JP2000214156A - Agent and method for detection - Google Patents

Abstract

PROBLEM TO BE SOLVED: To surely detect an organometallic compound in which a cyclopentadienyl ring is bonded to a metal by a method wherein a gas containing the organometallic compound in which the cyclopentadienyl ring is bonded to the metal is brought into contact with a detecting agent in which sulfuric acid is carried by an inorganic carrier, the metal is separated from the organometallic compound and the precipitation of the metal is detected. SOLUTION: A gas containing an organometallic compound in which a cyclopentadienyl ring is bonded to a metal is brought into contact with a detecting agent in which sulfuric acid is carried by an inorganic carrier. When the organometallic compound in which the cyclopentadienyl ring is bonded to the metal is brought into contact with the sulfuric acid which is carried by the inorganic carrier, the metal is separated from the organometallic compound so as to be precipitated. When the discoloration of the detecting agent during this time is detected, the organometallic compound in the gas can be detected. For example, when a gas which contains a metallocene is brought into contact with a detecting agent in which sulfuric acid is carried by white silical gel, a metal is separated from the metallocene so as to be precipitated, the metal is captured by the detecting agent, and the detecting agent is discolored sharply from a white color to a yellow color or a brown color.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organometallic compound detecting agent, and more particularly to nitrogen, hydrogen, argon, and the like.
The present invention relates to a detection agent and a detection method for an organometallic compound in which a metal is bonded to a cyclopentadienyl ring contained in a gas such as helium.

In recent years, with the development of the semiconductor industry, higher performance and higher integration of semiconductor devices have progressed, and various organometallic compounds have been used in place of conventionally used inorganic hydride gas and inorganic halide gas. It has become. Such organometallic compounds include, in addition to organometallic compounds having a carbon-metal bond, hydrides having a hydrogen-metal bond, amidates having a nitrogen-metal bond, β-diketone complex compounds having an oxygen-metal bond And alkoxides and organometallic compounds, and organometallic compounds in which a cyclopentadienyl ring is bonded to a metal.

As an organometallic compound in which a metal is bonded to a cyclopentadienyl ring, for example, bis (ethylcyclopentadienyl) ruthenium (Ru (C ₅ H ₄ C ₂ H ₅ ))
₂ ), bis (cyclopentadienyl) barium (Ba)
(C ₅ H ₅ ) ₂ ) and bis (cyclopentadienyl) strontium (Sr (C ₅ H ₅ ) ₂ ) are used as a CVD material for producing a ruthenium thin film, a barium thin film, and a strontium thin film by MOCVD or the like. It is used. In addition, one to four cyclopentadienyl rings and one or more of Ia-VIIa, VIII or Ib-I
Many organometallic compounds having a group IIb metal bonded thereto have been proposed as CVD materials.

[0004]

2. Description of the Related Art Although these organometallic compounds are indispensable materials for semiconductor production such as MOCVD, most of them are highly toxic or have not been confirmed to be safe. Therefore, it is necessary to confirm that the gas containing these organometallic compounds discharged from a semiconductor manufacturing process or the like is free from the organometallic compounds before being released to the atmosphere after being purified using a purifying device or the like. Therefore, a detecting agent is required. Therefore, there is a need for a detection agent or detection method for an organometallic compound in which a cyclopentadienyl ring is bonded to a metal, which is easy to handle and has high sensitivity. However, since many of these organometallic compounds are under research and development and have not been put into practical use, no detection agent or detection method capable of reliably detecting these organometallic compounds has been reported to date.

Conventionally, a large number of detecting agents or detecting methods have been developed for organometallic compounds other than those described above. For example, the present applicant also discloses in Japanese Patent Application Laid-Open No. 2-110370 an alkyl compound of tin, tellurium, cadmium, arsenic, mercury, aluminum, gallium and indium using a mixture of a copper (II) salt and a gold salt as a discoloring component. Are proposed. Also, Japanese Patent Application Laid-Open No. 2-285258 proposes a detecting agent for an alkyl compound of arsenic and phosphorus containing a nickel salt as a discoloring component. Also, Japanese Patent Application Laid-Open No. 6-273410 proposes an alkoxide detecting agent using a mixture of a copper (II) salt and a gold salt as a color-changing component. As other detecting agents, JP-A-7-839
No.13, an alkyl compound detecting agent comprising a mixture of a nickel salt and a gold salt.
JP-A-105879 discloses a detection agent such as a volatile inorganic hydride, a volatile inorganic halide, a volatile amine compound, an organometallic compound, etc., having bismuth chloride as a color-changing component.

[0006]

All of these conventionally known detecting agents are excellent, but cannot detect organometallic compounds in which a cyclopentadienyl ring and a metal are bonded. . Accordingly, an object of the present invention is to provide a detection agent or a detection method capable of practically and reliably detecting an organometallic compound in which a cyclopentadienyl ring and a metal are bonded.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve these problems, and as a result, a gas containing an organometallic compound in which a cyclopentadienyl ring and a metal are bonded is transferred to an inorganic carrier by sulfuric acid. Is brought into contact with the detection agent carrying
The present inventors have found that it is possible to detect the organometallic compound in the gas by separating the metal from the organometallic compound and detecting the deposition of the metal, and arrived at the present invention.

That is, the present invention is a detecting agent for a gas containing an organometallic compound in which a cyclopentadienyl ring and a metal are bonded, wherein sulfuric acid is supported on an inorganic carrier. Further, the present invention, a gas containing an organometallic compound in which a metal is bonded to a cyclopentadienyl ring and a metal are contacted with a detection agent having sulfuric acid supported on an inorganic carrier,
The present invention also provides a detection method comprising detecting the organometallic compound in the gas.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a detecting agent or a detecting method for detecting an organometallic compound having a cyclopentadienyl ring bonded to a metal, which is present in a gas such as nitrogen, hydrogen, argon or helium. Applied. In particular, according to the detection agent and the detection method of the present invention, even when an organic compound containing no metal is present in the detection target gas, without interference, the target organic metal compound alone is detected with high sensitivity. be able to.

The gas to be detected in the present invention is a gas mainly containing an organometallic compound in which a cyclopentadienyl ring is bonded to a metal of Group Ia to Group VIIa, Group VIII or Group Ib to Group IIIb. As an organometallic compound in which a cyclopentadienyl ring and a Group Ia metal are bonded, Li (C
₅ H _5), it can be exemplified Na _{(C 5 H} 5).
Examples of organometallic compounds in which a cyclopentadienyl ring and a Group IIa metal are bonded include Be (C ₅ H ₅ ) ₂ and Be (C ₅
H ₄ CH ₃ ) ₂ , Mg (C ₅ H ₅ ) ₂ , Mg (C ₅ H ₄
CH ₃ ) ₂ , Mg (C ₅ (CH ₃ ) ₅ ) ₂ , Ca (C _{5
H 5) 2, Ca (C} 5 (CH 3) 5) 2, Sr (C 5 H
₅ ) ₂ , Sr (C ₅ (CH ₃ ) ₅ ) ₂ , Ba (C
_{5 H 5) 2, Ba (} C 5 H 4 CH 3) 2, Ba (C
₅ (CH ₃ ) ₅ ) ₂ .

Cyclopentadienyl ring and Group IIIa metal
As an organometallic compound to which is bonded, Sc (C₅H₅)
₃, Y (C₅H₅)₃, Y (C₅H₄CH₃)₃, La
(C ₅H₅)₃, La (C₅H₄CH₃)₃, Ce (C
₅H₅)₃, Pr (C₅H₅)₃, Nd (C
₅H₅)₃, Nd (C₅H₄CH₃)₃, Sm (C₅H
₅)₃, Gd (C₅H₅)₃, Dy (C₅H₅)₃, E
r (C₅H₅)₃, Er (C₅H ₄CH₃)₃, Yb
(C₅H₅)₃, Yb (C₅H₄CH₃)₃Exemplify
be able to. Cyclopentadienyl ring and Group IVa metal
As the organometallic compound to which is bonded, Ti (C₅H₅)
₂, Ti (C₅H₅)₂(N₃)₂, Ti (C₅H₅)
₃, Ti (C₅H₅)₂(C₆H₅)₂, Zr (C₅H
₅)₂(N₃)₂Can be exemplified.

Examples of the organometallic compound in which a cyclopentadienyl ring and a Va group metal are bonded include V (C ₅ H ₅ ) ₂ ,
V (C ₅ H ₄ CH ₃ ) ₂ , V (C ₅ H ₅ ) ₂ (C
_{6 H 5) 2, Nb (} C 5 H 5) 2 C 4 H 7, Ta (C 5
_{H 5) 2 (N (CH} 3) 2) 2, Ta (C 5 H 5) 2 C
₄ H ₇ can be exemplified. As an organometallic compound in which a cyclopentadienyl ring and a metal of Group VIa are bonded,
Cr (C ₅ H ₅ ) ₂ , Cr (C ₅ H ₄ CH ₃ ) ₂ , Cr
_{(C 5 (CH 3) 5} ) 2, Mo (C 5 H 5) 4, W (C
₅ H ₅₎ can be exemplified ₂ H _2.

Cyclopentadienyl ring and Group VIIa metal
As an organometallic compound to which is bonded, Mn (C₅H₅)
₂, Mn (C₅H₄CH₃)₂, Mn (C₅H₄C₂H
₅) ₂, Mn (C₅H₄CH (CH)₂)₂, Mn (C
₅H₄C (CH)₃)₂, Mn (C₅H₃(C
H₃)₂)₂, Mn (C₅H (CH₃)₄)₂, Mn
(C₅(CH₃)₅)₂, Mn (C₅(CH₃)₄C₂
H₅)₂, Mn (C₅H₅) (C ₆H₅)₂, (Tc
(C₅H₅)₂)₂, Re (C₅H₅)₂H
be able to. Cyclopentadienyl ring and Group VIII metals
The organic metal compound to which is bonded is Fe (C₅H₅)
₂, Co (C₅H₅)₂, Ni (C₅H₅)₂, Ru
(C₅H ₅)₂, Ru (C₅H₄C₂H₅)₂Example
Can be

The cyclopentadienyl ring and the group Ib metal are
As the bonded organometallic compound, Cu (C₅H₅) P
(C₂H₅)₃Can be exemplified. Cyclopentane
An organometallic compound in which a dienyl ring is bonded to a metal of group IIb;
As a result, Zn (C₅H₅)₂, Hg (C₅H₅)₂The example
Can be shown. Cyclopentadienyl ring and IIIb
As an organometallic compound to which a group III metal is bonded, B (C₅
H₅)₃, Al (C₅H₅)₃, Tl (C₅H₅)₃,
In (C₅H ₅), In (C₅H₅)₃, In (C₅H
₄CH₃)₃Can be exemplified.

Next, the detecting agent of the present invention will be described in detail. The detecting agent of the present invention has sulfuric acid supported on an inorganic carrier,
It is a gas detecting agent containing an organometallic compound in which a metal is bonded to a cyclopentadienyl ring. In the present invention,
Sulfuric acid is carried on an inorganic carrier and used as a detecting agent. Examples of the inorganic carrier include silica gel, alumina, zirconia, titania, silica alumina, silica titania, etc. Among them, it is preferable to use silica gel which is resistant to sulfuric acid.

As the inorganic carrier, a white or colorless inorganic carrier is preferably used in order to easily detect the deposition of metal. Further, the inorganic carrier has a specific surface area of 50 to 400 m ² /
g is preferable, and if it is less than 50 m ² / g, the speed of separating and depositing the metal may be low, and
If it exceeds 0 m ² / g, the strength of the detecting agent may be weakened. As such an inorganic carrier, for example, silica gel having a specific surface area of about 450 to 800 m ² / g, which is commercially available for drying, can be used. Preferably, the specific surface area is 50 to 400 m ² by a hydrothermal synthesis method or the like. / G of silica gel prepared so as to be about 0.1 g / g.

Examples of the method of supporting sulfuric acid on an inorganic carrier include a method of immersing the inorganic carrier in sulfuric acid and evaporating water, and a method of dispersing sulfuric acid on the surface of the inorganic carrier. it can. The concentration of sulfuric acid used in the present invention is not particularly limited, but usually a concentration of 0.1N or more, preferably a concentration of 0.5N or more is used. In addition, the content of sulfuric acid with respect to the inorganic carrier is a weight ratio in a dry state, usually from 1: 0.01 to
0.5, preferably 1: 0.1 to 0.3. If the sulfuric acid content is less than 1/100 of the weight of the inorganic carrier, sufficient sensitivity cannot be obtained as a detecting agent, and if the sulfuric acid content exceeds 0.5 times the weight of the inorganic carrier, production is difficult. It is.

Next, the detection method of the present invention will be described in detail. The detection method of the present invention comprises contacting a gas containing an organometallic compound in which a cyclopentadienyl ring and a metal are bonded with a detecting agent in which sulfuric acid is supported on an inorganic carrier to remove the organometallic compound in the gas. This is a detection method for detecting. In the present invention, when the organometallic compound in which the cyclopentadienyl ring and the metal are bonded comes into contact with sulfuric acid supported on an inorganic carrier, the metal separates and precipitates from the organometallic compound, so that the discoloration of the detecting agent during this period is reduced. , The organometallic compound in the gas can be detected. For example,
When the gas containing the metallocene comes into contact with the detecting agent in which sulfuric acid is supported on white silica gel, the metal separates and precipitates from the metallocene, and the metal is captured in the detecting agent, and the detecting agent changes from white to yellow to brown. Discolors sharply.

The detecting agent of the present invention is usually a solid. For example, the detecting agent of the present invention is filled in a glass transparent tube to form a detecting tube, and a gas to be detected is sucked into the detecting tube from a gas sampling port such as a pipe. Thus, the target organometallic compound can be detected. Further, the detection agent of the present invention is filled in a transparent tube made of glass or plastic, and this is installed in a bypass pipe of a pipe for a gas to be detected, and the target organic compound is passed by passing the gas to be detected through the transparent tube. Metal compounds can be detected. Further, when the detecting agent of the present invention is used together with a purifying agent or the like, the detecting agent is provided on a downstream side of the purifying agent layer in the purifying cylinder, after the purifying cylinder or between plural purifying agent layers. It is used by installing it in a window.

When the detecting agent of the present invention is filled in a transparent tube and used in a bypass tube, or when the detecting agent of the present invention is used together with a purifying agent, etc.
The speed of the gas to be detected brought into contact with the detection agent is not particularly limited, but is usually 0.01 to 100 cm / sec in the linear velocity of the cylinder.
c. If the linear velocity of the cylinder is lower than the above range, the deposition is slow, and if the linear velocity is high, the pressure loss may increase. In addition, the temperature of the detection target gas at the time of contact is usually −
20 to 100 ° C., and the pressure is usually normal pressure.

[0021]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

(Preparation of Detecting Agent) (1) Detecting Agent A (Detecting agent in which sulfuric acid is supported on silica gel)
Preparation of particles having a size of 5 to 7 mesh and a specific surface area of 325 m ² /
g, pore volume 0.99 ml / g, packing density 0.420 g
/ Ml granular silica gel (manufactured by Fuji Silysia Chemical Ltd.)
Carrieract-10) 100 g of 2N sulfuric acid aqueous solution 2
After impregnation with 00 g and stirring, the mixture was dried under reduced pressure at a temperature of 80 ° C. using a rotary evaporator to prepare a detection agent A.

(2) Preparation of Detecting Agent B (Detecting Agent in Which Sulfuric Acid is Supported on Silica Titania)
mesh, specific surface area 362 m ² / g, pore volume 0.64
ml / g granular silica titania
Detector B was prepared in the same manner as described above.

(3) Detecting agent C (Activated alumina carrying sulfuric acid
Preparation of Detected Agent) The silica gel in the preparation of Detector A was treated with 6 to 10 mes.
h, specific surface area 210m ²/ G, pore volume 0.99 ml /
g, activated alumina with a packing density of 0.68 g / ml (Mizusawa Chemical
Neobeads GB8-16 manufactured by Gaku Co., Ltd.
Same as detecting agent A except that the amount of sulfuric acid aqueous solution was changed to 100 g
In this manner, a detecting agent C was prepared.

(Measurement of Detecting Ability) Example 1 A glass tube having an inner diameter of 19 mm filled with 2.0 g of a detecting agent A was prepared, and nitrogen gas containing 50 ppm of bis (ethylcyclopentadienyl) ruthenium was added thereto. The contact was performed at an air cylinder linear velocity of 10.5 cm / sec, and the time until the detection agent began to change color was measured. Table 1 shows the results.

Example 2 A glass tube having an inner diameter of 19 mm filled with 2.0 g of the detecting agent A was prepared, and nitrogen gas containing 1 ppm of bis (ethylcyclopentadienyl) ruthenium was charged with an air cylinder linear velocity of 10. Contact was made at 5 cm / sec, and the time until the detection agent began to change color was measured. Table 1 shows the results.

Example 3 The detection ability was measured in the same manner as in Example 1 except that the detection agent A in Example 1 was replaced with the detection agent B. Table 1 shows the results.

Example 4 The detection ability was measured in the same manner as in Example 2 except that the detection agent A in Example 2 was replaced with the detection agent B. Table 1 shows the results.

Example 5 The detection ability was measured in the same manner as in Example 1 except that the detecting agent A in Example 1 was replaced with the detecting agent C. Table 1 shows the results.

Example 6 The detection ability was measured in the same manner as in Example 2 except that the detecting agent A in Example 2 was changed to the detecting agent C. Table 1 shows the results.

[0031]

[Table 1]

[0032]

According to the detection agent and the detection method of the present invention, it has become possible to reliably detect an organometallic compound in which a cyclopentadienyl ring is bonded to a metal, which could not be detected conventionally.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Akira Asano 5181 Tamura, Hiratsuka-shi, Kanagawa F-Terminus, Hiratsuka Research Laboratories, Japan Pionics Co., Ltd. 2G042 AA01 BA03 BA04 BC02 BC09 BD01 BD17 CA01 CB01 DA08 FA01 FA11 FB06 GA04 HA02

Claims (4)

[Claims] 1. A detecting agent for a gas containing an organometallic compound in which a cyclopentadienyl ring and a metal are bonded, wherein sulfuric acid is supported on an inorganic carrier. 2. The detecting agent according to claim 1, wherein the inorganic carrier is at least one selected from silica gel, alumina, zirconia, titania, silica alumina, and silica titania. 3. The detecting agent according to claim 1, wherein the content of sulfuric acid with respect to the inorganic carrier is 1: 0.01 to 0.5 by weight in a dry state. 4. A gas containing an organometallic compound in which a cyclopentadienyl ring is bonded to a metal is brought into contact with a detection agent having sulfuric acid supported on an inorganic carrier to detect the organometallic compound in the gas. A detection method characterized in that: