JP5938847B2 - Halogen-containing gas supply device - Google Patents

Description

  The present invention relates to a halogen-containing gas supply device.

  Halogen gas plays an important role as an etching process gas for substrates in semiconductor manufacturing processes such as semiconductor devices, МEMS devices, liquid crystal TFT panels and solar cells, and a cleaning process gas for thin film forming equipment such as CVD equipment. ing.

  As a halogen gas supply device, there is a supply device including a cylinder filled with a high pressure of a halogen gas. The halogen gas in the cylinder is supplied to the semiconductor manufacturing apparatus through a valve for introduction.

  By improving the filling pressure of the halogen gas and reducing the replacement frequency of the cylinder, it is possible to reduce the transportation cost and work load of the cylinder. In addition, the cleaning process can be efficiently performed by using a high-concentration halogen gas. Therefore, it is desired to fill the cylinder with a high pressure and high concentration with a halogen gas and supply it safely and stably to the process side.

  Halogen gas is a highly reactive gas and is not easy to handle in semiconductor manufacturing equipment. In particular, development of a container valve suitable for highly reactive fluorine gas and a technique for supplying high-pressure fluorine gas to the process side safely and stably are desired.

  Patent Document 1 discloses a container valve that supplies a high concentration fluorine gas to a semiconductor manufacturing system at a high pressure.

  Patent Document 2 discloses a vacuum pumping performance and a purging performance as a container valve (valve) for supplying a high purity gas such as a semiconductor material gas, a purge gas, a standard gas, and a carrier gas used in the semiconductor industry. For the purpose of improving gas replacement characteristics, a direct diaphragm valve is disclosed in which an obstacle is removed from a gas flow path and a dead space in which gas stays is minimized.

  Further, Patent Document 3 discloses a valve in which a rubber seal is disposed in a portion recessed from a flame flow path in order to cope with burnout of the rubber seal and a decrease in the sealing function of the seal portion of the valve.

  Furthermore, Patent Document 4 discloses a linear servo valve that does not burn out the coil or deteriorates insulation by adopting a configuration in which the coil or bobbin that opens and closes the valve seat is air-cooled.

JP 2005-207480 A JP 2005-188672 A JP 2000-291500 A Japanese Utility Model Publication No. 5-62704

  However, since the container valve described in Patent Document 1 is a valve that opens and closes a gas flow path with a seat disk and seals the airtightness with the outside by a diaphragm, a dead space in which gas in the valve chamber tends to stay increases. .

  Patent Document 2 discloses that the influence of gas molecules such as moisture and particles adsorbing on the surface of the gas contact portion is reduced by polishing the inside of the valve. However, the detailed polishing portion and shape are not specifically described. Further, there is no description that it can be applied to fluorine and fluorine compound gas.

In conventional valves, when high-pressure, high-concentration fluorine gas is handled, the temperature in the valve chamber rises, causing problems such as surface corrosion in the valve chamber and deterioration of the sealing material. Also, resin materials are used for the sealing material. There was a problem that the resin material was burnt out by fluorine gas. This problem is also the same when handling flammable gases such as O ₂ and NO.

  The valve described in Patent Document 3 is a countermeasure against backfire, and cannot be applied to high-pressure, high-concentration fluorine gas. Further, the linear servo valve described in Patent Document 4 is such that coils and bobbins are air-cooled and cannot be applied to high-pressure, high-concentration fluorine gas.

  When introducing halogen gas from a container filled with high corrosive halogen gas such as fluorine gas through a supply valve, the halogen gas is likely to increase the internal temperature of the introduction valve on the introduction side. There has been a problem that surface corrosion in the valve chamber and deterioration of the sealing material are likely to occur.

  The present invention has been made in view of the above-described problems, and suppresses a temperature rise in the valve chamber of the introduction valve that introduces the halogen-containing gas to the external device. It aims at suppressing deterioration of the sealing material used.

The present invention is a halogen-containing gas supply device that supplies a halogen-containing gas from a container filled with the halogen-containing gas to an external device, the supply pipe connecting the container and the external device, A first supply valve provided in the supply pipe for supplying a halogen-containing gas from the container, and at least a part of the supply pipe downstream of the first supply valve has a gas flow cross-sectional area of 0.5 cm. It is characterized by being provided with details that are ² or less.

  The present invention further includes a bypass pipe connected to the supply pipe so as to bypass the details, and a second supply valve provided in the bypass pipe.

  In the present invention, the halogen of the halogen-containing gas is fluorine, chlorine, bromine, or iodine.

  Further, the present invention is characterized in that the halogen-containing gas filling pressure is 5 MPa or more and 20 MPa or less.

  In the present invention, an orifice plate is used for the details.

  In the present invention, a valve is used for the details.

According to the present invention, the supply pipe is provided with details having a gas flow cross-sectional area of 0.5 cm ² or less, so that the temperature rise in the valve chamber of the introduction valve, the surface corrosion of the introduction valve, and the seal used for the introduction valve Deterioration of the material can be suppressed.

The schematic of one Example of the halogen containing gas supply apparatus of this invention is shown. The schematic of the apparatus used for Example 1, 4-15, and the comparative example 2 is shown. The schematic of the apparatus used for Example 2 is shown. The schematic of the apparatus used for Example 3 is shown. The schematic of the apparatus used for the comparative example 1 is shown.

A halogen-containing gas supply apparatus according to an embodiment of the present invention supplies a halogen-containing gas from a container filled with the halogen-containing gas to an external device, and connects the container and the external device. A supply pipe, and a first supply valve provided in the supply pipe for supplying the halogen-containing gas from the container. At least a part of the supply pipe is provided with details with a gas flow cross-sectional area of 0.5 cm ² or less. An introduction valve for introducing the halogen-containing gas into the external device is provided downstream of the first supply valve. The introduction valve may be provided in the external device, or may be provided in the halogen-containing gas supply device.

  The external apparatus is a semiconductor manufacturing apparatus that manufactures semiconductors used for semiconductor devices, МEMS devices, liquid crystal TFT panels, solar cells, and the like. The halogen-containing gas is used as a cleaning process gas or an etching process gas in a semiconductor manufacturing process.

  Hereinafter, a halogen-containing gas supply device according to an embodiment of the present invention will be described in detail.

  A container filled with a halogen-containing gas at a high pressure includes an on-off valve. The container only needs to have a sealing property capable of maintaining a high pressure of at least 5 MPaG and a structure capable of releasing a halogen-containing gas with an on-off valve. Desirably, it preferably has a hermeticity capable of maintaining a high pressure of 20 MPaG or more.

  The material of the container is preferably one having corrosion resistance against the halogen gas to be filled, and examples thereof include manganese steel, stainless steel, and nickel-containing alloys (Hastelloy, Inconel, Monel, etc.).

  The halogen of the halogen-containing gas is fluorine, chlorine, bromine, or iodine, and any two or more of these may be mixed.

Any halogen-containing gas may be used as long as it contains halogen, and fluorine gas, chlorine gas, bromine gas, iodine gas halogen gas, or halogen compounds such as NF ₃ , BF ₃ , ClF, ClF ₃ , and IF ₇ . These gases may be mixed with an inert gas such as N ₂ , Ar, or He. Alternatively, a mixed gas of a halogen gas and a halogen compound gas may be mixed with an inert gas.

The concentration of the halogen gas or halogen compound gas in the halogen-containing gas is not particularly limited. For example, fluorine gas, chlorine gas, bromine gas, iodine gas, NF ₃ gas, BF ₃ gas, ClF gas, ClF ₃ gas, And at least any one of IF ₇ gas is in the range of 0.1 vol% or more and 100% or less.

  The filling pressure of the halogen-containing gas is desirably 5 MPaG or more and 20 MPaG or less. If the pressure is less than 5 MPaG, the temperature inside the introduction valve on the introduction side is unlikely to increase, and surface corrosion in the valve chamber of the introduction valve and deterioration of the sealing material used for the introduction valve are unlikely to occur. On the other hand, if it exceeds 20 MPaG, the temperature inside the introduction valve will not increase due to the provision of the supply device of the present invention, but corrosion of the surface of the gas contact part due to halogen gas tends to occur, which is not preferable.

The detailed structure of the supply pipe is not particularly limited, as long as the gas flow cross-sectional area can be specified, such as a valve or an orifice plate that makes the gas flow cross-sectional area smaller than other parts. Moreover, you may make it comprise a detail with a linear tube. That is, the first supply valve and the introduction valve may be connected by a tube having a uniform pipe diameter. The gas cross-sectional area in detail is preferably 0.5 cm ² or less. The minimum minimum gas flow cross-sectional area is not limited as long as the gas can flow, and is specifically preferably 0.0001 cm ² or more. Furthermore, in consideration of the sealing time of the halogen-containing gas up to the connection portion between the supply pipe and the external device, it is particularly preferably 0.001 cm ² or more.

Furthermore, a bypass pipe may be connected to the supply pipe so as to bypass details, and a second supply valve may be provided in the bypass pipe. Thus, when supplying the halogen-containing gas to the external device, the halogen-containing gas flows through the bypass pipe by sealing the halogen-containing gas up to the connection portion between the supply pipe and the external device and then opening the second supply valve. Therefore, the supply flow rate of the halogen-containing gas can be improved. Accordingly, the gas flow cross-sectional area of the bypass pipe is preferably more than 0.5 cm ² .

  The supply pipe may have a plurality of details. For example, a plurality of details may be arranged in series or in parallel.

  It is desirable to use a metal material for the portions where the halogen gas contacts the opening / closing valve, supply pipe, first supply valve, bypass pipe, second supply valve, and introduction valve of the container. Examples of the metal material include stainless steel, inconel, or hastelloy.

  The valve structures of the on-off valve, the first supply valve, and the second supply valve are not particularly limited.

  A case where the halogen-containing gas supply apparatus of the present invention is connected to, for example, a semiconductor manufacturing apparatus as an external apparatus and a halogen-containing gas is supplied to the semiconductor manufacturing apparatus will be described with reference to FIG.

In the embodiment shown in FIG. 1, the first supply valve 3 is connected via a conduit 6 to the on-off valve 2 of the container 1 filled with a halogen-containing gas at a high pressure. A supply pipe 4 is connected to the first supply valve 3, and a semiconductor manufacturing apparatus 101 is connected to the downstream end of the supply pipe 4. The supply pipe 4 is provided with an introduction valve 100 for guiding the halogen-containing gas supplied through the first supply valve 3 to the semiconductor manufacturing apparatus 101. In the supply pipe 4, the details 5 (for example, the opening has a cross-sectional area of 0.001 cm ² or more and 0 or less between the first supply valve 3 and the introduction valve 100 having a smaller gas flow cross-sectional area than other parts). (Orifice plate of 5 cm ² or less). The on-off valve 2 and the first supply valve 3 are diaphragm valves whose gas contact parts are all metal.

  In FIG. 1, with the first supply valve 3 opened and the on-off valve 2 and the introduction valve 100 closed, the inside of the conduit 6 and the supply pipe 4 from the on-off valve 2 to the introduction valve 100 is separated by a vacuum line (not shown). Set to vacuum. Thereafter, the first supply valve 3 is closed, the on-off valve 2 is opened, and a halogen-containing gas is sealed in the conduit 6 from the container 1 to the first supply valve 3. Thereafter, by opening the first supply valve 3, the pressure in the supply pipe 4 from the first supply valve 3 to the introduction valve 100 increases, and the internal pressure becomes constant. As a result, the semiconductor manufacturing apparatus 101 can be supplied with a halogen-containing gas. Further, when a bypass pipe that bypasses the details 5 is connected to the supply pipe 4 and a second supply valve is provided in the bypass pipe (not shown), the supply pipe 4 from the first supply valve 3 to the introduction valve 100 is provided. After the internal pressure rises and the internal pressure becomes constant, the halogen supply gas can be supplied to the semiconductor manufacturing apparatus 101 by opening the second supply valve.

  When supplying a high-pressure halogen-containing gas by opening the supply valve, the internal temperature of the introduction valve for introducing the halogen-containing gas into the external device is likely to increase, and surface corrosion or introduction in the valve chamber of the introduction valve The sealing material used for the valve is likely to deteriorate. This is presumed that due to the opening of the supply valve, a shock wave is generated in the supply pipe through which the halogen-containing gas flows, and it grows in the process of propagation of the generated shock wave and reaches the introduction valve. Is done. Therefore, in the present invention, the generation or growth of shock waves is suppressed by providing the details 5 having a small gas flow cross-sectional area between the first supply valve 3 and the introduction valve 100 of the supply pipe 4. Thereby, the temperature rise inside the introduction valve, the surface corrosion inside the valve chamber of the introduction valve, and the deterioration of the sealing material can be suppressed.

  Hereinafter, the present invention will be described in detail by way of examples.

FIG. 2 shows a schematic diagram of this embodiment. Manganese steel container 1 is filled with 20 vol% F ₂ gas diluted with N _{2 at} a pressure of 5 MPaG. An opening / closing valve 2 is attached to the container 1. The on-off valve 2 and the first supply valve 3 are connected by a straight stainless steel conduit 6 having an outer diameter of ½ inch, a thickness of 1 mm, and a length of 200 mm. A stainless steel supply pipe 4 having the same shape as the conduit 6 is connected to the downstream side of the first supply valve 3. A stainless steel orifice plate 25 is interposed in the middle of the supply pipe 4, and a stainless steel cylinder 26 having an internal capacity of 50 cc is connected to the downstream side of the orifice plate 25. The gas flow sectional area of the orifice plate 25 is 0.1 cm ² .

  A vacuum line 29 is connected to the downstream side of the cylinder 26 via a manual valve 28. A PCTFE (ethylene trifluoride chloride) chip 27 having a side of 3 mm is sealed at the bottom of the downstream end in the cylinder 26.

  The on-off valve 2 and the first supply valve 3 are all-metal diaphragm automatic valves. The manual valve 28 and the vacuum line 29 are for performing gas replacement in the conduit 6 and the supply pipe 4.

  Next, the operation will be described. With the on-off valve 2 closed and the other valves opened, the inside of the conduit 6 and the supply pipe 4 is evacuated through the vacuum line 29. Then, after all the valves were closed, the on-off valve 2 was opened, and the pressure in the conduit 6 from the container 1 to the first supply valve 3 was set to 5 MPaG.

  Further, the first supply valve 3 was opened, and the pressure in the supply pipe 4 from the container 1 to the cylinder 26 was set to 5 MPaG. Thereafter, the on-off valve 2 was closed and the gas in the conduit 6 and the supply tube 4 was replaced through the vacuum line 29.

  After the above operation was repeated 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, there was no visual change and the weight loss rate was 0.5% by mass or less. Met. Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

FIG. 3 shows a schematic diagram of this embodiment. In this embodiment, a valve 35 is provided instead of the orifice plate 25. Other configurations are the same as those in the first embodiment. The valve 35 is an all-metal diaphragm automatic valve, and the minimum gas flow cross-sectional area in the valve when the valve is opened is 0.1 cm ² .

  Next, the operation will be described. With the open / close valve 2 closed and the other valves opened, the inside of the conduit 6 and the supply pipe 4 is evacuated by the vacuum line 29. Then, after all the valves were closed, the on-off valve 2 was opened, and the pressure in the conduit 6 from the container 1 to the first supply valve 3 was set to 5 MPaG.

  Further, after the valve 35 was opened, the first supply valve 3 was opened, and the pressure in the supply pipe 4 from the container 1 to the cylinder 26 was set to 5 MPaG. Thereafter, the on-off valve 2 was closed, and the gas in the conduit 6 and the supply pipe 4 was replaced through the vacuum line 29.

  After the above operation was repeated 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, there was no visual change and the weight loss rate was 0.5% by mass or less. Met. Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

  FIG. 4 shows a schematic diagram of this embodiment. In this embodiment, a stainless steel orifice plate 45 is interposed in the middle of a linear stainless steel supply pipe 4 having an outer diameter of 1/2 inch and a wall thickness of 1 mm. Further, a stainless steel bypass pipe 411 having an outer diameter of ½ inch and a wall thickness of 1 mm through which the second supply valve 410 is interposed is connected to the supply pipe 4 so as to bypass the orifice plate 45. Other configurations are the same as those in the first embodiment.

  Next, the operation will be described. With the open / close valve 2 closed and the other valves opened, the inside of the conduit 6 and the supply pipe 4 is evacuated by the vacuum line 29. Then, after all the valves were closed, the on-off valve 2 was opened, and the pressure in the conduit 6 from the container 1 to the first supply valve 3 was set to 5 MPaG.

  Furthermore, after the first supply valve 3 was opened and the pressure in the supply pipe 4 from the container 1 to the cylinder 26 was set to 5 MPaG, the second supply valve 410 was opened. Thereafter, the on-off valve 2 was closed, and the gas in the conduit 6 and the supply pipe 4 was replaced through the vacuum line 29.

  After the above operation was repeated 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, there was no visual change and the weight loss rate was 0.5% by mass or less. Met. Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 20 vol% F ₂ gas diluted with N _{2 at} a pressure of 14.7 MPaG. Other configurations are the same as those of the first embodiment.

  Next, the operation will be described. With the open / close valve 2 closed and the other valves opened, the inside of the conduit 6 and the supply pipe 4 is evacuated by the vacuum line 29. Then, after all the valves were closed, the on-off valve 2 was opened, and the pressure in the conduit 6 from the container 1 to the first supply valve 3 was set to 14.7 MPaG.

  Further, the first supply valve 3 was opened, and the pressure in the conduit from the container 1 to the cylinder 26 was set to 14.7 MPaG. Thereafter, the on-off valve 2 was closed, and the gas in the conduit 6 and the supply pipe 4 was replaced through the vacuum line 29.

  After the above operation was repeated 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, there was no visual change and the weight loss rate was 0.5% by mass or less. Met. Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In the present embodiment, the gas flow cross-sectional area of the orifice plate 25 is 0.0002 cm ² . Other configurations are the same as those in the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In the present embodiment, the gas flow cross-sectional area of the orifice plate 25 is 0.001 cm ² . Other configurations are the same as those in the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the gas flow sectional area of the orifice plate 25 is 0.49 cm ² . Other configurations are the same as those in the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 10 vol% Cl ₂ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 0.5 vol% Br ₂ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 0.1 vol% iodine gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with a 10 vol% F ₂ + Cl ₂ mixed gas (50% by volume of F ₂ and Cl ₂ are 50 vol% each) diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 20 vol% F ₂ gas diluted with N _{2 at} a pressure of 3.6 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 10 vol% F ₂ gas diluted with N _{2 at} a pressure of 19 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 10 vol% F ₂ gas diluted with N _{2 at} a pressure of 21 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After the operation was repeated 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, although the tip surface was slightly discolored, the weight reduction rate was 0. It was 5 mass% or less. Since no change in weight occurred and the change in visual observation was slight, the burnout of PCTFE was in a range where there was no problem.

In this embodiment, the container 1 is filled with 50 vol% F ₂ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 100 vol% NF ₃ gas at a pressure of 14.7 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 100 vol% O ₂ gas at a pressure of 14.7 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 20 vol% BF ₃ gas diluted with N _{2 at} a pressure of 14.7 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 20 vol% ClF gas diluted with N _{2 at} a pressure of 14.7 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 0.1 vol% ClF ₃ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

  After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.

In this embodiment, the container 1 is filled with 0.1 vol% IF ₇ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first embodiment. The operation was performed in the same manner as in Example 1.

After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, there was no visual change and the weight reduction rate was 0.5% by mass or less. . Since no visual change or weight loss occurred, it can be determined that no PCTFE burnout occurred.
[Comparative Example 1]
FIG. 5 shows a schematic diagram of this comparative example. In this comparative example, the manganese steel container 1 is filled with 20 vol% F ₂ gas diluted with N _{2 at} a pressure of 5 MPaG. An opening / closing valve 2 is attached to the container 1. The on-off valve 2 and the first supply valve 3 are connected by a straight stainless steel conduit 6 having an outer diameter of ½ inch, a thickness of 1 mm, and a length of 200 mm. A stainless steel cylinder 26 with an internal capacity of 50 cc is connected to the downstream side of the first supply valve 3 via a stainless steel supply pipe 4 having the same shape as the conduit 6.

  A vacuum line 29 is connected to the downstream side of the cylinder 26 via a manual valve 28. A PCTFE chip 27 having a side of 3 mm is enclosed at the bottom of the downstream end in the cylinder 26.

  The on-off valve 2 and the first supply valve 3 are all-metal diaphragm automatic valves. The manual valve 28 and the vacuum line 29 are for performing gas replacement in the conduit 6 and the supply pipe 4.

  Next, the operation will be described. With the on-off valve 2 closed and the other valves opened, the inside of the conduit 6 and the supply pipe 4 is evacuated through the vacuum line 29. Then, after all the valves were closed, the on-off valve 2 was opened, and the pressure in the conduit 6 from the container 1 to the first supply valve 3 was set to 5 MPaG.

  Further, the first supply valve 3 was opened, and the pressure in the supply pipe 4 from the container 1 to the cylinder 26 was set to 5 MPaG. Thereafter, after 5 minutes, the on-off valve 2 was closed, and the gas in the conduit 6 and the supply tube 4 was replaced through the vacuum line 29.

After repeating the above operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, about 50% of the PCTFE surface was discolored due to burning. The weight reduction rate was 12% by mass. Since visual change and weight loss occurred, it can be determined that PCTFE burnout occurred.
[Comparative Example 2]
In this comparative example, the gas flow cross-sectional area of the orifice plate 25 is 0.6 cm ² . Other configurations are the same as those in the first embodiment. The operation was performed in the same manner as in Example 1.

After repeating this operation 10 times, the PCTFE tip 27 in the cylinder 26 was taken out and visually observed and the weight reduction rate was measured. As a result, about 30% of the PCTFE surface was discolored due to burnout. The weight reduction rate was also 7% by mass. Since visual change and weight loss occurred, it can be determined that PCTFE burnout occurred.
[Comparative Example 3]
In this comparative example, the container 1 is filled with 100 vol% NF ₃ gas at a pressure of 14.7 MPaG. Other configurations are the same as those of the first comparative example. The operation was performed in the same manner as in Comparative Example 1.

After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, although the weight change rate was 0.5% by mass or less, discoloration due to burnout was observed on the surface, though slight, by visual observation.
[Comparative Example 4]
In this comparative example, the container 1 is filled with 100 vol% O ₂ gas at a pressure of 14.7 MPaG. Other configurations are the same as those of the first comparative example. The operation was performed in the same manner as in Comparative Example 1.

After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, although the weight change rate was 0.5% by mass or less, discoloration due to burnout was observed on the surface, though slight, by visual observation.
[Comparative Example 5]
In this comparative example, the container 1 is filled with 20 vol% BF ₃ gas diluted with N _{2 at} a pressure of 14.7 MPaG. Other configurations are the same as those of the first comparative example. The operation was performed in the same manner as in Comparative Example 1.

After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, although the weight change rate was 0.5% by mass or less, discoloration due to burnout was observed on the surface, though slight, by visual observation.
[Comparative Example 6]
In this comparative example, the container 1 is filled with 20 vol% ClF gas diluted with N _{2 at} a pressure of 14.7 MPaG. Other configurations are the same as those of the first comparative example. The operation was performed in the same manner as in Comparative Example 1.

After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, although the weight change rate was 0.5% by mass or less, discoloration due to burnout was observed on the surface, though slight, by visual observation.
[Comparative Example 7]
In this comparative example, the container 1 is filled with 0.1 vol% ClF ₃ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first comparative example. The operation was performed in the same manner as in Comparative Example 1.

After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, although the weight change rate was 0.5% by mass or less, discoloration due to burnout was observed on the surface, though slight, by visual observation.
[Comparative Example 8]
In this comparative example, the container 1 is filled with 0.1 vol% IF ₇ gas diluted with N _{2 at} a pressure of 5 MPaG. Other configurations are the same as those of the first comparative example. The operation was performed in the same manner as in Comparative Example 1.

After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, although the weight change rate was 0.5% by mass or less, discoloration due to burnout was observed on the surface, though slight, by visual observation.
[Comparative Example 9]
In this comparative example, the gas flow cross-sectional area of the orifice plate 25 is 0.6 cm ² . Other configurations are the same as those in the seventeenth embodiment. The operation was performed in the same manner as in Example 17.

  After repeating this operation 10 times, the PCTFE chip 27 in the cylinder 26 was taken out and visually observed and the weight loss rate was measured. As a result, visual observation revealed slight discoloration due to burning on the surface, and the weight reduction rate was 0.6% by mass.

In the above embodiment, the apparatus for supplying the halogen-containing gas filled with high pressure from the container to the external apparatus has been described. However, as shown in Example 17, Comparative Example 4, and Comparative Example 9, the same effects can be obtained when a flammable gas such as O ₂ or NO is used instead of the halogen-containing gas. That is, even if the gas to be applied is changed from the halogen-containing gas to the combustion-supporting gas and the other configurations are the same, the invention is established.

Specifically, a combustion-supporting gas supply device that supplies a combustion-supporting gas from a container filled with the combustion-supporting gas to a external device, the supply connecting the container and the external device A pipe and a first supply valve that is provided in the supply pipe and supplies a combustion-supporting gas from the container, and a gas flow cross-sectional area is provided in at least a part of the supply pipe downstream of the first supply valve. Even if it is configured that details of 0.5 cm ² or less are provided, the present invention is established.

  Further, in addition to the above-described configuration, the invention may be realized as a configuration further including a bypass pipe connected to the supply pipe so as to bypass the details and a second supply valve provided in the bypass pipe.

  Further, the filling pressure of the combustion-supporting gas is preferably 5 MPa or more and 20 MPa or less.

  For details, an orifice plate or a valve is used.

Even in this configuration in which a combustion-supporting gas is used, the supply pipe is provided with details with a gas flow cross-sectional area of 0.5 cm ² or less, so that the temperature rise in the valve chamber of the introduction valve, surface corrosion of the introduction valve, It is possible to suppress the deterioration of the sealing material used for the introduction valve.

  The present invention is not limited to the above-described embodiment, and it is obvious that various modifications can be made within the scope of the technical idea.

  The halogen-containing gas supply apparatus of the present invention can be used as a cleaning gas supply apparatus for safely supplying a cleaning gas to a semiconductor manufacturing apparatus.

1: Container 2: Opening / closing valve 3: First supply valve 4: Supply pipe 6: Conduit 25: Orifice plate 26: Cylinder (50cc)
27: PCTFE chip (3 × 3 × 3 mm ³ )
28: Manual valve 29: Vacuum line 35: Valve 100: Introduction valve 101: Semiconductor manufacturing device (external device)
410: Second supply valve 411: Bypass pipe

Claims (4)

A halogen-containing gas supply device that supplies a halogen-containing gas to an external device from a container filled with the halogen-containing gas at a high pressure,
A supply pipe connecting the container and the external device;
A first supply valve provided in the supply pipe for supplying a halogen-containing gas from the container;
Wherein at least a portion downstream of the first supply valve of the supply tube, details are provided gas flow cross-sectional area is 0.0001 cm ² or more 0.5 cm ² or less,
A halogen-containing gas supply device , wherein an orifice plate is used for the details . A bypass pipe connected to the supply pipe to bypass the details;
A second supply valve provided in the bypass pipe;
The halogen-containing gas supply device according to claim 1, further comprising:   The halogen-containing gas supply apparatus according to claim 1 or 2, wherein the halogen of the halogen-containing gas is fluorine, chlorine, bromine, or iodine.   The halogen-containing gas supply apparatus according to any one of claims 1 to 3, wherein a filling pressure of the halogen-containing gas is 5 MPa or more and 20 MPa or less.

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