JPH06273408A - Detecting agent for volatile inorganic hydride - Google Patents

Abstract

PURPOSE:To expedite the color-changing speed at the time of contact with a volatile inorganic hydride and to make it hard to cause discoloration by light by constituting detecting agent of the mixture of a zinc slat and gold salt or the mixture of a nickel salt and gold salt. CONSTITUTION:For the gold salt, various kinds or inorganic and organic acid salts of gold such as gold chloride and chloroanric acid and the lie can be utilized. For zinc salt, various kinds of inorganic an organic acid salts of zinc such as zinc sulfate can be utilized. For nickel salt, various kinds of inorganic and organic acid salts of nickel such as nickel sulfate can be utilized. For various kinds of inorganic acid salts, ortho acid salts such as carbonate and halides such as chloride can be utilized. For various kinds of organic acid salts, formate and the like can be utilized. It is most preferable that the weight ratio of the gold in the gold salt with respect to zinc slat, zinc in nickel salt and nickel is made to be the range of 0.01-0.5. These materials change their color in a short time at the time of contact with the volatile inorganic hydride. Especially in the case of the mixture of nickel salt and gold salt, the effect of the light is very small.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、揮発性無機水素化物の
検知剤に関し、詳しくは、シラン，アルシン，ホスフィ
ン等の揮発性無機水素化物の検知に用いる検知剤に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detecting agent for volatile inorganic hydrides, and more particularly to a detecting agent used for detecting volatile inorganic hydrides such as silane, arsine and phosphine.

【０００２】[0002]

【従来の技術】例えば、半導体製造工程で用いられるシ
ラン等の半導体材料ガスは、有毒もしくは可燃性なので
取扱いに注意を要する。そこで、これらのガスの有無を
検知管内に充填した検知剤の発色により検知することが
行われており、従来から種々の検知剤が提案されてい
る。2. Description of the Related Art For example, a semiconductor material gas such as silane used in a semiconductor manufacturing process is poisonous or flammable, and thus requires careful handling. Therefore, the presence or absence of these gases is detected by the color development of the detection agent filled in the detection tube, and various detection agents have been conventionally proposed.

【０００３】例えば、米国特許明細書第３１１２９９８
号には、塩化第二水銀と金塩の一種である塩化金との混
合物からなる検知剤が提案されているが、有毒な水銀を
含むことと、変色速度が遅いこと等の理由で問題があ
り、近時は、特開平２−３２５５４号公報に見られるよ
うに、第二銅塩と金塩との混合物でなる検知剤が提案さ
れている。For example, US Pat. No. 3,112,998.
In JP-A No. 2003-242242, a detection agent composed of a mixture of mercuric chloride and gold chloride, which is a kind of gold salt, is proposed, but there are problems due to the fact that it contains toxic mercury and the slow discoloration rate. However, recently, as disclosed in Japanese Patent Laid-Open No. 32554/1993, a detection agent composed of a mixture of a cupric salt and a gold salt has been proposed.

【０００４】[0004]

【発明が解決しようとする課題】しかし、上記の第二銅
塩と金酸との混合物でなる前記従来の検知剤は、これま
でのものより速く変色するとはいえ、未だ十分な変色速
度とはいえない。また、蛍光灯程度の弱い光の場合には
余り問題はないが、太陽光のような強い光を受けると変
色し易く、このため、外光を避けて室内で保管しても、
外光の数分の１以下の光強度で部屋の窓から入射する光
や、部屋の窓から入射した光の反射光（光の強さは外光
の数１０分の１以下）により変色して、保管中に使用不
能になったり、室内で使用中の検知剤が同様の原因で変
色し、ガスを検知して変色したのか、光により変色した
のかが不明確になってしまうという不都合があった。However, although the conventional detection agent comprising a mixture of the cupric salt and gold acid described above discolors faster than the conventional ones, it still has a sufficient discoloration rate. I can't say. Also, in the case of weak light such as fluorescent light, there is not much problem, but it is easy to discolor when receiving strong light such as sunlight, so even if it is stored indoors while avoiding external light,
Discolored by light entering from a window of a room with a light intensity less than a few tenths of outside light or reflected light of light entering from a window in a room (light intensity is a few tenths or less of outside light) As a result, it becomes unusable during storage, and the detection agent used in the room discolors due to the same reason, and it is unclear whether the gas discolored by detecting gas or discolored by light. there were.

【０００５】そこで本発明は、揮発性無機水素化物と接
触したときの変色速度が速く、また、光による変色を生
じにくい検知剤を提供することを目的としている。Therefore, an object of the present invention is to provide a detecting agent which has a fast discoloring rate when brought into contact with a volatile inorganic hydride, and which hardly causes discoloration by light.

【０００６】[0006]

【課題を解決するための手段】上記した目的を達成する
ため、本発明の揮発性無機水素化物の検知剤は、亜鉛塩
と金塩との混合物、又は、ニッケル塩と金塩との混合物
でなることを特徴としている。In order to achieve the above-mentioned object, the volatile inorganic hydride detection agent of the present invention is a mixture of a zinc salt and a gold salt or a mixture of a nickel salt and a gold salt. It is characterized by becoming.

【０００７】本発明の検知剤に用いる金塩としては、塩
化金や塩化金酸等の金の各種無機酸塩，各種有機酸塩を
利用することができ、亜鉛塩としては、硫酸亜鉛等の亜
鉛の各種無機酸塩，各種有機酸塩を、また、ニッケル塩
としては、硫酸ニッケル等のニッケルの各種無機酸塩，
各種有機酸塩を、それぞれ利用することができる。前記
各種無機酸塩としては、炭酸塩，珪酸塩，硝酸塩，硫酸
塩，リン酸塩，塩素酸塩等のオルソ酸塩や塩化物，臭素
化物等のハロゲン化物を利用でき、各種有機酸塩として
は、ギ酸塩，酢酸塩，シュウ酸塩等を利用することがで
きる。As the gold salt used in the detecting agent of the present invention, various inorganic acid salts of gold such as gold chloride and chloroauric acid, and various organic acid salts can be used. As the zinc salt, zinc sulfate such as zinc sulfate can be used. Various inorganic acid salts of zinc, various organic acid salts, and nickel salts such as various inorganic acid salts of nickel such as nickel sulfate,
Various organic acid salts can be used respectively. As the various inorganic acid salts, ortho acid salts such as carbonates, silicates, nitrates, sulfates, phosphates, chlorates, and halides such as chlorides and bromides can be used. For example, formate, acetate, oxalate and the like can be used.

【０００８】亜鉛塩又はニッケル塩に対する金塩の混合
割合は、特に制限はないが、変色状況を容易に目視でき
るようにする点で、亜鉛塩，ニッケル塩中の亜鉛又はニ
ッケルに対する金塩中の金の割合（重量比）を０．００
１〜１．０とすることが望ましく、更に望ましくは、
０．０１〜０．５の範囲とするのが良い。The mixing ratio of the gold salt to the zinc salt or the nickel salt is not particularly limited, but from the viewpoint of facilitating visual observation of the discoloration state, the zinc salt in the zinc salt or the nickel salt, or the gold salt in the gold salt relative to the nickel salt. The ratio of gold (weight ratio) is 0.00
1 to 1.0 is preferable, and more preferably,
It is preferable to set it in the range of 0.01 to 0.5.

【０００９】本発明の検知剤における変色主剤は金塩で
あるが、金塩に混合する亜鉛塩又はニッケル塩が、単に
変色促進剤として作用するのか、それ自体も変色するの
かは明かではない。しかしながら、金塩に亜鉛塩又はニ
ッケル塩を混合してなる本発明の検知剤は、揮発性無機
水素化物に接触したときに、従来の検知剤よりも短時間
で変色する。特に、ニッケル塩と金塩との混合物でなる
本発明の検知剤の場合は、従来の検知剤より光に対する
影響を生じにくい。これらは、本発明者らが種々考究し
た結果得た知見である。The main color-changing agent in the detecting agent of the present invention is a gold salt, but it is not clear whether the zinc salt or nickel salt mixed with the gold salt merely acts as a color-changing accelerator or the color itself changes. However, the detection agent of the present invention, which is a mixture of a gold salt with a zinc salt or a nickel salt, discolors in a shorter time than conventional detection agents when contacted with a volatile inorganic hydride. In particular, in the case of the detection agent of the present invention composed of a mixture of nickel salt and gold salt, the influence on light is less likely to occur than the conventional detection agent. These are findings obtained as a result of various investigations by the present inventors.

【００１０】本発明の両検知剤は、粉末状のまま、もし
くはペレット状に成型して用いることができ、また、シ
リカゲル，アルミナゲル等の適宜な担体に担持させて用
いても良い。Both of the detection agents of the present invention can be used in the form of powder or molded into pellets, or may be used by being carried on an appropriate carrier such as silica gel or alumina gel.

【００１１】また、本発明の両検知剤は、シラン（モノ
シラン，ジシラン，トリシラン等を含む），アルシン，
ホスフィン，ジボラン，セレン化水素，ゲルマン等の揮
発性無機水素化物を検知可能で、これらの揮発性無機水
素化物に接触すると初期の淡黄色から茶褐色乃至紫色へ
と鋭敏に変色する。Both detection agents of the present invention include silane (including monosilane, disilane, trisilane, etc.), arsine,
Volatile inorganic hydrides such as phosphine, diborane, hydrogen selenide, and germane can be detected, and when they contact these volatile inorganic hydrides, the initial pale yellow color is rapidly changed to brown or purple.

【００１２】[0012]

【実施例】以下、本発明に係る検知剤の有効性を確認す
るために行った実験例及び比較例を説明する。 製造例 亜鉛塩と金塩との混合物でなる本発明の検知剤（以下、
Ｚｎ検知剤という）と、ニッケル塩と金塩との混合物で
なる本発明の検知剤（以下、Ｎｉ検知剤という）とを、
下記の製法により製造した。また、比較のため、特公平
２−３２２５４号公報を参照して第二銅塩と金塩との混
合物でなる検知剤（以下、従来検知剤という）を下記の
通り製造した。EXAMPLES Experimental examples and comparative examples conducted for confirming the effectiveness of the detection agent according to the present invention will be described below. Production Example The detection agent of the present invention comprising a mixture of zinc salt and gold salt (hereinafter,
Zn detection agent) and the detection agent of the present invention composed of a mixture of nickel salt and gold salt (hereinafter referred to as Ni detection agent),
It was manufactured by the following manufacturing method. For comparison, a detecting agent (hereinafter referred to as a conventional detecting agent) made of a mixture of cupric salt and gold salt was manufactured as described below with reference to JP-B-2-32254.

【００１３】Ｚｎ検知剤 硫酸亜鉛０．０５３ｇと塩化金酸０．０２５ｇとを水５
０ｍｌに溶解させた溶液を、３０ｇの粒状シリカゲル
（５〜１０メッシュ，比表面積２００ｍ² ／ｇ）に含浸
させた後、自然乾燥した。Zn detection agent 0.053 g of zinc sulfate and 0.025 g of chloroauric acid were added to 5 parts of water.
The solution dissolved in 0 ml was impregnated with 30 g of granular silica gel (5 to 10 mesh, specific surface area 200 m ² / g), and then naturally dried.

【００１４】Ｎｉ検知剤 硫酸ニッケル０．０５３ｇと塩化金酸０．０２７ｇとに
より、上記Ｚｎ検知剤と同様にして製造した。Ni detecting agent A nickel detecting agent was prepared in the same manner as the above Zn detecting agent, using 0.053 g of nickel sulfate and 0.027 g of chloroauric acid.

【００１５】従来検知剤 硫酸銅０．１８ｇと塩化金塩０．０１９ｇとにより、上
記Ｚｎ検知剤と同様にして製造した。Conventional detecting agent [0016] A 0.18 g of copper sulfate and 0.019 g of a gold chloride salt were prepared in the same manner as the Zn detecting agent.

【００１６】実験例１ 前記３種類の各検知剤を、それぞれ２ｇずつ内径３０ｍ
ｍのプラスチックカラムに充填し、該カラム内に下記３
種類の試料ガスＡ，Ｂ，Ｃを、それぞれ線速度０．２４
ｃｍ／秒で通して変色する迄の時間（単位は分）を測定
するとともに、変色状況を観察した。この結果を表１に
示す。Experimental Example 1 2 g of each of the above-mentioned three types of detection agents, and an inner diameter of 30 m
m plastic column and the following 3 in the column.
Linear velocity of 0.24 for each of the sample gases A, B, and C
The time (unit: minutes) until the color changed through cm / sec was measured, and the color change condition was observed. The results are shown in Table 1.

【００１７】 試料ガスＡ：アルシン１００ｐｐｍを含有する窒素ガス 試料ガスＢ：ホスフィン１００ｐｐｍを含有する窒素ガ
ス 試料ガスＣ：モノシラン１５ｐｐｍを含有する窒素ガスSample gas A: Nitrogen gas containing 100 ppm arsine Sample gas B: Nitrogen gas containing 100 ppm phosphine Sample gas C: Nitrogen gas containing 15 ppm monosilane

【００１８】[0018]

【表１】 [Table 1]

【００１９】表１から明らかなように、アルシン，ホス
フィン，シランの全てに対し、Ｚｎ検知剤及びＮｉ検知
剤は、共に従来検知剤よりも短時間で変色し、特にＺｎ
検知剤の変色速度が速いことが判る。As is clear from Table 1, both Zn detection agent and Ni detection agent discolored in a shorter time than conventional detection agents for all of arsine, phosphine and silane.
It can be seen that the discoloration speed of the detection agent is fast.

【００２０】実験例２ プラスチックカラムに充填された前記３種類の検知剤
を、屋外の同一の場所に並べて太陽光に当て、変色する
迄の時間（日没後はカウントしない）を測定するととも
に、変色状況を観察した。この結果を表２に示す。Experimental Example 2 The above-mentioned three kinds of detecting agents packed in a plastic column were arranged in the same outdoor place and exposed to sunlight to measure the time until discoloration (not counted after sunset) and discoloration. I observed the situation. The results are shown in Table 2.

【００２１】[0021]

【表２】 [Table 2]

【００２２】表２から明らかなように、Ｚｎ検知剤は、
従来検知剤よりも太陽光の影響をやや受け易いものの、
Ｎｉ検知剤は、従来検知剤に比べて太陽光の影響を受け
にくいことが判る。また、本実験例では、検知剤を直射
日光に曝しているので、従来検知剤の６時間に対してＮ
ｉ検知剤は２４時間で変色したが、室内で保管，使用す
るときに検知剤が受ける光は、窓からの入射光及び該入
射光の反射光であり、外光に比べて光の強度が小さいか
ら、従来検知剤とＮｉ検知剤とにおける光に対する安定
性は格段に広がることになる。したがって、Ｎｉ検知剤
によれば、室内での保管中や使用中に、検知剤が光によ
り変色するという不都合を大幅に低減できる。As is clear from Table 2, the Zn detecting agent is
Although it is slightly more susceptible to sunlight than conventional detection agents,
It can be seen that the Ni detecting agent is less susceptible to sunlight than the conventional detecting agents. In addition, in the present experimental example, since the detection agent is exposed to direct sunlight, N is compared with 6 hours of the conventional detection agent.
i The color of the detecting agent changed in 24 hours, but the light received by the detecting agent when it was stored and used indoors was the incident light from the window and the reflected light of the incident light, and the intensity of the light was higher than that of the outside light. Since it is small, the stability of the conventional detecting agent and the Ni detecting agent against light is significantly widened. Therefore, according to the Ni detecting agent, it is possible to greatly reduce the inconvenience that the detecting agent is discolored by light during storage or use indoors.

【００２３】[0023]

【発明の効果】以上説明したように、本発明の検知剤に
よれば、揮発性無機水素化物に接触したときに、従来の
検知剤より短時間で変色するので、揮発性無機水素化物
の有無を迅速に確認することができる。As described above, according to the detecting agent of the present invention, when it comes into contact with a volatile inorganic hydride, the color changes in a shorter time than that of the conventional detecting agent. Can be confirmed quickly.

【００２４】特に、ニッケル塩と金塩との混合物でなる
検知剤の場合は、従来の検知剤より光の影響を受けにく
いので、室内で保管したり使用した場合に、従来の検知
剤より遥かに安定して使用することができ、極めて実用
性が高い。In particular, the detection agent composed of a mixture of nickel salt and gold salt is less affected by light than the conventional detection agent, so that it is far better than the conventional detection agent when stored or used indoors. It can be used stably and extremely highly practical.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 亜鉛塩と金塩との混合物でなることを特
徴とする揮発性無機水素化物の検知剤。1. A volatile inorganic hydride detecting agent comprising a mixture of a zinc salt and a gold salt. 【請求項２】 ニッケル塩と金塩との混合物でなること
を特徴とする揮発性無機水素化物の検知剤。2. A volatile inorganic hydride detection agent comprising a mixture of a nickel salt and a gold salt.