduit.
除害筒と、吸着筒の出口側の導管から分岐するパージ用
不活性ガスの供給管とが設けられた請求項４に記載の酸
素分析装置。5. The purging apparatus according to claim 4, further comprising: an abatement cylinder branched and connected from a sample gas introduction pipe, and a purge inert gas supply pipe branched from an outlet pipe of the adsorption cylinder. Oxygen analyzer.
去剤が充填されてなる乾式の除害筒である請求項５に記
載の酸素分析装置。6. The oxygen analyzer according to claim 5, wherein the abatement cylinder is a dry abatement cylinder filled with a remover containing a heavy metal oxide as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3316282A JP3051231B2 (en) | 1991-11-29 | 1991-11-29 | Method and apparatus for analyzing oxygen in hydride gas-containing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3316282A JP3051231B2 (en) | 1991-11-29 | 1991-11-29 | Method and apparatus for analyzing oxygen in hydride gas-containing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05149842A JPH05149842A (en) | 1993-06-15 |
| JP3051231B2 true JP3051231B2 (en) | 2000-06-12 |
Family
ID=18075373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3316282A Expired - Fee Related JP3051231B2 (en) | 1991-11-29 | 1991-11-29 | Method and apparatus for analyzing oxygen in hydride gas-containing gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3051231B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4594487B2 (en) * | 2000-04-06 | 2010-12-08 | 新コスモス電機株式会社 | Constant potential electrolytic gas sensor |
| JP4791856B2 (en) * | 2006-03-02 | 2011-10-12 | 大陽日酸株式会社 | Exhaust gas abatement device for trace oxygen concentration meter, trace oxygen concentration meter equipped with the same, and exhaust gas elimination method for trace oxygen concentration meter |
| JP4909614B2 (en) * | 2006-03-28 | 2012-04-04 | 大陽日酸株式会社 | Method and apparatus for analyzing trace impurities in hydride gas |
| JP5181072B1 (en) * | 2012-06-01 | 2013-04-10 | 株式会社神鋼環境ソリューション | Biogas deoxygenation method and apparatus |
| JP6935241B2 (en) * | 2017-06-15 | 2021-09-15 | 株式会社堀場製作所 | Removal member, calibration device, and gas analyzer |
-
1991
- 1991-11-29 JP JP3316282A patent/JP3051231B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05149842A (en) | 1993-06-15 |
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