JPS6221061A - Detecting agent - Google Patents

Abstract

PURPOSE:To obtain a detecting agent of low level of fading after change of color by making a copper salt of organic acid a color-changing component of a toxious gas detecting agent and detecting hydrogenated gases. CONSTITUTION:By making aliphatic carboxylic acid, aromatic carboxylic acid, amino acid, glycolic acid, etc., as copper salts of organic acid as color-changing components, a hydride-based gas containing one kind and more of arsine, phos phine, diborane, etc. are detected and fading after change of color is reduced.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a detection agent for hydride-based gases, and more specifically to arsine, phosphine, diborane, hydrogen selenide, and hydrogen sulfide used in semiconductor manufacturing processes. , germane, monosilane, disilane 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 they must be handled with great care.

Therefore, when handling these gases, it is necessary to constantly measure the working environment, and in the unlikely event that these gases leak, measures must be taken 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.

[Conventional technology]

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, and this method utilizes the fact that the detection agent changes color due to the reaction between the detection agent and the gas to be measured. . Conventional detection agents include, for example, mercury or its complex salts alone or a mixture of ferric salts or cupric salts adsorbed on silica gel particles for detecting phosphine, and gold compounds. is adsorbed onto silica gel particles for the detection of phosphine, arsine, and diborane, and lead acetate or copper sulfate is adsorbed onto the silica gel particles for the detection of 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. In addition, once these detectors change color, the color fades in a short time and returns to the original color, so there is a risk that the color change may be missed in cases where hydride gas is present only temporarily. There was also. Furthermore, since there is 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 there was.

[Problem that the invention seeks to solve]

Therefore, it is necessary to obtain a detecting agent that can be applied to the detection of many types of hydride gases and that exhibits less fading after discoloration.

[Means for solving problems]

The inventors of the present invention have conducted extensive studies to solve these problems in the conventional technology, and have found that copper salts of organic acids are extremely effective as color-changing components for detecting hydride gases used in semiconductor manufacturing processes. They discovered this and arrived at the present invention.

The present invention contains one or more of arsine, phosphine, diborane, hydrogen selenide, hydrogen sulfide, germane, monosilane, disilane, and dichlorosilane (hereinafter referred to as hydride gas), which has a copper salt of an organic acid as a discoloration component. It is a detection agent for harmful gases.

The detection agent of the present invention includes nitrogen gas, hydrogen gas, argon gas,
It can be commonly used to detect harmful gases such as helium gas and air containing the above-mentioned hydride gases. When these gases are brought into contact with the detection agent of the present invention, the blue to green copper salt of an organic acid sensitively changes color to black, and this color is maintained for a long time.

In the present invention, as the copper salt of an organic acid, copper salts of aliphatic carboxylic acids, aromatic carboxylic acids, amino acids, glycolic acids, etc. are usually used, and among these, the acid dissociation index PKa is 4.0 to 6. Copper salts of aliphatic or aromatic carboxylic acids in the range of 0 are preferred in terms of fading speed and sensitivity;
For example, aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, oleic acid, stearic acid, oxalic acid, malonic acid, and benzoic acid, 0-toluic acid, m- ) toluic acid, p-toluic acid, p-chlorobenzoic acid, p-fluorobenzoic acid,
p-furomobenzoic acid, 0-anisic acid, m-anisic acid, p
- Examples include copper salts of aromatic carboxylic acids such as anisic acid and phthalic acids.

Even when a copper salt of an inorganic acid is used as a color-changing component in a detecting agent, it will change color upon contact with the hydride gas mentioned above, but the color will fade and return to its original color in a short period of time, which is suitable for the purpose of the present invention. do not have.

In the present invention, a commercially available copper salt of an organic acid may be used as it is as a color-changing component, or a copper salt of an organic acid prepared by a conventionally known method may be used as a color-changing component.

In the present invention, the copper salt of an organic acid, which is a discoloration component, may be used as a detection agent in powder form or formed into a pellet or the like, or it may be supported on a carrier, preferably a porous carrier, as a detection agent. However, 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 preferably less than 50 m" / , particularly less than 2.17 y. A light-colored carrier is usually used, and white to colorless ones are preferably used. When using a carrier, There are no particular restrictions on the method of supporting the discoloration component, but for example, the carrier may be immersed in a solution prepared by dissolving or suspending a copper salt of an organic acid in water or a solvent, or after spraying such a solution on the surface of the carrier. May be dried.

The supported amount is usually 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight of the copper salt of an organic acid per 100 parts by weight of the carrier.
5 parts by weight.

The concentration of hydride gas detected by the detection agent of the present invention is usually 10 ppm or more for arsine, phosphine, hydrogen sulfide, and hydrogen selenide, and 50 ppm or more for diborane, germane, monosilane, disilane, and dichlorosilane. . The flow rate of the gas brought into contact with the detection agent is usually a linear velocity of o, o i ~i o 0js
It is considered as ec. The temperature and pressure of the gas during contact are usually -20 to 100°C and 0.001 to 20 k+?
/ cd 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 by putting it in a detection tube, but it can also be used in a more convenient form. For example, by placing the gas in a transparent container such as glass or plastic and passing the gas through the container, the presence of hydride gas in the gas can be easily detected.
be able to.

In this case, the detection agent is used after the removal agent layer or between multiple layers of the hydride gas removal cylinder, or by placing it inside the detection cylinder and connecting the detection cylinder after the removal cylinder. Ru.

[action, effect]

The detection agent of the present invention has the following excellent effects and is extremely useful industrially.

(1) It has high sensitivity for detecting most hydride gases used in semiconductor manufacturing processes, etc. (and can be used commonly).

(2) Once a detecting agent has changed color due to contact with a hydride gas, the color does not return to its original color within a short period of time, so the change in color cannot be overlooked.

(3) It can be used to detect breakthrough by filling the outlet of a gas adsorption cylinder or other abatement device, or can be used to detect leaks in a workplace, and has a wide range of applications.

〔Example〕

A hard polyvinyl chloride column with an inner diameter of 13 mH2f was filled with a detection agent in which 1 ton of spherical silica gel with an average diameter of 3 mm was loaded with 50 blades each of copper acetate and copper oleate, and 10 ppm of arsine, phosphine, hydrogen selenide or Hydrogen sulfide or 50 ppm diborane,
Nitrogen gas containing germane, monosilane, disilane or dichlorosilane at a linear velocity of 0.1 cx/sec
After each sample was brought into contact with a detection agent to completely turn black, it was taken out from the column and left in the atmosphere, and the time until the color faded to its original color was measured.

[Comparative example]

Similarly, a detection agent in which 5011 g of copper sulfate was supported on 1 ton of spherical silica gel was also turned black, and then the time required for the detection agent to fade to its original color was measured.

The results are shown in Table 1.

Claims (1)

[Claims] Arsine, phosphine, which contains copper salts of organic acids as color-changing ingredients.
A detection agent for toxic gases containing one or more of diborane, hydrogen selenide, hydrogen sulfide, germane, monosilane, disilane, and dichlorosilane.