JP3895604B2 - Germanium detection agent and detection method - Google Patents
Germanium detection agent and detection method Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、ゲルマンの検知剤及び検知方法に関する。さらに詳細には、半導体製造工程等から排出されるゲルマンを高感度で検知できる検知剤及び検知方法に関する。
【０００２】
【従来の技術】
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。また、例えば乾式浄化法によりゲルマンを浄化する場合は、浄化筒の破過を検知する必要がある。このため、取り扱いが容易で感度が高いゲルマンを検知するための検知剤あるいは検知方法が開発されてきた。
【０００３】
従来より、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）、無機質担体に変色成分としてモリブデン酸及びモリブデン酸塩の少なくとも一種が担持されてなる検知剤（特開平８−１２９００９号公報）が知られている。また、検知方法としては、ガラス管にこれらの検知剤を充填した検知管にサンプリングしたガスを通し、その変色により水素化物ガスの有無を検知する方法、有害ガスの浄化筒の覗き窓部等に検知剤を充填し、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。
【０００４】
【発明が解決しようとする課題】
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、無機質担体に変色成分としてモリブデン酸及びモリブデン酸塩の少なくとも一種が担持されてなる検知剤は、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、ゲルマンの検知については充分な感度が得られなかった。ゲルマンは他の水素化物に比べて反応性が低く、短時間で鋭敏に変色するようなゲルマンの検知剤の開発は困難であった。
【０００５】
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を、雰囲気ガスに影響されることなく高感度で検知できる検知剤あるいは検知方法を提供することである。
【０００６】
【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べく鋭意検討した結果、アルカリ金属の過マンガン酸塩が、感度が高く変色速度が速いゲルマンの検知剤の変色成分として使用し得ること、アルカリ金属の過マンガン酸塩をシリカゲルに対して０．００１〜０．３ｗｔ％の含有量で担持させることにより、優れた検出感度が得られることを見い出し、本発明のゲルマンの検知剤及び検知方法に到達した。
すなわち本発明は、シリカゲルに変色成分としてアルカリ金属の過マンガン酸塩を、シリカゲルに対して０．００１〜０．３ｗｔ％の含有量で担持させた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、ゲルマンを含有するガスを、シリカゲルに変色成分としてアルカリ金属の過マンガン酸塩をシリカゲルに対して０．００１〜０．３ｗｔ％の含有量で担持させた検知剤と接触させて、該検知剤の変色を検知することにより該ガスに含まれるゲルマンを検知することを特徴とするゲルマンの検知方法でもある。
【０００７】
【発明の実施の形態】
本発明は、窒素、水素、アルゴン、ヘリウム等を含むガス中に存在するゲルマンを検知する検知剤あるいは検知方法に適用されが、特に水素を含むガス中のゲルマン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。
【０００８】
本発明のゲルマンの検知剤は、シリカゲルに変色成分としてアルカリ金属の過マンガン酸塩を担持させた検知剤である。また、本発明のゲルマンの検知方法は、ゲルマンを含有するガスを、シリカゲルに変色成分としてアルカリ金属の過マンガン酸塩を担持させた検知剤と接触させて、検知剤の変色を検知することにより前記ガスに含まれるゲルマンを検知する検知方法である。
【０００９】
以下、本発明の検知剤について詳細に説明する。
本発明のゲルマンの検知剤においては、アルカリ金属の過マンガン酸塩がシリカゲルに対して０．００１〜０．３ｗｔ％の含有量で担持せしめられて検知剤とされる。アルミナ、ジルコニア、チタニア、シリカアルミナ、シリカチタニア等のシリカゲル以外の無機質担体を使用した場合は、比表面積が大きいものほど無機質担体の作用により光で過マンガン酸塩が分解しやすくなるので、高比表面積の無機質担体が使用できず高感度の検知剤が得られ難いという不都合がある。シリカゲルは、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。
【００１０】
本発明の検知剤における過マンガン酸塩としては、過マンガン酸リチウム、過マンガン酸ナトリウム、過マンガン酸カリウムを挙げることができるが、ゲルマンを検知しやすく、また容易に入手できることから、過マンガン酸カリウムを用いることが好ましい。アルカリ金属の過マンガン酸塩の含有量は、無機質担体に対して、通常は０．００１〜０．３ｗｔ％、好ましくは０．００５〜０．１ｗｔ％である。アルカリ金属の過マンガン酸塩の含有量が無機質担体に対して０．００１ｗｔ％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、ゲルマンは他の水素化物に比べて反応性が低く、ＡＣＧＩＨが定めている許容濃度（０．２ｐｐｍ）近辺のゲルマンを検知する際、アルカリ金属の過マンガン酸塩の含有量が無機質担体に対して０．３ｗｔ％を超える場合は検知剤の検出感度が悪くなる不都合を生じる。
【００１１】
アルカリ金属の過マンガン酸塩をシリカゲルに担持させる方法としては、アルカリ金属の過マンガン酸塩を含む水溶液をシリカゲルに含浸させた後乾燥する方法、あるいはシリカゲルをかき混ぜながら前記水溶液を振りかけて乾燥させる方法を例示することができる。
【００１２】
次に本発明の検知方法について詳細に説明する。
本発明のゲルマンの検知方法においては、半導体製造工程等から排出されるゲルマンを含有するガスを、前述の検知剤と接触させることによりガスに含まれるゲルマンが検知される。
本発明において、ゲルマンがアルカリ金属の過マンガン酸塩と接触すると、ゲルマンが酸化されるとともにアルカリ金属の過マンガン酸塩が変色するので、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を検知することができる。例えば、ゲルマンが白色のシリカゲルに過マンガン酸カリウムを担持させた検知剤と接触した場合、検知剤は赤紫色から白色に鋭敏に変色する。
【００１３】
本発明のゲルマンの検知剤は通常固体であり、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の配管のバイパス管に設置して、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を検知することができる。また、本発明のゲルマン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配置して使用される。
【００１４】
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。
【００１５】
本発明の検知剤及び検知方法においては、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を乾式浄化法により浄化する場合、ゲルマン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。
【００１６】
【実施例】
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。
【００１７】
実施例１
（検知剤の調製）
濃度１０ｇ／Ｌの過マンガン酸カリウム水溶液７．５ｍｌに１０００ｍｌの水を加えたものを、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（過マンガン酸カリウムの含有量：シリカゲルに対して０．０１５ｗｔ％）を調製した。
【００１８】
（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、これに１０ｐｐｍ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の条件で接触させ、検知剤が赤紫色から白色に変色し始めるまでの時間を測定した。その結果を表１に示す。
【００１９】
実施例２
実施例１におけるアルカリ金属の過マンガン酸塩を、過マンガン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。
【００２０】
実施例３，４
実施例１における検知対象ガス中のゲルマンの濃度を、各々１ｐｐｍ、２０ｐｐｍ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。
【００２１】
実施例５，６
実施例１における検知対象ガスの空筒線速度を、各々１ｃｍ／ｓｅｃ、５０ｃｍ／ｓｅｃ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。
【００２２】
実施例７
実施例１における検知対象ガス中のゲルマンの濃度を０．２ｐｐｍに、検知対象ガスの空筒線速度を５０ｃｍ／ｓｅｃ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。
【００２３】
実施例８〜１０
実施例１における過マンガン酸カリウムのシリカゲルに対する含有量を、各々０．０１ｗｔ％、０．１０ｗｔ％、０．３０ｗｔ％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。
これら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。
【００２４】
【表１】
【発明の効果】
本発明のゲルマンの検知剤及び検知方法により、半導体製造工程等から排出されるゲルマンを、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。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a germane detection agent and a detection method. More specifically, the present invention relates to a detection agent and a detection method that can detect germane discharged from a semiconductor manufacturing process or the like with high sensitivity.
[0002]
[Prior art]
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 into the atmosphere as it is. Has a detrimental effect on the human body and the environment, so it is necessary to purify the gas containing germane and ensure that it is not included prior to release to the atmosphere. For example, when germane is purified by a dry purification method, it is necessary to detect breakthrough of the purification cylinder. For this reason, detection agents or detection methods for detecting germane that are easy to handle and have high sensitivity have been developed.
[0003]
Conventionally, as a detecting agent for detecting hydride gas such as germane, for example, a detecting agent using a mixture of cupric salt and palladium salt as a discoloring component (Japanese Patent Laid-Open No. Sho 62-22062), No. 2 A detection agent comprising a mixture of a copper salt and a gold salt as a color change component (JP-A-2-32254), a detection agent comprising at least one of molybdic acid and molybdate as a color change component on an inorganic carrier No. 8-129009) is known. In addition, as a detection method, the sampled gas is passed through a detection tube filled with these detection agents into a glass tube, and the presence or absence of hydride gas is detected by the discoloration. A method of filling a detection agent and detecting breakthrough of the purification cylinder by its discoloration is generally used.
[0004]
[Problems to be solved by the invention]
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 impossible to detect breakthrough of the purification cylinder in which germane and the purification agent react to generate hydrogen. In addition, a detection agent comprising a mixture of cupric salt and gold salt as a color change component, a detection agent in which at least one of molybdic acid and molybdate as a color change component is supported on an inorganic carrier is highly sensitive to arsine and phosphine. However, sufficient sensitivity was not obtained for detection of germane. It has been difficult to develop a detection agent for germane that is less reactive than other hydrides and that changes its color sharply in a short time.
[0005]
Therefore, the problem to be solved by the present invention is to provide a detection agent or detection method that can detect germane discharged from a semiconductor manufacturing process or the like with high sensitivity without being affected by atmospheric gas.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve these problems, the present inventors have found that alkali metal permanganate can be used as a color-changing component of a Germanic detector having a high sensitivity and a fast color-changing speed . It has been found that excellent detection sensitivity can be obtained by loading the permanganate with a content of 0.001 to 0.3 wt% with respect to the silica gel, and has reached the germane detection agent and detection method of the present invention. .
That is, the present invention provides a permanganate of an alkali metal as a discoloring component to the silica gel, which is germane detection agent characterized by having supported thereon in a content of 0.001～0.3Wt% relative silica gel.
Further, the present invention is a gas containing germane, is contacted with a detecting agent which was supported by the content of 0.001～0.3Wt% permanganate respect silica gel alkali metal as discoloring component to silica gel Thus, the germane detection method is characterized by detecting germane contained in the gas by detecting discoloration of the detection agent.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is applied to a detection agent or detection method for detecting germane present in a gas containing nitrogen, hydrogen, argon, helium and the like, and is particularly effective in detecting germane in a gas containing hydrogen. The germane in the present invention includes digermane (Ge 2 H 6 ) and trigermane (Ge 3 H 8 ) in addition to monogermane (GeH 4 ).
[0008]
The germane detection agent of the present invention is a detection agent in which an alkali metal permanganate is supported on silica gel as a discoloration component. Further, the germane detection method of the present invention is to detect the discoloration of the detection agent by bringing a gas containing germane into contact with a detection agent in which an alkali metal permanganate is supported as a discoloration component on silica gel. It is a detection method for detecting germane contained in the gas.
[0009]
Hereinafter, the detection agent of the present invention will be described in detail.
In the germane detection agent of the present invention, an alkali metal permanganate is loaded on the silica gel at a content of 0.001 to 0.3 wt% to form a detection agent. When using an inorganic carrier other than silica gel, such as alumina, zirconia, titania, silica alumina, silica titania, etc. There is an inconvenience that an inorganic carrier having a surface area cannot be used and it is difficult to obtain a highly sensitive detection agent. As the silica gel, those having a specific surface area of 0.1 to 400 m 2 / g can be used.
[0010]
Examples of the permanganate in the detection agent of the present invention include lithium permanganate, sodium permanganate, and potassium permanganate. Permanic acid is easy to detect germanium and is easily available. It is preferable to use potassium. The content of the alkali metal permanganate is usually 0.001 to 0.3 wt%, preferably 0.005 to 0.1 wt% with respect to the inorganic support. When the content of the alkali metal permanganate is less than 0.001 wt% with respect to the inorganic carrier, the color of the discoloration component of the detection agent is too light, which makes it difficult to detect. In addition, germane is less reactive than other hydrides, and when detecting germane near the permissible concentration (0.2 ppm) specified by ACGIH, the content of alkali metal permanganate in the inorganic carrier On the other hand, when it exceeds 0.3 wt%, the detection sensitivity of the detection agent is disadvantageously deteriorated.
[0011]
METHOD The method of drying sprinkling the aqueous solution with stirring method or silica gel, dried was impregnated with an aqueous solution containing a permanganate of an alkali metal to silica gel supporting the permanganate of an alkali metal to silica gel Can be illustrated.
[0012]
Next, the detection method of the present invention will be described in detail.
In the germane detection method of the present invention, the germane contained in the gas is detected by bringing the gas containing germane discharged from the semiconductor manufacturing process or the like into contact with the aforementioned detection agent.
In the present invention, when germane comes into contact with an alkali metal permanganate, the germane is oxidized and the alkali metal permanganate is discolored. Therefore, by detecting the discoloration of the detection agent during this period, the germane in the gas is detected. Can be detected. For example, when germane comes into contact with a detection agent in which potassium permanganate is supported on white silica gel , the detection agent changes its color sharply from red purple to white.
[0013]
The detection agent of the germane of the present invention is usually solid, for example, the detection agent of the present invention is filled into a transparent tube made of glass to form a detection tube, and the detection target gas is sucked into the detection tube from a gas sampling port such as a pipe Thus, the target germane can be detected. In addition, the detection agent of the present invention is filled in a transparent tube made of glass or plastic, installed in a bypass pipe of the detection target gas piping, and the target germane is passed through the transparent tube. Can be detected. Further, when the detection agent for germane of the present invention is used to detect breakthrough of the purification cylinder, the detection agent is provided 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 being placed in a transparent viewing window provided between the windows.
[0014]
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).
[0015]
In the detection agent and detection method of the present invention, since no color change is caused by hydrogen even in the presence of hydrogen, germane in a gas containing hydrogen can be selectively detected with high sensitivity. Further, when the germane discharged from the semiconductor manufacturing process is purified by the dry purification method, breakthrough of the purification cylinder in which germane and the purification agent react to generate hydrogen can be detected with high sensitivity.
[0016]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
[0017]
Example 1
(Preparation of detection agent)
After impregnating 7.5 g of a potassium permanganate aqueous solution having a concentration of 10 g / L with 1000 ml of water into 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 rotary evaporator is used. Was dried under reduced pressure at a temperature of 80 ° C. to prepare a detection agent (potassium permanganate content: 0.015 wt% with respect to silica gel).
[0018]
(Measurement of detection ability)
A detection tube filled with 20 g of this detection agent in a glass tube having an inner diameter of 20 mm was manufactured, and nitrogen gas containing 10 ppm germane and 10% hydrogen was added thereto at 25 ° C., normal pressure, and an empty tube linear velocity of 5 cm / sec. The contact time was measured, and the time until the detection agent started to change color from reddish purple to white was measured. The results are shown in Table 1.
[0019]
Example 2
A detection agent was prepared in the same manner as in Example 1 except that the alkali metal permanganate in Example 1 was replaced with sodium permanganate.
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.
[0020]
Examples 3 and 4
The detection ability was measured in the same manner as in Example 1 except that the germane concentration in the detection target gas in Example 1 was changed to 1 ppm and 20 ppm, respectively. The results are shown in Table 1.
[0021]
Examples 5 and 6
The detection ability was measured in the same manner as in Example 1 except that the cylinder linear velocity of the detection target gas in Example 1 was changed to 1 cm / sec and 50 cm / sec, respectively. The results are shown in Table 1.
[0022]
Example 7
The detection ability was measured in the same manner as in Example 1 except that the concentration of germane in the detection target gas in Example 1 was changed to 0.2 ppm and the cylinder linear velocity of the detection target gas was changed to 50 cm / sec. The results are shown in Table 1.
[0023]
Examples 8-10
A detection agent was prepared in the same manner as in Example 1 except that the content of potassium permanganate in silica gel in Example 1 was changed to 0.01 wt%, 0.10 wt%, and 0.30 wt%, respectively.
The detection ability was measured in the same manner as in Example 1 except that these detection agents were used. The results are shown in Table 1.
[0024]
[Table 1]
【The invention's effect】
With the germane detection agent and detection method of the present invention, germane discharged from a semiconductor manufacturing process or the like can be detected with high sensitivity without being affected by atmospheric gas.
Claims (5)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002008199A JP3895604B2 (en) | 2002-01-17 | 2002-01-17 | Germanium detection agent and detection method |
| PCT/JP2002/013542 WO2003060510A1 (en) | 2002-01-17 | 2002-12-25 | Agent and method for detecting germane |
| TW92100844A TW200302348A (en) | 2002-01-17 | 2003-01-16 | Detector and method for detecting germane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002008199A JP3895604B2 (en) | 2002-01-17 | 2002-01-17 | Germanium detection agent and detection method |
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| JP2003207500A JP2003207500A (en) | 2003-07-25 |
| JP3895604B2 true JP3895604B2 (en) | 2007-03-22 |
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| US4420567A (en) * | 1981-10-22 | 1983-12-13 | Mda Scientific, Inc. | Hydride gas detecting tape |
| JPS6380830A (en) * | 1986-09-25 | 1988-04-11 | Osaka Oxygen Ind Ltd | Exhaust gas treatment agent in semiconductor industry |
| JPH03137917A (en) * | 1989-10-24 | 1991-06-12 | Iwatani Internatl Corp | Dry treatment of hydride type waste gas |
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| JP2003207500A (en) | 2003-07-25 |
| WO2003060510A1 (en) | 2003-07-24 |
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