JP2013008976A - Cleaning method of electronic material member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing apparatus and a manufacturing method of carbonated water capable of simply and rapidly manufacturing high-concentration carbonated water, and a method for cleaning electronic material members by the carbonated water manufactured by this manufacturing apparatus.SOLUTION: Raw water is supplied to a liquid phase chamber 1b of a deaeration membrane module 1 through a raw water pipe 11. A vacuum pump 3 is operated to decompress the inside of a gas phase chamber 1c. A dissolved gas dissolved in the raw water permeates through a gas permeation membrane 1a and is exhausted out of the system through the gas phase chamber and an exhaust pipe 13. Deaerated water flows into a liquid phase chamber 2b of a carbon dioxide dissolution membrane module 2 through a deaerated water pipe 12. Meanwhile, carbon dioxide is supplied from a carbon dioxide supplier 4 through a carbon dioxide pipe 15 to the gas phase chamber 1c. A prescribed amount of carbon dioxide permeates through a gas permeation membrane 2a and is dissolved in the deaerated water in the liquid phase chamber 2b. The deaerated water in which the carbon dioxide is dissolved flows out of a carbonated water pipe 14.

Description

  The present invention relates to an apparatus for producing carbonated water, a production method, and an electronic material member cleaning method, and more specifically, an apparatus for producing carbonated water having a carbon dioxide gas dissolving portion for dissolving carbon dioxide gas in water, and the production apparatus. The present invention relates to a method for producing carbonated water and a method for cleaning an electronic material member with carbonated water produced by the production apparatus.

  Electronic material members such as a semiconductor silicon substrate and a liquid crystal glass substrate are washed with ultrapure water. However, since ultrapure water has high insulating properties, the electronic material member may be charged by friction between the ultrapure water and the electronic material member during cleaning. When the electronic material member is charged in this way, there is a problem that the circuit is destroyed when a fine circuit pattern is provided on the electronic material member.

  In order to prevent such charging, it is known to use carbonated water in which carbon dioxide gas is dissolved in ultrapure water as cleaning water. Since this carbonated water has higher conductivity than ultrapure water, charging of the electronic material member during cleaning can be prevented.

  For example, JP 2001-293344 describes an example of a method for producing carbonated water. In the method of the same number, warm water is allowed to flow through the hollow portion of the hollow fiber membrane, carbon dioxide gas is supplied to the outer surface side of the hollow fiber membrane, and the carbon dioxide gas is dissolved in the warm water in the hollow portion to produce carbonated water. In the method, the warm water is repeatedly flowed into the hollow portion of the hollow fiber membrane, whereby carbon dioxide gas is gradually dissolved in the warm water.

Further, in cleaning an electronic material member such as a silicon wafer, the unevenness (flatness) allowed on the surface of the electronic material member is extremely small, about several inches, as the circuit pattern becomes finer. For this reason, an increase in flatness due to erosion by OH ⁻ ions existing in a very small amount in ultrapure water is also regarded as a problem.

JP 2001-293344 A

  In the method of Japanese Patent Application Laid-Open No. 2001-293344, hot water is repeatedly flowed into the hollow portion of the hollow fiber membrane to gradually increase the dissolved carbon dioxide concentration in the hot water, and thus high concentration carbonated water cannot be rapidly produced. .

  The present invention provides an apparatus and method for producing carbonated water that can produce highly concentrated carbonated water simply and quickly, and a method for cleaning an electronic material member with carbonated water produced by the production apparatus. With the goal.

  The apparatus for producing carbonated water of the present invention (Claim 1) includes a dissolved gas degassing unit for degassing a dissolved gas dissolved in water, and a carbon dioxide gas dissolving unit for dissolving carbon dioxide gas in the degassed water. It is characterized by having.

  The apparatus for producing carbonated water according to claim 2 is the apparatus for producing carbonated water according to claim 1, wherein the carbon dioxide gas dissolving unit has a membrane module having an interior partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. The module supplies degassed water degassed by the degassing unit to the liquid phase chamber, supplies the carbon dioxide gas to the gas phase chamber, and removes the carbon dioxide gas through the gas permeable membrane. The carbon dioxide gas is dissolved in the degassed water by supplying it to the air water.

  The apparatus for producing carbonated water according to claim 3 is characterized in that, in claim 1 or 2, the dissolved gas deaeration unit has a membrane module whose interior is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. The membrane module deaerates the dissolved gas by supplying the water to the liquid phase chamber and discharging the dissolved gas dissolved in the water to the gas phase chamber through the gas permeable membrane. It is a thing to do.

  The method for producing carbonated water according to the present invention (Claim 4) is characterized by producing carbonated water using the carbonated water production apparatus according to any one of Claims 1 to 3.

  The method for cleaning an electronic material member according to the present invention (Claim 5) produces carbonated water using the carbonated water production apparatus according to any one of Claims 1 to 3, and uses the carbonated water to produce an electronic material member. The surface of the substrate is washed.

  According to a sixth aspect of the present invention, there is provided the electronic material member cleaning method according to the fifth aspect, wherein a part or all of the surface of the electronic material member is made of silicon.

  According to a seventh aspect of the present invention, there is provided the electronic material member cleaning method according to the sixth aspect, wherein the electronic material member is a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid.

  An electronic material member cleaning method according to an eighth aspect of the present invention is the method according to the seventh aspect, wherein the hydrofluoric acid-containing liquid is an aqueous solution containing hydrofluoric acid and an acid other than hydrofluoric acid.

  According to a ninth aspect of the present invention, there is provided the electronic material member cleaning method according to any one of the fifth to eighth aspects, wherein a dissolved carbon dioxide concentration of the carbonated water is 500 mg / L or more.

  The present inventor degassed dissolved gas such as nitrogen gas dissolved in water and then dissolved carbon dioxide in this degassed water, so that the dissolved carbon dioxide concentration was high and used as a cleaning liquid under atmospheric pressure. It was found that carbonated water suppressed to a concentration at which dissolved carbon dioxide gas does not appear as bubbles is obtained.

  According to the apparatus for producing carbonated water according to claims 1 to 3 and the apparatus for producing carbonated water according to claim 4, the dissolved gas dissolved in water is degassed in the dissolved gas degassing part, and then in the carbon dioxide gas dissolving part. Since carbon dioxide gas is dissolved in the degassed water, a large amount of carbon dioxide gas can be easily and quickly dissolved in the degassed water. Thereby, high concentration carbonated water can be manufactured simply and rapidly.

  As claimed in claim 2, it is preferable that the carbon dioxide gas dissolving part has a membrane module which is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. In this case, the apparatus can be made compact and the carbon dioxide gas can be dissolved in water without waste.

  As described in claim 3, it is preferable that the dissolved gas deaeration unit has a membrane module that is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. In this case, the dissolved gas dissolved in water can be easily degassed.

Moreover, this inventor discovered that the increase in the unevenness | corrugation (flatness) of the surface of an electronic material member was suppressed by using high concentration carbonated water for washing | cleaning of an electronic material member. This is presumed to be because, by dissolving carbon dioxide gas in ultrapure water at a high concentration, the concentration of OH ⁻ ions existing in the water is reduced, and erosion of the electronic material member by OH ⁻ ions is reduced.

  According to claim 5, by producing carbonated water using the carbonated water production apparatus according to any one of claims 1 to 3, and washing the surface of the electronic material member using the carbonated water, an electronic material is obtained. An increase in unevenness (flatness) on the surface of the member is suppressed.

  As in claim 6, the carbonated water may be used for cleaning an electronic material member in which part or all of the surface of the electronic material member is made of silicon. In this case, cleaning can be performed without roughening the silicon on the surface.

  As in claim 7, the electronic material member may be a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid. As in claim 8, the hydrofluoric acid-containing liquid is an acid other than hydrofluoric acid and hydrofluoric acid. An aqueous solution containing Even in this case, the carbonate-containing water can sufficiently remove the fluorine-containing liquid remaining on the surface of the silicon wafer without roughening the surface of the silicon wafer.

  As in claim 9, the concentration of dissolved carbon dioxide in carbonated water is preferably 500 mg / L or more.

It is drawing explaining the manufacturing apparatus and manufacturing method of carbonated water of the gas dissolution water which concern on embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a system diagram illustrating a carbonated water production apparatus and production method according to an embodiment.

  The inside of the deaeration membrane module 1 is divided into a liquid phase chamber 1b and a gas phase chamber 1c by a gas permeable membrane 1a. Similarly, the carbon dioxide-dissolving membrane module 2 is also divided into a liquid phase chamber 2b and a gas phase chamber 2c by a gas permeable membrane 2a.

  These gas permeable membranes 1a and 2a are not particularly limited as long as they do not allow water to permeate and allow gas dissolved in water to permeate. For example, polypropylene, polydimethylsiloxane, polycarbonate-polydimethylsiloxane block Examples include copolymers, polyvinylphenol-polydimethylsiloxane-polysulfone block copolymers, polymer films such as poly (4-methylpentene-1), poly (2,6-dimethylphenylene oxide), and polytetrafluoroethylene. be able to.

  A raw water pipe 11 provided with a flow meter 11 a is connected to the liquid phase chamber 1 b of the deaeration membrane module 1. The gas phase chamber 1 c of the deaeration membrane module 1 is connected to the suction port of the vacuum pump 3 via the exhaust pipe 13.

  Although there is no restriction | limiting in particular in the vacuum pump 3, What can take in water vapor | steam like a water-sealed vacuum pump or a scroll pump provided with the water vapor removal function, for example is preferable.

  The liquid phase chamber 1 b of the degassing membrane module 1 and the liquid phase chamber 2 b of the carbon dioxide-dissolving membrane module 2 are connected by a degassing water pipe 12. A carbonated water pipe 14 is connected to the liquid phase chamber 2 b of the dissolved membrane module 2. The gas phase chamber 2c of the dissolved membrane module 2 is connected to a carbon dioxide supply device 4 such as a carbon dioxide cylinder through a carbon dioxide pipe 15 provided with a flow rate control valve 15a.

  The material of the carbonated water pipe 14 is preferably a material having durability against a weak acid having a pH of about 4. This pH of about 4 corresponds to the pH of carbonated water of about 1000 mg / L. The carbonated water pipe 14 is preferably a material having durability against carbonated water of about 1500 mg / L.

  When carbon dioxide is produced using the carbon dioxide production apparatus configured as described above, raw water is supplied to the liquid phase chamber 1 b of the degassing membrane module 1 via the raw water pipe 11. At this time, the flow rate of the raw water passing through the raw water pipe 11 is measured by the flow meter 11a. Further, the vacuum pump 3 is operated to depressurize the gas phase chamber 1c. Thereby, the dissolved gas dissolved in the raw water in the liquid phase chamber 1 b passes through the gas permeable membrane 1 a and is discharged out of the system via the gas phase chamber and the exhaust pipe 13. In this way, the raw water is degassed.

  Here, the inside of the gas phase chamber 1c is preferably decompressed to 10 kPa or less, particularly 5 kPa or less.

  The deaerated water deaerated in the liquid phase chamber 1 b in this way flows into the liquid phase chamber 2 b of the carbon dioxide-dissolving membrane module 2 via the deaerated water pipe 12. Further, carbon dioxide gas is supplied from the carbon dioxide supply device 4 to the gas phase chamber 2 c via the carbon dioxide gas pipe 15. At this time, the opening degree of the flow control valve 15a is adjusted based on the flow rate of the raw water measured by the flow meter 11a to control the supply amount of carbon dioxide gas to the gas phase chamber 2c. Thereby, a predetermined amount of carbon dioxide gas permeates the gas permeable membrane 2a and dissolves in the deaerated water in the liquid phase chamber 2b.

  The deaerated water in which the carbon dioxide gas is dissolved flows out from the carbonated water pipe 14. In this way, carbonated water is produced.

  According to this carbonated water production apparatus and production method, carbon dioxide gas can be dissolved to a maximum of about 1500 mg / l (25 ° C.), which is the saturation solubility of carbon dioxide gas.

Thus carbonated water produced by the cleaning of electronic material member, in particular OH ^- is preferably used to clean electronic materials member etching by ions is concerned. Examples of the electronic material member include an electronic material member whose surface is partly or entirely made of silicon, particularly a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid. In particular, even a slight roughness of the silicon surface is useful for cleaning the silicon surface in a high-k gate forming process that significantly deteriorates the quality.

As described above, when used for cleaning an electronic material member, the concentration of carbon dioxide dissolved in carbonated water is 500 mg / L or more, particularly 1000 to 1500 mg / L at a standard state (1 atm) and 25 ° C. It is preferable. When it is 500 mg / L or more, the surface of the electronic material member is sufficiently suppressed from being damaged (etched) by OH ⁻ ions.

  The above embodiment is an example of the present invention, and the present invention is not limited to the above embodiment.

  For example, in the above-described embodiment, the opening of the flow rate control valve 15a is adjusted based on the flow rate of the raw water measured by the flow meter 11a, and the amount of carbon dioxide gas supplied to the gas phase chamber 2c is controlled. Although the dissolved carbon dioxide concentration of water is controlled, the method for controlling the dissolved carbon dioxide concentration is not limited to this. For example, the concentration of dissolved carbon dioxide in the carbonated water may be controlled by controlling the pressure in the gas phase chamber of the carbon dioxide-dissolved membrane module 2 and adjusting the amount of carbon dioxide dissolved in the deaerated water. Further, the degree of deaeration of the deaerated water may be adjusted by controlling the pressure in the gas phase chamber 1c of the deaeration membrane module 1 by controlling the vacuum pump. In this case, the dissolved carbon dioxide concentration in the carbonated water is controlled by dissolving the carbon dioxide in the carbon dioxide-dissolving membrane module 2 by the amount deaerated.

  In the above embodiment, the raw water is deaerated using the deaeration membrane module. However, the raw water is not limited to this, and the raw water may be deaerated by, for example, vacuum deaeration or distillation.

  In the above embodiment, the carbon dioxide gas is dissolved in the deaerated water using the carbon dioxide-dissolving membrane module. However, the present invention is not limited to this. Carbon dioxide gas may be dissolved in water.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1]
Carbonated water was produced using the apparatus shown in FIG. Details of the apparatus and measurement conditions are as follows.

Degassing membrane (gas permeable membrane 1a): “Lixel G284” manufactured by Celgard Co., Ltd.
Dissolved membrane (gas permeable membrane 2a): “Lixel G284” manufactured by Celgard Co., Ltd.
Raw water: Ultrapure water in which nitrogen gas is dissolved to saturation concentration Raw water supply amount: 20 L / min
Water temperature: 25 ° C
Pressure in the gas phase chamber of the deaeration chamber: 2 kPa (equivalent to 98% deaeration)
Carbon dioxide supply rate: 15.3 L (standard state) / min
Here, the carbon dioxide supply amount is a value obtained by calculating the carbon dioxide supply amount necessary to produce carbonated water having a dissolved carbon dioxide concentration of 1500 mg / L from the raw water of the raw water supply amount.

  The carbonated water produced in this way was supplied to a washing tank (volume 40 L). At this time, no bubbles were generated from the carbonated water. As a result of measuring the pH in this washing tank, it was about pH 3.9.

  Further, the silicon wafer immersed in a 0.5% hydrofluoric acid-containing aqueous solution (DHF) and subjected to surface treatment was immediately put into the cleaning tank, and held for 10 minutes with carbonated water overflowing into the cleaning tank. . Thereafter, the silicon wafer was taken out of the cleaning tank and dried. The wafer flatness after processing was 3 mm.

  Thus, according to Example 1, high concentration carbonated water was able to be manufactured, without being oversaturated. Further, the surface roughness of the wafer due to rinsing could be sufficiently suppressed.

[Comparative Example 1]
The experiment was performed in the same manner as in Example 1 except that the degassing of the raw water by the degassing membrane module was omitted.

  As a result, bubbles were generated when carbonated water was introduced into the washing tank. Further, when the silicon wafer was put into the cleaning tank, the bubbles adhered to the wafer surface, and the flatness was so rough that it could not be measured.

  Thus, according to Comparative Example 1, the silicon wafer surface could not be rinsed uniformly. The surface of the silicon wafer was extremely rough as compared with Example 1.

  In addition, when the silicon wafer was washed with ultrapure water as usual without using carbonated water, the flatness was about 5 mm, which was rough as compared with Example 1.

DESCRIPTION OF SYMBOLS 1 Deaeration membrane module 2 Carbon dioxide gas melt | dissolution membrane module 1a, 2a Gas permeable membrane 1b, 2b Liquid phase chamber 1c, 2c Gas phase chamber 3 Vacuum pump 4 Carbon dioxide gas supply device 11a Flow meter

The present invention relates to a method for cleaning electronic materials member, more particularly, to a method of cleaning an electronic material member with carbonated water produced in production equipment of carbonated water with a carbonic acid gas dissolver to dissolve the carbonic acid gas in water .

  Electronic material members such as a semiconductor silicon substrate and a liquid crystal glass substrate are washed with ultrapure water. However, since ultrapure water has high insulating properties, the electronic material member may be charged by friction between the ultrapure water and the electronic material member during cleaning. When the electronic material member is charged in this way, there is a problem that the circuit is destroyed when a fine circuit pattern is provided on the electronic material member.

  In order to prevent such charging, it is known to use carbonated water in which carbon dioxide gas is dissolved in ultrapure water as cleaning water. Since this carbonated water has higher conductivity than ultrapure water, charging of the electronic material member during cleaning can be prevented.

  For example, JP 2001-293344 describes an example of a method for producing carbonated water. In the method of the same number, warm water is allowed to flow through the hollow portion of the hollow fiber membrane, carbon dioxide gas is supplied to the outer surface side of the hollow fiber membrane, and the carbon dioxide gas is dissolved in the warm water in the hollow portion to produce carbonated water. In the method, the warm water is repeatedly flowed into the hollow portion of the hollow fiber membrane, whereby carbon dioxide gas is gradually dissolved in the warm water.

Further, in cleaning an electronic material member such as a silicon wafer, the unevenness (flatness) allowed on the surface of the electronic material member is extremely small, about several inches, as the circuit pattern becomes finer. For this reason, an increase in flatness due to erosion by OH ⁻ ions existing in a very small amount in ultrapure water is also regarded as a problem.

JP 2001-293344 A

  In the method of Japanese Patent Application Laid-Open No. 2001-293344, hot water is repeatedly flowed into the hollow portion of the hollow fiber membrane to gradually increase the dissolved carbon dioxide concentration in the hot water, and thus high concentration carbonated water cannot be rapidly produced. .

The present invention aims to provide a method for cleaning electronic materials member carbonated water produced by the production equipment of the carbonated water can be produced with high concentration of carbonated water easily and quickly.

The method for cleaning an electronic material member of the present invention (Claim 1 ) includes a dissolved gas degassing section for degassing a dissolved gas dissolved in water, and carbon dioxide dissolution for dissolving carbon dioxide in the degassed water. A carbonated water is produced using a carbonated water production apparatus having a section, and the surface of the electronic material member is washed using the carbonated water.

According to a second aspect of the present invention, there is provided the electronic material member cleaning method according to the first aspect , wherein a part or all of the surface of the electronic material member is made of silicon.

According to a third aspect of the present invention, there is provided the electronic material member cleaning method according to the second aspect , wherein the electronic material member is a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid.

According to a fourth aspect of the present invention, there is provided the electronic material member cleaning method according to the third aspect , wherein the hydrofluoric acid-containing liquid is an aqueous solution containing hydrofluoric acid and an acid other than hydrofluoric acid.

The method of cleaning electronic materials member according to claim 5, in any one of claims 1 to 4, dissolved carbon dioxide concentration of the carbonated water and wherein the at 500 mg / L or more.

The electronic material member cleaning method according to claim 6 is the membrane module according to any one of claims 1 to 5, wherein the carbon dioxide gas dissolving portion is divided into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. The membrane module supplies degassed water degassed by the degassing unit to the liquid phase chamber, supplies the carbon dioxide gas to the gas phase chamber, and supplies the carbon dioxide gas to the liquid phase chamber. The carbon dioxide gas is dissolved in the deaerated water by supplying the deaerated water through a gas permeable membrane.

The electronic material member cleaning method according to claim 7 is the film according to any one of claims 1 to 6, wherein the dissolved gas degassing part is a film whose inside is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable film. The membrane module supplies the water to the liquid phase chamber and discharges the dissolved gas dissolved in the water to the gas phase chamber through the gas permeable membrane, The dissolved gas is degassed.

  The present inventor degassed dissolved gas such as nitrogen gas dissolved in water and then dissolved carbon dioxide in this degassed water, so that the dissolved carbon dioxide concentration was high and used as a cleaning liquid under atmospheric pressure. It was found that carbonated water suppressed to a concentration at which dissolved carbon dioxide gas does not appear as bubbles is obtained.

According to the manufacturing equipment of the carbonated water according to the present invention, degassed dissolved gas dissolved in water at a dissolved gas degassing unit, then carbon dioxide gas in the carbon dioxide gas dissolver in the deaerated water Since it dissolves, a large amount of carbon dioxide can be easily and quickly dissolved in this degassed water. Thereby, high concentration carbonated water can be manufactured simply and rapidly.

As described in claim 6 , it is preferable that the carbon dioxide gas dissolving portion has a membrane module having an interior partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. In this case, the apparatus can be made compact and the carbon dioxide gas can be dissolved in water without waste.

As described in claim 7 , it is preferable that the dissolved gas deaeration unit has a membrane module that is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane. In this case, the dissolved gas dissolved in water can be easily degassed.

Moreover, this inventor discovered that the increase in the unevenness | corrugation (flatness) of the surface of an electronic material member was suppressed by using high concentration carbonated water for washing | cleaning of an electronic material member. This is presumed to be because, by dissolving carbon dioxide gas in ultrapure water at a high concentration, the concentration of OH ⁻ ions existing in the water is reduced, and erosion of the electronic material member by OH ⁻ ions is reduced.

As claimed in claim 1 , by producing carbonated water using the carbonated water production apparatus according to the present invention and cleaning the surface of the electronic material member using the carbonated water, the surface of the electronic material member is uneven (flat Increase) is suppressed.

As in claim 2, the carbonated water may be used for cleaning an electronic material member in which part or all of the surface of the electronic material member is made of silicon. In this case, cleaning can be performed without roughening the silicon on the surface.

As in claim 3 , the electronic material member may be a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid. As in claim 4 , the hydrofluoric acid-containing liquid is an acid other than hydrofluoric acid and hydrofluoric acid. An aqueous solution containing Even in this case, the carbonate-containing water can sufficiently remove the fluorine-containing liquid remaining on the surface of the silicon wafer without roughening the surface of the silicon wafer.

As in claim 5 , the dissolved carbon dioxide concentration of the carbonated water is preferably 500 mg / L or more.

It is drawing explaining the manufacturing apparatus and manufacturing method of carbonated water of the gas dissolution water which concern on embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a system diagram illustrating a carbonated water production apparatus and production method according to an embodiment.

  The inside of the deaeration membrane module 1 is divided into a liquid phase chamber 1b and a gas phase chamber 1c by a gas permeable membrane 1a. Similarly, the carbon dioxide-dissolving membrane module 2 is also divided into a liquid phase chamber 2b and a gas phase chamber 2c by a gas permeable membrane 2a.

  These gas permeable membranes 1a and 2a are not particularly limited as long as they do not allow water to permeate and allow gas dissolved in water to permeate. For example, polypropylene, polydimethylsiloxane, polycarbonate-polydimethylsiloxane block Examples include copolymers, polyvinylphenol-polydimethylsiloxane-polysulfone block copolymers, polymer films such as poly (4-methylpentene-1), poly (2,6-dimethylphenylene oxide), and polytetrafluoroethylene. be able to.

  A raw water pipe 11 provided with a flow meter 11 a is connected to the liquid phase chamber 1 b of the deaeration membrane module 1. The gas phase chamber 1 c of the deaeration membrane module 1 is connected to the suction port of the vacuum pump 3 via the exhaust pipe 13.

  Although there is no restriction | limiting in particular in the vacuum pump 3, What can take in water vapor | steam like a water-sealed vacuum pump or a scroll pump provided with the water vapor removal function, for example is preferable.

  The liquid phase chamber 1 b of the degassing membrane module 1 and the liquid phase chamber 2 b of the carbon dioxide-dissolving membrane module 2 are connected by a degassing water pipe 12. A carbonated water pipe 14 is connected to the liquid phase chamber 2 b of the dissolved membrane module 2. The gas phase chamber 2c of the dissolved membrane module 2 is connected to a carbon dioxide supply device 4 such as a carbon dioxide cylinder through a carbon dioxide pipe 15 provided with a flow rate control valve 15a.

  The material of the carbonated water pipe 14 is preferably a material having durability against a weak acid having a pH of about 4. This pH of about 4 corresponds to the pH of carbonated water of about 1000 mg / L. The carbonated water pipe 14 is preferably a material having durability against carbonated water of about 1500 mg / L.

  When carbon dioxide is produced using the carbon dioxide production apparatus configured as described above, raw water is supplied to the liquid phase chamber 1 b of the degassing membrane module 1 via the raw water pipe 11. At this time, the flow rate of the raw water passing through the raw water pipe 11 is measured by the flow meter 11a. Further, the vacuum pump 3 is operated to depressurize the gas phase chamber 1c. Thereby, the dissolved gas dissolved in the raw water in the liquid phase chamber 1 b passes through the gas permeable membrane 1 a and is discharged out of the system via the gas phase chamber and the exhaust pipe 13. In this way, the raw water is degassed.

  Here, the inside of the gas phase chamber 1c is preferably decompressed to 10 kPa or less, particularly 5 kPa or less.

  The deaerated water deaerated in the liquid phase chamber 1 b in this way flows into the liquid phase chamber 2 b of the carbon dioxide-dissolving membrane module 2 via the deaerated water pipe 12. Further, carbon dioxide gas is supplied from the carbon dioxide supply device 4 to the gas phase chamber 2 c via the carbon dioxide gas pipe 15. At this time, the opening degree of the flow control valve 15a is adjusted based on the flow rate of the raw water measured by the flow meter 11a to control the supply amount of carbon dioxide gas to the gas phase chamber 2c. Thereby, a predetermined amount of carbon dioxide gas permeates the gas permeable membrane 2a and dissolves in the deaerated water in the liquid phase chamber 2b.

  The deaerated water in which the carbon dioxide gas is dissolved flows out from the carbonated water pipe 14. In this way, carbonated water is produced.

  According to this carbonated water production apparatus and production method, carbon dioxide gas can be dissolved to a maximum of about 1500 mg / l (25 ° C.), which is the saturation solubility of carbon dioxide gas.

Thus carbonated water produced by the cleaning of electronic material member, in particular OH ^- is preferably used to clean electronic materials member etching by ions is concerned. Examples of the electronic material member include an electronic material member whose surface is partly or entirely made of silicon, particularly a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid. In particular, even a slight roughness of the silicon surface is useful for cleaning the silicon surface in a high-k gate forming process that significantly deteriorates the quality.

As described above, when used for cleaning an electronic material member, the concentration of carbon dioxide dissolved in carbonated water is 500 mg / L or more, particularly 1000 to 1500 mg / L at a standard state (1 atm) and 25 ° C. It is preferable. When it is 500 mg / L or more, the surface of the electronic material member is sufficiently suppressed from being damaged (etched) by OH ⁻ ions.

  The above embodiment is an example of the present invention, and the present invention is not limited to the above embodiment.

  For example, in the above-described embodiment, the opening of the flow rate control valve 15a is adjusted based on the flow rate of the raw water measured by the flow meter 11a, and the amount of carbon dioxide gas supplied to the gas phase chamber 2c is controlled. Although the dissolved carbon dioxide concentration of water is controlled, the method for controlling the dissolved carbon dioxide concentration is not limited to this. For example, the concentration of dissolved carbon dioxide in the carbonated water may be controlled by controlling the pressure in the gas phase chamber of the carbon dioxide-dissolved membrane module 2 and adjusting the amount of carbon dioxide dissolved in the deaerated water. Further, the degree of deaeration of the deaerated water may be adjusted by controlling the pressure in the gas phase chamber 1c of the deaeration membrane module 1 by controlling the vacuum pump. In this case, the dissolved carbon dioxide concentration in the carbonated water is controlled by dissolving the carbon dioxide in the carbon dioxide-dissolving membrane module 2 by the amount deaerated.

  In the above embodiment, the raw water is deaerated using the deaeration membrane module. However, the raw water is not limited to this, and the raw water may be deaerated by, for example, vacuum deaeration or distillation.

  In the above embodiment, the carbon dioxide gas is dissolved in the deaerated water using the carbon dioxide-dissolving membrane module. However, the present invention is not limited to this. Carbon dioxide gas may be dissolved in water.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1]
Carbonated water was produced using the apparatus shown in FIG. Details of the apparatus and measurement conditions are as follows.

Degassing membrane (gas permeable membrane 1a): “Lixel G284” manufactured by Celgard Co., Ltd.
Dissolved membrane (gas permeable membrane 2a): “Lixel G284” manufactured by Celgard Co., Ltd.
Raw water: Ultrapure water in which nitrogen gas is dissolved to saturation concentration Raw water supply amount: 20 L / min
Water temperature: 25 ° C
Pressure in the gas phase chamber of the deaeration chamber: 2 kPa (equivalent to 98% deaeration)
Carbon dioxide supply rate: 15.3 L (standard state) / min
Here, the carbon dioxide supply amount is a value obtained by calculating the carbon dioxide supply amount necessary to produce carbonated water having a dissolved carbon dioxide concentration of 1500 mg / L from the raw water of the raw water supply amount.

  The carbonated water produced in this way was supplied to a washing tank (volume 40 L). At this time, no bubbles were generated from the carbonated water. As a result of measuring the pH in this washing tank, it was about pH 3.9.

  Further, the silicon wafer immersed in a 0.5% hydrofluoric acid-containing aqueous solution (DHF) and subjected to surface treatment was immediately put into the cleaning tank, and held for 10 minutes with carbonated water overflowing into the cleaning tank. . Thereafter, the silicon wafer was taken out of the cleaning tank and dried. The wafer flatness after processing was 3 mm.

  Thus, according to Example 1, high concentration carbonated water was able to be manufactured, without being oversaturated. Further, the surface roughness of the wafer due to rinsing could be sufficiently suppressed.

[Comparative Example 1]
The experiment was performed in the same manner as in Example 1 except that the degassing of the raw water by the degassing membrane module was omitted.

  As a result, bubbles were generated when carbonated water was introduced into the washing tank. Further, when the silicon wafer was put into the cleaning tank, the bubbles adhered to the wafer surface, and the flatness was so rough that it could not be measured.

  Thus, according to Comparative Example 1, the silicon wafer surface could not be rinsed uniformly. The surface of the silicon wafer was extremely rough as compared with Example 1.

  In addition, when the silicon wafer was washed with ultrapure water as usual without using carbonated water, the flatness was about 5 mm, which was rough as compared with Example 1.

DESCRIPTION OF SYMBOLS 1 Deaeration membrane module 2 Carbon dioxide gas melt | dissolution membrane module 1a, 2a Gas permeable membrane 1b, 2b Liquid phase chamber 1c, 2c Gas phase chamber 3 Vacuum pump 4 Carbon dioxide gas supply device 11a Flow meter

Claims (9)

A dissolved gas degassing part for degassing dissolved gas dissolved in water;
An apparatus for producing carbonated water, comprising: a carbon dioxide gas dissolving section for dissolving carbon dioxide gas in the degassed water. In Claim 1, the carbon dioxide gas dissolving part has a membrane module whose inside is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane,
The membrane module supplies degassed water degassed by the degassing unit to the liquid phase chamber, and also supplies the carbon dioxide gas to the gas phase chamber, and passes the carbon dioxide gas through the gas permeable membrane. An apparatus for producing carbonated water, wherein the carbon dioxide gas is dissolved in the deaerated water by supplying the deaerated water. In Claim 1 or 2, the dissolved gas deaeration part has a membrane module that is partitioned into a gas phase chamber and a liquid phase chamber by a gas permeable membrane,
The membrane module degasses the dissolved gas by supplying the water to the liquid phase chamber and discharging the dissolved gas dissolved in the water to the gas phase chamber through the gas permeable membrane. An apparatus for producing carbonated water,   A method for producing carbonated water, comprising producing carbonated water using the carbonated water production apparatus according to any one of claims 1 to 3.   A method for cleaning an electronic material member, comprising: producing carbonated water using the carbonated water production apparatus according to any one of claims 1 to 3, and washing the surface of the electronic material member using the carbonated water. .   6. The method for cleaning an electronic material member according to claim 5, wherein a part or all of the surface of the electronic material member is made of silicon.   The method of cleaning an electronic material member according to claim 6, wherein the electronic material member is a silicon wafer after surface treatment with a hydrofluoric acid-containing liquid.   The method for cleaning an electronic material member according to claim 7, wherein the hydrofluoric acid-containing liquid is an aqueous solution containing hydrofluoric acid and an acid other than hydrofluoric acid.   9. The method for cleaning an electronic material member according to claim 5, wherein a dissolved carbon dioxide concentration of the carbonated water is 500 mg / L or more.

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