WO2013099619A1

WO2013099619A1 - Chemical mixer

Info

Publication number: WO2013099619A1
Application number: PCT/JP2012/082287
Authority: WO
Inventors: 泰幸小山; 孝昌安達; 高橋　章; 博文庄盛
Original assignee: 株式会社ジェイ・イー・ティ
Priority date: 2011-12-28
Filing date: 2012-12-13
Publication date: 2013-07-04
Also published as: JP2013138062A; TW201342459A

Abstract

The present invention proposes a chemical mixer that can supply a chemical mixture to a substrate treating device without degradation over time, and can suppress variations in a mixing ratio for sulfuric acid and hydrogen peroxide and produce a chemical mixture that maintains a constant mixing ratio when producing a chemical mixture. In a chemical mixer (10), a sulfuric acid flow rate is stabilized by pressure feeding the sulfuric acid by a pressure feeding means (35), and also a hydrogen peroxide flow rate is stabilized by injecting the hydrogen peroxide with a supply rate lower than that of the sulfuric acid using a metering pump (38) in a fixed small amount. The mixture is produced from the sulfuric acid and hydrogen peroxide in an interflow part (105), and the chemical mixture is supplied to a substrate treating device (1) as is, directly after production. Thus, the chemical mixture can be supplied to the substrate treating device (1) without degradation over time, and variations in the mixing ratio for the sulfuric acid and hydrogen peroxide can be suppressed when producing the chemical mixture, allowing for production of a chemical mixture in which a fixed mixing ratio is maintained.

Description

Chemical liquid mixing device

The present invention relates to a chemical-liquid mixing apparatus, for example by mixing the sulfuric acid (H ₂ SO ₄₎ and hydrogen peroxide (H 2 _O _2), the semiconductor substrate (hereinafter, simply referred to as substrate) used in the resist removing surface mixing It is suitable for application when producing a chemical solution.

Conventionally, as a cleaning method for removing a resist on a substrate surface and washing the substrate, sulfuric acid and hydrogen peroxide are mixed to generate a mixed chemical solution, and the mixed chemical solution is used to remove the resist on the substrate surface. A chemical treatment method is known (see, for example, Patent Document 1). Here, the mixed chemical solution generates caroic acid (H ₂ SO ₅ , also called peroxo acid) by reaction heat generated when sulfuric acid and hydrogen peroxide are mixed, and is further heated to about 180 ° C. to 200 ° C. This promotes the production of caroic acid. In the chemical solution processing method, the mixed chemical solution in a state where caroic acid is sufficiently generated is supplied to the substrate surface, and the resist adhering to the substrate surface is dissolved by the caloic acid in the mixed chemical solution to clean the substrate surface. ing.

Here, it is known that the caroic acid produced in the mixed chemical solution has a very short lifetime, the decomposition starts immediately after the production, and gradually decreases with time. Therefore, for example, a mixed chemical solution generated by mixing hydrogen peroxide and sulfuric acid is stored in advance in a chemical storage tank, and a resist solution is removed from the substrate surface using this mixed chemical solution (hereinafter referred to as this). In this case, the mixed chemical solution is deteriorated with time in the chemical solution storage tank, and the caloic acid is reduced. Therefore, in the chemical solution storage method, it is necessary to add hydrogen peroxide solution and sulfuric acid to the mixed chemical solution as needed, and always generate new caroic acid in the mixed chemical solution. As a result, this chemical solution storage system has a problem that a large amount of hydrogen peroxide solution and sulfuric acid are required.

Therefore, in order to solve such problems, there is also a chemical processing method in which a mixed chemical solution is generated immediately before resist removal on the substrate surface, and the mixed chemical solution is used for resist removal on the substrate surface before the mixed chemical solution deteriorates with time. It is considered. In this type of chemical solution processing method, it is only necessary to generate a mixed chemical solution by a necessary minimum amount, and the usage amount of the mixed chemical solution can be significantly reduced as compared with the above-described chemical solution storage method.

Here, FIG. 4 shows the substrate cleaning apparatus 101 that removes the resist on the substrate surface using the mixed chemical liquid immediately after the mixed chemical liquid is generated. In practice, the substrate cleaning apparatus 101 includes a substrate processing apparatus 102 that supplies a mixed chemical solution to the substrate surface to remove the resist on the substrate surface, and a hydrogen peroxide solution and a substrate immediately before the resist removal is performed in the substrate processing apparatus 102. It has a chemical mixing device 100 that mixes sulfuric acid to produce a mixed chemical and supplies the mixed chemical to the substrate processing apparatus 102.

Here, the chemical liquid mixing apparatus 100 includes a hydrogen peroxide solution storage tank 103, a sulfuric acid storage tank 104, and a mixed chemical liquid generation unit 108, and the mixed chemical liquid generation unit 108 is connected to the substrate processing apparatus 102. In addition, the mixed chemical solution generation unit 108 supplies the hydrogen peroxide solution supply pipe 111a that supplies the hydrogen peroxide solution in the hydrogen peroxide solution storage tank 103 to the junction unit 105, and the sulfuric acid in the sulfuric acid storage tank 104 to the junction unit 105. A sulfuric acid supply pipe 111b, a joining part 105 where the hydrogen peroxide water supply pipe 111a and the sulfuric acid supply pipe 111b join together, and a mixed chemical solution supply pipe 111c that supplies the mixed chemical liquid generated in the joining part 105 to the substrate processing apparatus 102. I have.

In practice, the hydrogen peroxide solution supply pipe 111a is provided with a bellows pump 106a between the hydrogen peroxide solution storage tank 103 and the junction 105, and between the bellows pump 106a and the junction 105. Is provided with a valve 113a. The hydrogen peroxide solution supply pipe 111a is provided with a circulation pipe 114a connected to the hydrogen peroxide solution storage tank 103 between the bellows pump 106a and the valve 113a. As a result, when the bellows pump 106a is driven with the valve 113a closed, the hydrogen peroxide solution supply pipe 111a receives the hydrogen peroxide solution discharged from the hydrogen peroxide solution storage tank 103 by the bellows pump 106a. Then, the circulation path 110a returning to the hydrogen peroxide solution storage tank 103 again via the circulation pipe 114a can be formed.

On the other hand, the sulfuric acid supply pipe 111b is also provided with a bellows pump 106b between the sulfuric acid storage tank 104 and the junction 105, and a valve 113b is provided between the bellows pump 106b and the junction 105. Yes. The sulfuric acid supply pipe 111b is provided with a circulation pipe 114a connected to the sulfuric acid storage tank 104 between the bellows pump 106b and the valve 113b. Thus, in the sulfuric acid supply pipe 111b, when the bellows pump 106b is driven with the valve 113b closed, the sulfuric acid discharged from the sulfuric acid storage tank 104 by the bellows pump 106b passes through the circulation pipe 114b. A circulation path 110b returning to the sulfuric acid storage tank 104 can be formed.

When the

valves

113a and 113b of the hydrogen peroxide solution supply pipe 111a and the sulfuric acid supply pipe 111b are opened from this state, the chemical mixing device 100 uses the pressure displacement caused by the expansion and contraction of the bellows portions of the

bellows pumps

106a and 106b. Then, the hydrogen peroxide solution and the sulfuric acid can be supplied up to the junction 105, respectively. As a result, the merging unit 105 can mix the hydrogen peroxide solution and sulfuric acid to generate a mixed chemical solution, and supply this to the substrate processing apparatus 102 via the mixed chemical solution supply pipe 111c. The mixed chemical liquid supply pipe 111c connected to the substrate processing apparatus 102 is provided with a mixed chemical liquid pressure feeding means 118, and the mixed chemical liquid supplied from the chemical liquid mixing apparatus 100 is used as an inert gas such as N ₂ gas, for example. Thus, the mixed chemical solution can be reliably supplied to the substrate processing apparatus 102.

Here, it is desirable that the mixed chemical solution supplied to the substrate processing apparatus 102 is set to, for example, hydrogen peroxide solution and sulfuric acid at 1: 4 to 8 as an optimal mixing ratio for generating caroic acid. Therefore, in the chemical liquid mixing apparatus 100, the mixing ratio of the mixed chemical liquid can be adjusted by adjusting the discharge flow rates of the

bellows pumps

106a and 106b. In practice, the discharge flow rates of the

bellows pumps

106a and 106b in the chemical liquid mixing apparatus 100 are individually set so that the mixing ratio of the mixed chemical liquids becomes an optimum value (for example, hydrogen peroxide solution and sulfuric acid are 1: 4). did. Next, each flow rate variation of the hydrogen peroxide solution flow rate and sulfuric acid flow rate when the mixed chemical solution is generated by the flow meters (not shown) provided in the hydrogen peroxide solution supply tube 111a and the sulfuric acid supply tube 111b, respectively. Was actually measured. As a result, with this chemical liquid mixing apparatus 100, a result as shown in FIG. 5 was obtained.

In this chemical mixing device 100, although the pressure fluctuation by the

bellows pumps

106a and 106b at the junction 105 is small as 0.02 MPa, it greatly affects the supply of hydrogen peroxide and sulfuric acid, as shown in FIG. Due to various other causes such as pulsations of the

bellows pumps

106a and 106b, large flow rate fluctuations occur irregularly in the hydrogen peroxide water flow rate and the sulfuric acid flow rate, which are different from the desired mixing ratio. Thus, in the chemical mixing device 100 having such a configuration, when mixing the hydrogen peroxide solution and sulfuric acid, the mixing ratio of the hydrogen peroxide solution and sulfuric acid in the mixed chemical solution always fluctuates. There is a problem in that it is difficult to stably supply the mixed chemical solution that maintains a constant value to the substrate processing apparatus 102.

Incidentally, such flow rate fluctuations can be obtained by adjusting the mixing ratio of the mixed chemical solution in the chemical solution storage tank when the mixed chemical solution is generated in advance and stored in the chemical solution storage tank. Even if the mixing ratio immediately after mixing is slightly changed, it does not become a big problem. However, when the resist solution is removed by supplying the mixed chemical solution directly to the substrate surface immediately after the mixed chemical solution is generated, the mixing ratio of the hydrogen peroxide solution and sulfuric acid in the mixed chemical solution is not adjusted to a desired value. Then, there is a possibility that carolic acid is not sufficiently generated in the mixed chemical solution, which causes a serious problem that it is difficult to remove the resist on the substrate surface.

Therefore, in order to solve such unstable fluctuations in the mixing ratio of the mixed chemical solution caused by the pulsation of the

bellows pumps

106a and 106b, the same reference numerals are assigned to the corresponding parts as in FIG. In addition, a substrate cleaning apparatus 121 including a chemical liquid mixing apparatus 120 that does not use a bellows pump is also considered. This chemical liquid mixing device 120 replaces the bellows pump, which causes pulsation when hydrogen peroxide solution and sulfuric acid are supplied, by replacing the pressure-feeding means 127a, 127b without pulsation with the hydrogen peroxide solution storage tank 103 and the sulfuric acid storage tank 104. Respectively. In this case, in the chemical liquid mixing device 120, an inert gas such as N ₂ gas is supplied into the hydrogen peroxide solution storage tank 103 and the sulfuric acid storage tank 104 from the pressure feeding means 127a and 127b.

Thus, the hydrogen peroxide solution in the hydrogen peroxide solution storage tank 103 can be pressurized by the inert gas sent from the pressure feeding means 127a and supplied to the hydrogen peroxide solution supply pipe 124a. The sulfuric acid in the sulfuric acid storage tank 104 can also be pressurized by the inert gas sent from the pressure feeding means 127b and supplied to the sulfuric acid supply pipe 124b. The chemical liquid mixing device 120 is a peroxidizer pressurized by an inert gas of the pressure feeding means 127a, 127b by

opening valves

126a, 126b provided in the hydrogen peroxide solution supply pipe 124a and the sulfuric acid supply pipe 124b, respectively. Hydrogen water and sulfuric acid can be supplied to the junction 105, respectively. Thus, the chemical liquid mixing apparatus 120 can supply the mixed chemical liquid generated in the merging portion 105 to the substrate processing apparatus 102 via the mixed chemical liquid supply pipe 111c immediately after the generation.

JP 2008-41794 A

Here, the chemical mixing device 120 is also provided with a flow meter (not shown) in each of the hydrogen peroxide solution supply pipe 124a and the sulfuric acid supply tube 124b, and each flow rate variation between the hydrogen peroxide solution flow rate and the sulfuric acid flow rate is adjusted. Examined. Specifically, after setting the inert gas supply amount of each of the pumping means 127a and 127b so that the mixing ratio of the mixed chemical solution becomes an optimum value, the hydrogen peroxide when the mixed chemical solution is actually generated is set. Each flow rate variation of the water flow rate and the sulfuric acid flow rate was measured with each flow meter. As a result, with this chemical liquid mixing apparatus 120, a result as shown in FIG. 7 was obtained.

From the results of FIG. 7, for the sulfuric acid having a large flow rate and a relatively high viscosity when the mixed chemical solution is generated, the former chemical solution mixing device 100 (FIG. 3) described above after a predetermined time has elapsed after opening the valve 126a. Compared with, stable sulfuric acid flow without pulsation could be maintained. On the other hand, however, for hydrogen peroxide solution having a low flow rate and a relatively low viscosity, the hydrogen peroxide solution flow rate may be irregularly disturbed even after a predetermined time elapses after the valve 126b is opened. It was difficult to maintain a stable hydrogen peroxide flow rate.

The reason why the hydrogen peroxide solution and the sulfuric acid are different in this way is presumed to be that the amount of the hydrogen peroxide solution contained in the mixed chemical solution is much smaller than that of the sulfuric acid. That is, in order to supply a small amount of the hydrogen peroxide solution to the junction 105, it is necessary to reduce the pressurization by the inert gas by the pressure feeding means 127a. As a result, it is considered that the hydrogen peroxide solution flow rate becomes uneasy even when pressurized with an inert gas. In this way, in both the former and the latter chemical

liquid mixing devices

100, 120, immediately after the generation of the mixed chemical liquid, the mixing ratio of sulfuric acid and hydrogen peroxide solution in the mixed chemical liquid fluctuates irregularly, and the mixing ratio of the mixed chemical liquid There is a problem that it is difficult to maintain a constant value.

Therefore, the present invention has been made in consideration of the above points, and can be supplied to a substrate processing apparatus without causing deterioration of the mixed chemical solution over time, and at the time of producing the mixed chemical solution, a mixture of sulfuric acid and hydrogen peroxide water is mixed. It is an object of the present invention to propose a chemical liquid mixing apparatus that can produce a mixed chemical liquid that suppresses fluctuations in the ratio and maintains a constant mixing ratio.

In order to solve this problem, claim 1 of the present invention provides a substrate processing apparatus for mixing a sulfuric acid and a hydrogen peroxide solution to generate a mixed chemical solution, and removing the resist from the substrate using the mixed chemical solution. A chemical liquid mixing device for supplying a chemical liquid, wherein the sulfuric acid is pressurized with an inert gas, and the sulfuric acid is pumped to a merging portion; A metering pump for injecting to the junction, and a mixed chemical supply means for supplying the mixed chemical generated by mixing the hydrogen peroxide solution and the sulfuric acid in the junction to the substrate processing apparatus. It is the chemical | medical solution mixing apparatus characterized.

According to the first aspect of the present invention, the flow rate of sulfuric acid is stabilized by pumping sulfuric acid by the pumping means, and the hydrogen peroxide flow rate is stabilized by injecting a certain small amount of hydrogen peroxide solution by the metering pump. The mixed chemical solution is generated from sulfuric acid and hydrogen peroxide solution at the junction, and the mixed chemical solution immediately after generation is supplied to the substrate processing apparatus as it is, so that the mixed chemical solution is not deteriorated over time. While being able to be supplied to the apparatus, it is possible to produce a mixed chemical liquid that suppresses fluctuations in the mixing ratio of sulfuric acid and hydrogen peroxide water and maintains a constant mixing ratio when producing the mixed chemical liquid.

It is the schematic which shows the whole structure of the substrate processing apparatus connected to the chemical | medical solution mixing apparatus of this invention. It is the schematic which shows the whole structure of the board | substrate cleaning apparatus provided with the chemical | medical solution mixing apparatus by this invention. It is a graph which shows the sulfuric acid flow rate of the chemical | medical solution mixing apparatus by this invention. It is the schematic which shows the whole structure of the board | substrate cleaning apparatus which has the conventional chemical | medical solution mixing apparatus using a bellows pump. It is a graph which shows the hydrogen peroxide water flow rate and sulfuric acid flow rate of the chemical | medical solution mixing apparatus shown in FIG. It is the schematic which shows the whole structure of the board | substrate cleaning apparatus which has the conventional chemical | medical solution mixing apparatus using a pumping means. It is a graph which shows the hydrogen peroxide water flow rate and sulfuric acid flow rate of the chemical | medical solution mixing apparatus shown in FIG.

1 Substrate processing equipment 10 Chemical liquid mixing equipment 25a Circulation path 25b Auxiliary circulation path 26 In-pipe heater (heating means)
28c Mixed chemical supply pipe (mixed chemical supply means)
33 Quantitative storage pipe (quantitative storage means)
35 Pumping means 38 Metering pump 31a Upstream valve (path switching means)
31b Downstream valve (path switching means)
32a Sulfuric acid supply valve (route switching means)
32b Auxiliary circulation side valve (route switching means)
105 Junction

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(1) Outline of Substrate Processing Apparatus Used for Chemical Solution Mixing Apparatus of the Present Invention In FIG. 1, reference numeral 1 denotes a substrate processing apparatus that uses a mixed chemical solution generated by the chemical liquid mixing apparatus of the present invention described later. Here, first, the configuration of the substrate processing apparatus 1 capable of removing the resist on the substrate surface 3a using a small amount of the mixed chemical solution will be described, and then the chemical solution mixing apparatus of the present invention will be described. In practice, the substrate processing apparatus 1 includes a housing 1d having a bottomed cylindrical shape and an opening 1a on the upper surface, and a rotary table 2 made of a plate-like member is provided horizontally in the housing 1d. The substrate 3 can be held by the turntable 2. A plurality of clamping members 4 for holding the substrate 3 are formed on one surface of the turntable 2, and a cylindrical member 5 serving as a rotation shaft extending from the bottom surface 1b of the housing 1d is connected to the other surface.

The plurality of sandwiching members 4 are provided at intervals along the outer periphery of the turntable 2, and sandwich the substrate 3 from the outer periphery, and hold the substrate 3 with respect to the turntable 2 while maintaining a predetermined distance from the turntable 2. It can be held almost parallel. In the case of this embodiment, the clamping member 4 has a pin shape and is provided with a predetermined distance from the tip to form a stepped portion 4a, and the substrate 3 abuts on the stepped portion 4a, so that a predetermined height position is obtained. In addition, the substrate 3 can be reliably positioned horizontally. The step 4a is formed so that the height from the turntable 2 to the substrate 3 is an optimal position. Here, when holding the substrate 3 on the clamping member 4, the processing surface (substrate surface 3a) on which the circuit is finally formed and the resist is formed for circuit formation is arranged on the turntable 2. The substrate 3 is positioned so as to face the substrate.

Also, the substrate processing apparatus 1 can hold the substrate 3 on the turntable 2 so that the substrate surface 3a is directed to the bottom surface 1b of the housing 1d and can hold the substrate 3 in the vicinity of the opening 1a of the housing 1d. Thereby, in the substrate processing apparatus 1, a small gap can be formed between the facing portions of the periphery of the opening 1a and the outer periphery of the substrate 3. On the other hand, the cylindrical member 5 connected to the other surface of the turntable 2 is rotatably supported by a bearing 5a provided on the bottom surface 1b of the housing 1d. Further, the rotational driving force of the electric motor M can be transmitted to the cylindrical member 5 via the belt 7 and the pulley 6. As a result, the cylindrical member 5 is rotated while being supported by the bearing 5a when the electric motor M is driven, so that the turntable 2 provided at the other end can be rotated.

In addition to this, the cylindrical member 5 includes a processing liquid pipe 8 that supplies a mixed chemical solution that is a processing liquid for resist removal into the housing 1d, and a water supply pipe 9 that supplies pure water as a cleaning liquid into the housing 1d. These are arranged in parallel along the longitudinal direction of the hollow portion. The treatment liquid pipe 8 is connected to one end of a mixed chemical liquid supply pipe of a chemical liquid mixing apparatus 10 to be described later, and the other end opening is arranged so as to face the central portion of the substrate 3 held by the holding member 4. Has been. As a result, the treatment liquid tube 8 can discharge the mixed chemical liquid supplied from the chemical liquid mixing apparatus 10 from the front end opening and supply the mixed chemical liquid toward the central portion of the substrate surface 3a. On the other hand, a cleaning liquid supply means 11 is connected to the water pipe 9 at one end. The water supply pipe 9 has a tip opening at the other end so as to face the central portion of the substrate 3 sandwiched by the sandwiching member 4, and discharges pure water supplied from the cleaning liquid supply means 11 from the tip opening, The pure water can be supplied toward the central portion of the substrate surface 3a.

Further, the housing 1d has a discharge port 1c connected to the suction means 12 in the bottom surface 1b, and the inside of the housing 1d is sucked by the suction means 12 so that the gap between the opening 1a and the substrate 3 is removed. The outside air is sucked to form an air flow that flows downward from above, and by this air flow, the mixed chemical liquid and vapor in the housing 1d can be discharged to the outside from the lower discharge port 1c. Further, an infrared lamp 13 as a substrate heating means is provided above the opening 1a of the housing 1d. The infrared lamp 13 is supported by the support mechanism 15 so as to be retractable from the opening 1a, and is positioned above the opening 1a so as to face the back surface of the substrate 3 held by the turntable 2 in the housing 1d. The substrate 3 can be heated by directly irradiating infrared rays from the opening 1a. An upper water supply pipe 16 for supplying pure water is provided above the opening 1a, and the back surface of the substrate 3 can be cleaned with pure water supplied from the upper water supply pipe 16.

In the above-described configuration, the substrate processing apparatus 1 first drives the electric motor M to rotate the rotary table 2 holding the substrate 3 during chemical processing, and sucks the gas in the housing 1d by the suction means 12. As a result, outside air is sucked into the housing 1d from the opening 1a, and an airflow is formed in which the outside air from above flows to the lower discharge port 1c. In this state, the substrate processing apparatus 1 is supplied with the mixed chemical liquid supplied from the chemical liquid mixing apparatus 10 from the front end opening of the processing liquid pipe 8 toward the central portion of the substrate surface 3a. As a result, the mixed chemical liquid flows uniformly toward the outer periphery while spreading radially toward the circumferential side by the rotation of the substrate 3. At this time, the infrared lamp 13 is disposed above the opening 1a, and the substrate 3 is heated to about 130 ° C. to 300 ° C. from the back side by the infrared lamp 13. As a result, the mixed chemical solution in contact with the substrate surface 3a is brought to an optimum temperature by the heat of the substrate 3, the generation of caroic acid is promoted, and the resist on the substrate surface 3a can be further removed by the caloic acid.

Incidentally, if the mixed chemical solution is simply supplied to the substrate 3 without heating the substrate 3 with the infrared lamp 13, the heat of the mixed chemical solution is generated when the mixed chemical solution comes into contact with the substrate 3 having a low temperature. As a result, the temperature of the mixed chemical solution is lowered and the production of caroic acid is not promoted. Therefore, in this case, it is necessary to supply a large amount of the mixed chemical solution heated to a high temperature to the substrate 3 to prevent the temperature of the mixed chemical solution from decreasing.

On the other hand, in this substrate processing apparatus 1, since the substrate 3 is preheated by the infrared lamp 13 and the substrate 3 itself is also heated to a high temperature, there is no temperature drop of the mixed chemical solution due to contact with the substrate 3. Thus, it is not necessary to supply a large amount of the mixed chemical solution to the substrate 3, and the resist of the substrate 3 can be efficiently removed with a small amount of the mixed chemical solution of, for example, about 50 [ml / min]. In this way, the substrate processing apparatus 1 can reduce the amount of the mixed chemical solution used, and as a result, the generation of the mixed chemical solution to be generated by the chemical solution mixing apparatus 10 immediately before performing the resist removal in the substrate processing apparatus 1 The amount can also be reduced.

Incidentally, in this substrate processing apparatus 1, although steam is generated from the mixed chemical liquid that has contacted the substrate 3 heated to a high temperature, the steam is generated up to the discharge port 1c by the airflow flowing from above to below the outside air taken in from the opening 1a. It is guided and discharged to the outside of the housing 1d. Thus, in the substrate processing apparatus 1, the mixed chemical liquid or vapor can be prevented from leaking from the opening 1a to the outside of the housing 1d, and the mixed chemical liquid or vapor hardly adheres to the inner wall of the housing 1d. The number of times can be reduced. Further, in the substrate processing apparatus 1, the substrate 3 is provided between the opening 1a above the housing 1d and the front end opening of the processing liquid pipe 8 below the housing 1d, and the substrate 3 functions as a cover for the opening 1a to perform mixing. It is also possible to prevent the chemical liquid or vapor from being discharged from the opening 1a by the substrate 3, and without separately providing a ceiling surface or cover covering the opening 1a, as a result, cleaning and drying of these ceiling surfaces and covers Work can be saved.

(2) Configuration of the chemical liquid mixing apparatus according to the present invention Next, the chemical liquid mixing apparatus 10 of the present invention that generates a mixed chemical liquid and supplies the mixed chemical liquid immediately after generation to the substrate processing apparatus 1 described above will be described. In FIG. 2, reference numeral 21 denotes a substrate cleaning apparatus. The substrate cleaning apparatus 21 includes a plurality of substrate processing apparatuses 1 and a plurality of chemical liquid mixing apparatuses 10. On the other hand, one chemical mixing device 10 can be installed. Incidentally, in FIG. 2, attention is paid only to one substrate processing apparatus 1 and one chemical liquid mixing apparatus 10 provided corresponding to this substrate processing apparatus 1, and other substrate processing apparatuses and chemical liquid mixing apparatuses are described. Since all have the same configuration, the description is omitted.

Actually, the substrate cleaning apparatus 21 includes one sulfuric acid storage tank 104 in which sulfuric acid is stored, and the sulfuric acid storage tank 104 is configured to be shared by a plurality of chemical liquid mixing apparatuses 10. Each chemical solution mixing device 10 includes a hydrogen peroxide solution supply pipe 28a that supplies hydrogen peroxide solution to the merge unit 105, a sulfuric acid supply tube 28b that supplies sulfuric acid to the merge unit 105, a hydrogen peroxide solution supply tube 28a, A joining portion 105 where the sulfuric acid supply pipe 28b joins, and a mixed chemical solution supply pipe 28c that supplies the mixed chemical solution generated in the joining portion 105 to the processing solution pipe 8 (FIG. 1) of the substrate processing apparatus 1 are provided.

A sulfuric acid storage tank 104 is connected to the sulfuric acid supply pipe 28b, and an in-pipe heater 26, a circulation pump 27, an upstream valve 31a and an upstream valve 31a are connected between the sulfuric acid storage tank 104 and the junction 105 in order from the sulfuric acid storage tank 104 side. A sulfuric acid supply valve 32a is provided. Further, between the sulfuric acid supply valve 32a and the sulfuric acid storage tank 104, the circulation path 25a and the auxiliary circulation path 25b return the sulfuric acid discharged from the sulfuric acid storage tank 104 by the circulation pump 27 to the sulfuric acid storage tank 104 again. A system path is provided. In practice, the sulfuric acid supply pipe 28b is closed by closing the sulfuric acid supply valve 32a, so that the supply path to the merging portion 105 is blocked, and the sulfuric acid discharged from the sulfuric acid storage tank 104 is not supplied to the merging portion 105. Circulation is continued through either the circulation path 25a or the auxiliary circulation path 25b.

In this case, the sulfuric acid supply pipe 28b is provided with a circulation pipe 30a extending to the sulfuric acid storage tank 104 between the upstream valve 31a and the sulfuric acid supply valve 32a, and the circulation path 25a is formed by the circulation pipe 30a. Can be formed. The circulation path 25a is configured such that the sulfuric acid discharged from the sulfuric acid storage tank 104 by the circulation pump 27 passes through the pipe heater 26, the circulation pump 27, and the upstream valve 31a, and then passes through the circulation pipe 30a and the downstream of the quantitative storage pipe 33 and the downstream side. It is formed so as to return to the sulfuric acid storage tank 104 again via the valve 31b. In addition, the sulfuric acid supply pipe 28b includes an auxiliary circulation pipe 30b that communicates between the circulation pump 27 and the upstream side valve 31a, and between the downstream side valve 31b and the sulfuric acid storage tank 104, and an auxiliary to the auxiliary circulation pipe 30b. It has a circulation side valve 32b, and the auxiliary circulation path 25b can be formed by the auxiliary circulation pipe 30b.

Here, first, the sulfuric acid supply pipe 28b is configured so that the sulfuric acid supply valve 32a and the auxiliary circulation side valve 32b are closed, and the upstream side valve 31a and the downstream side valve 31b disposed in the circulation path 25a are opened to open the circulation path. 25a can be formed. As a result, in the sulfuric acid supply pipe 28b, the sulfuric acid discharged from the sulfuric acid storage tank 104 by the circulation pump 27 again passes through the in-pipe heater 26, the circulation pump 27, the upstream valve 31a, the quantitative storage pipe 33, and the downstream valve 31b in sequence. It flows through the circulation path 25a returning to the sulfuric acid storage tank 104. At this time, in the circulation path 25a, fresh sulfuric acid preheated to about 60 [° C.] by the in-pipe heater 26 is constantly supplied to the quantitative storage pipe 33.

Here, the quantitative storage tube 33 has a cylindrical tube body having an inner diameter larger than that of the sulfuric acid supply tube 28b, and the substrate processing apparatus 1 removes the resist from the substrate 3 installed in the housing 1d. The sulfuric acid at the required flow rate (25 [ml] in this case) can be stored in the pipe body. Specifically, the pipe body of the quantitative storage pipe 33 is formed with, for example, a vertical length of 315 [mm] and an inner diameter of 22 [mm]. (Cross-sectional area perpendicular to the direction) is formed substantially the same, and when pressure is applied from the top to the bottom, the pressure is uniformly applied along the longitudinal direction in the tube body.

Further, a pressure feeding means 35 for supplying an inert gas such as N ₂ gas from the upper side of the quantitative storage pipe 33 into the quantitative storage pipe 33 is provided between the quantitative storage pipe 33 and the downstream valve 31b. . The pumping means 35 is configured to be capable of pumping the sulfuric acid stored in the quantitative storage pipe 33 to the mixed chemical solution supply pipe 28c via the junction 105 by pressurization with an inert gas. Actually, when the upstream valve 31a and the downstream valve 31b are closed while sulfuric acid is circulating in the circulation path 25a, the sulfuric acid supply pipe 28b is shut off and supplied to the quantitative storage pipe 33. The sulfuric acid that has been stored is isolated, and the sulfuric acid can be temporarily stored in the quantitative storage tube 33.

At this time, in the sulfuric acid supply pipe 28b, the auxiliary circulation side valve 32b provided in the auxiliary circulation path 25b is opened, and the sulfuric acid discharged from the sulfuric acid storage tank 104 by the circulation pump 27 is converted into the pipe heater 26, the circulation pump 27, It flows through the auxiliary circulation path 25b that returns to the sulfuric acid storage tank 104 again via the auxiliary circulation pipe 30b. In this way, in the sulfuric acid supply pipe 28b, even when sulfuric acid is temporarily stored in the quantitative storage pipe 33, the path through which the sulfuric acid flows is switched from the circulation path 25a to the auxiliary circulation path 25b, and the freshly preheated by the in-pipe heater 26 is used. It is possible to always circulate fresh sulfuric acid in the auxiliary circulation path 25b. As a result, when the flow path of the sulfuric acid is switched again from the auxiliary circulation path 25b to the circulation path 25a, the preheated fresh sulfuric acid is supplied as it is to the quantitative storage pipe 33, and the optimum solution for generating the mixed chemical solution is generated. The sulfuric acid adjusted to the temperature in advance can be quickly stored again in the quantitative storage tube 33.

When the sulfuric acid supply pipe 28b starts removing the resist of the substrate 3 in the substrate processing apparatus 1, an inert gas is supplied from the pressure feeding means 35 into the quantitative storage pipe 33, and the sulfuric acid supply valve 32a is opened. The sulfuric acid in the quantitative storage pipe 33 can be pumped to the junction 105 by pressurization with an inert gas supplied from the pumping means 35. At this time, the sulfuric acid storage pipe 33 does not discharge all the sulfuric acid stored in the pipe main body, and the sulfuric acid can remain slightly in the pipe main body. As a result, the sulfuric acid supply pipe 28b can supply only the sulfuric acid stored in the quantitative storage pipe 33 to the junction 105, and the inert gas supplied to the quantitative storage pipe 33 is supplied to the junction 105 as it is. It is designed to prevent this.

Thereafter, in the sulfuric acid supply pipe 28b, the sulfuric acid supply valve 32a and the auxiliary circulation side valve 32b are closed again, the upstream side valve 31a and the downstream side valve 31b are opened, and the path through which the sulfuric acid flows is a circulation path from the auxiliary circulation path 25b. Switching to 25a, the sulfuric acid in the sulfuric acid storage tank 104 starts to circulate again through the circulation path 25a. Thus, in this sulfuric acid supply pipe 28b, when the removal of the resist of the substrate 3 is started in the substrate processing apparatus 1, the sulfuric acid temporarily stored in the quantitative storage pipe 33 is pumped with an inert gas and supplied to the junction 105. Thereafter, when the resist removal of the substrate 3 is completed in the substrate processing apparatus 1, sulfuric acid can be supplied to the quantitative storage tube 33 and stored again. As described above, in the sulfuric acid supply pipe 28b, the storage and pumping operation of sulfuric acid is repeated in the quantitative storage pipe 33 in accordance with the resist removal operation of the substrate processing apparatus 1.

On the other hand, the hydrogen peroxide solution supply pipe 28a through which the hydrogen peroxide solution flows is connected to a hydrogen peroxide solution storage tank 36 provided for each chemical liquid mixing device 10, and is joined to the hydrogen peroxide solution storage tank 36. A metering pump 38 is provided between the metering unit 105 and the hydrogen peroxide solution stored in the hydrogen peroxide solution storage tank 36 so that the metering pump 38 can supply the hydrogen peroxide solution to the junction 105. In practice, the metering pump 38 can inject a fixed minute amount of hydrogen peroxide water into the merging portion 105 in one shot, and this is repeated at a high speed for a certain time to make a plurality of shots. A certain amount of hydrogen peroxide solution required to remove the resist can be supplied to the merging portion 105.

Here, the metering pump 38 discharges a very small amount of one shot discharged in one shot, and at a high pressure, the small amount of hydrogen peroxide water is instantaneously transferred to the hydrogen peroxide solution supply pipe 28a at high speed. Injecting, it is possible to always stabilize the instantaneous one-shot discharge amount. In addition, although the metering pump 38 intermittently repeats such one shot at a predetermined cycle, the gap between one shot and one shot is instantaneous and extremely short. When the flow rate of the continuous hydrogen peroxide solution to be supplied is observed, the hydrogen peroxide solution flow is not disturbed irregularly, and becomes a regular hydrogen peroxide solution flow rate. It can always be supplied to the junction 105.

Actually, in the case of this embodiment, as the metering pump 38, for example, an electromagnetically driven diaphragm metering pump is used, and the one-shot discharge amount is 0.7 [sce] per shot, the discharge amount is 0.8 [ml], and the number of strokes Is adjusted to 65 to 240 [spm] and the discharge pressure is 0.2 [Mpa] depending on the mixing ratio and flow rate. Incidentally, an electromagnetically driven diaphragm metering pump applies a voltage to a solenoid to drive a plunger using the driving force generated in the solenoid, and reciprocates a diaphragm provided at the tip of the plunger at a constant distance in the pump chamber. It is made to be able to let you. Thus, in the electromagnetically driven diaphragm type metering pump, the hydrogen peroxide solution is sucked from the hydrogen peroxide solution storage tank 36 in accordance with the reciprocating motion of the diaphragm, and the hydrogen peroxide solution as it is sucked is discharged to the junction 105, It is possible to achieve a stable hydrogen peroxide flow rate without irregular disturbance in the hydrogen peroxide solution flow rate.

Incidentally, in the case of this embodiment, the metering pump 38 is arranged in the vicinity of the merging portion 105, so that although the discharge amount of one shot is small, this small amount of hydrogen peroxide water is surely combined. It is made to be able to reach up to.

In this way, the hydrogen peroxide solution having a stable hydrogen peroxide flow rate without irregular disturbances is supplied from the hydrogen peroxide solution supply pipe 28a to the junction 105, and at the same time, irregular disturbances are similarly produced. Sulfuric acid having a stable flow rate of sulfuric acid is supplied from the sulfuric acid supply pipe 28b, and the hydrogen peroxide solution and sulfuric acid can be mixed to produce a mixed chemical solution.

Here, in the merging section 105, the pre-adjusted hydrogen peroxide flow rate is stably supplied from the hydrogen peroxide solution supply pipe 28a, and the pre-adjusted sulfuric acid flow rate is stably supplied from the sulfuric acid supply pipe 28b. Therefore, a mixed chemical solution in which the mixing ratio is maintained at a constant value as compared with the conventional one can be generated without disturbing the mixing ratio of the hydrogen peroxide solution and sulfuric acid. The junction 105 is configured to be able to supply the mixed chemical liquid to the substrate processing apparatus 1 via the mixed chemical liquid supply pipe 28c by opening a valve 39 provided in the mixed chemical liquid supply pipe 28c. Yes.

Incidentally, in the mixed chemical solution supplied to the substrate processing apparatus 102 from the chemical solution mixing apparatus 10 according to the present invention, for example, hydrogen peroxide solution and sulfuric acid are set to 1: 4 to 8 as an optimum mixing ratio for generating caroic acid. In the chemical mixing device 10, the pressure feeding means 35 and the metering pump 38 are adjusted so that the mixing ratio of hydrogen peroxide solution and sulfuric acid is 1: 4, for example. A mixed chemical solution having a mixing ratio can be supplied to the substrate processing apparatus 1 at a flow rate of 50 to 100 [ml / min] for about 30 [sec].

The mixed chemical solution supply pipe 28c is provided with a branching portion and a mixed chemical solution pressure feeding means 118, and the mixed chemical solution supplied from the merging portion 105 is caused by an inert gas such as N ₂ gas supplied from the mixed chemical solution pressure sending means 118. It can be pumped to the bifurcation. Here, the branch section includes a substrate processing apparatus connection pipe 43a connected to the substrate processing apparatus 1 on one side, and a recovery section connection pipe 43b connected to a mixed chemical solution recovery section (not shown) on the other side. In this case, when the mixed chemical liquid starts to be supplied from the merging section 105, the valve 42a provided in the substrate processing apparatus connection pipe 43a is closed, and the valve 42b provided in the collection section connection pipe 43b is opened. . Accordingly, the mixed chemical solution supplied from the merging unit 105 can be supplied to the mixed chemical solution recovery unit via the recovery unit connection pipe 43b without being supplied to the substrate processing apparatus 1.

Here, as shown in FIG. 3, the sulfuric acid at the start of being supplied from the sulfuric acid supply pipe 28b to the merging section 105 fluctuates greatly instantaneously, and a predetermined time (FIG. 3) after the start of the generation of the mixed chemical solution. In this graph, when about 50 [sec], hereinafter referred to as supply stabilization time), a stable sulfuric acid flow rate is obtained without irregular disturbance. For this reason, the mixing ratio of the initial mixed chemical liquid when the hydrogen peroxide solution and sulfuric acid are started to be mixed in the confluence portion 105 varies depending on the variation of the sulfuric acid flow rate. Therefore, in the mixed chemical solution supply pipe 28c, the valve 42a of the substrate processing apparatus connection pipe 43a is closed and the valve 42b of the recovery part connection pipe 43b is opened, and the initial mixed chemical liquid whose mixing ratio has changed is supplied to the recovery part connection pipe 43b. It can be supplied only to the mixed chemical recovery part.

After that, the mixed chemical solution supply pipe 28c opens the valve 42a of the substrate processing apparatus connection pipe 43a and opens the valve of the collection part connection pipe 43b when the supply stable time set in advance after the start of the generation of the mixed chemical solution at the junction 105 42b is closed. As a result, the mixed chemical solution supply pipe 28c supplies the mixed chemical solution in which the flow rate of sulfuric acid from the sulfuric acid supply tube 28b is stable and the mixing ratio of the mixed chemical solution generated in the merging unit 105 is stable via the substrate processing apparatus connection pipe 43a. Can be supplied to the substrate processing apparatus 1. Thus, in the substrate processing apparatus 1, the mixed chemical solution selected at the optimal mixing ratio for the production of caroic acid is supplied from the chemical solution mixing apparatus 10 so that the resist on the substrate 3 can be reliably removed using the mixed chemical solution. Has been made.

(3) Operation and effect In the above configuration, the chemical liquid mixing apparatus 10 pressurizes the sulfuric acid stored in the quantitative storage pipe 33 with an inert gas by the pressure feeding means 35, and pumps the sulfuric acid to the junction 105, and from this sulfuric acid The hydrogen peroxide solution, which is a small supply amount, is intermittently injected to the confluence 105 with a fixed amount by the metering pump 38, and the hydrogen peroxide solution and sulfuric acid are mixed in the confluence 105 to produce a mixed chemical solution. The Further, in the chemical liquid mixing apparatus 10, the mixed chemical liquid immediately after being generated in the merging unit 105 is supplied to the substrate processing apparatus as it is through the mixed chemical liquid supply pipe 28c.

As described above, in the chemical liquid mixing apparatus 10, since the mixed chemical liquid immediately after generation is directly stored in the substrate processing apparatus 1 without temporarily storing it, the mixed chemical liquid that has not deteriorated with time in the substrate processing apparatus 1 is used. The resist can be removed from the substrate. Further, in this chemical mixing apparatus 10, since sulfuric acid is pumped by the pumping means, a stable sulfuric acid flow without pulsation can be maintained when sulfuric acid is supplied to the merging section 105. Furthermore, in this chemical liquid mixing apparatus, a small amount of hydrogen peroxide solution to be injected in one shot can be obtained by supplying the hydrogen peroxide solution with a small supply amount to the confluence unit 105 with the metering pump 33. In addition to being able to inject stably, by repeating one shot intermittently at high speed, there is no irregular disturbance in the continuous hydrogen peroxide solution flow rate supplied to the confluence 105, and a stable hydrogen peroxide solution flow rate is achieved. It can be supplied to the junction 105.

Further, in this chemical mixing device 10, a circulation path 25a for returning the sulfuric acid discharged from the sulfuric acid storage tank 104 to the sulfuric acid storage tank 104 is provided, and the sulfuric acid circulating in the circulation path 25a is provided by the in-pipe heater 26 provided in the circulation path 25a. Was always preheated. As described above, in the chemical liquid mixing apparatus 10, the sulfuric acid is preheated immediately before being supplied to the substrate processing apparatus, so that it is necessary to promote the generation of caroic acid immediately before performing the resist removal in the substrate processing apparatus 1. The temperature of the mixed chemical solution can be easily and quickly raised to a high temperature region. As a result, in this chemical solution mixing apparatus 10, the time required for heating the mixed chemical solution to the high temperature region in the substrate processing apparatus 1 can be shortened compared to the case where the mixed chemical solution is heated from the normal temperature to the high temperature region in the substrate processing apparatus 1. Accordingly, the resist removal of the substrate 3 can be performed quickly.

Furthermore, in this chemical solution mixing apparatus 10, separately from the sulfuric acid storage tank 104, the used amount of sulfuric acid used for one resist removal operation of the substrate 3 in the substrate processing apparatus 1 is temporarily stored in the quantitative storage pipe 33, The sulfuric acid in the fixed quantity storage tube 33 was pressurized with an inert gas from the pressure feeding means 35 so that the sulfuric acid was supplied to the junction 105. As a result, in the chemical mixing apparatus 10, compared with the case where pressure is applied to the entire sulfuric acid storage tank 104 in which the sulfuric acid used for the next resist removal operation and all the sulfuric acid used in other chemical mixing apparatuses are stored, the capacity is large. Since it is only necessary to pressurize only the minimum necessary sulfuric acid used for one resist removal operation, the sulfuric acid can be stably pumped to the junction 105 with a small pressurization.

Further, in the chemical liquid mixing apparatus 10, an inert gas is supplied to the quantitative storage pipe 33 with a small capacity, and the sulfuric acid stored in the quantitative storage pipe 33 is vigorously pumped to the junction 105 by the inert gas. Thus, a stable sulfuric acid flow rate can be maintained in the merging portion 105 without being affected by the supply pressure of the hydrogen peroxide solution supplied from the metering pump 38 to the merging portion 105.

Furthermore, in this chemical liquid mixing apparatus 10, since the quantitative storage pipe 33 is individually installed corresponding to the substrate processing apparatus 1, the quantitative storage pipe 33 can be installed in the vicinity of the substrate processing apparatus 1, and thus the substrate Compared to the case where the inert gas is supplied to the sulfuric acid storage tank 104 installed far away from the processing apparatus 1 to pump the sulfuric acid, the sulfuric acid in the quantitative storage pipe 33 is reduced while lowering the supply pressure of the inert gas. It is possible to reliably reach the junction 105 and the mixed chemical supply pipe 28c.

In addition, in this chemical mixing device 10, in addition to the circulation path 25a provided with the quantitative storage pipe 33, an auxiliary circulation path 25b for returning sulfuric acid back to the sulfuric acid storage tank 104 is provided, and an upstream valve 31a as a path switching means, downstream By opening and closing the side valve 31b, the sulfuric acid supply valve 32a, and the auxiliary circulation side valve 32b, sulfuric acid from the sulfuric acid storage tank 104 is supplied to one of the circulation path 25a and the auxiliary circulation path 25b. Further, in this chemical solution mixing apparatus 10, the upstream side valve 31a, the downstream side valve 31b, the sulfuric acid supply valve 32a, and the auxiliary circulation side valve 32b are controlled to open and close the supply path of sulfuric acid, so that At the same time as the sulfuric acid is temporarily stored, the sulfuric acid can be circulated while being preheated in the auxiliary circulation path 25b while the sulfuric acid is stored in the quantitative storage pipe 33. Thereby, in the chemical mixing device 10, when the auxiliary circulation path 25b is switched again to the circulation path 25a and sulfuric acid is stored in the quantitative storage pipe 33, the fresh sulfuric acid that has been preheated by the in-tube heater 26 is again replaced with the quantitative storage pipe. 33 can be stored quickly.

According to the above configuration, in the chemical liquid mixing device 10, the flow rate of sulfuric acid is stabilized by pumping sulfuric acid by the pumping means 35, and the hydrogen peroxide solution having a smaller supply amount than sulfuric acid is fixed to the fixed amount by the metering pump 38. A small amount is injected at high speed (high-speed injection) to stabilize the hydrogen peroxide flow rate, and a mixed chemical solution is generated from sulfuric acid and hydrogen peroxide solution at the junction 105, and the mixed chemical solution immediately after generation is processed directly into the substrate. By supplying to the device 1, the mixed chemical solution can be supplied to the substrate processing device 1 without deterioration over time, and fluctuation of the mixing ratio of sulfuric acid and hydrogen peroxide solution is suppressed when the mixed chemical solution is generated Thus, a mixed chemical liquid maintained at a constant mixing ratio can be generated.

(4) Other Embodiments The present invention is not limited to the present embodiment, and various modifications can be made within the scope of the present invention. Other heating means other than those may be used. Further, when supplying sulfuric acid to the merging section 105, it is not always necessary to temporarily store the sulfuric acid in the quantitative storage pipe 33. For example, a pressure feeding means is provided in the sulfuric acid storage tank 104, and sulfuric acid is directly supplied from the sulfuric acid storage tank 104 to the merging section 105. You may make it pump.

Furthermore, in the above-described embodiment, the case where the quantitative storage pipe 33 is arranged in the circulation path 25a has been described. However, the present invention is not limited thereto, and sulfuric acid supply other than the circulation path 25a and the auxiliary circulation path 25b is performed. The quantitative storage pipe 33 may be arranged at various positions of the pipe 28b, or a sulfuric acid supply pipe 28b without the circulation path 25a and the auxiliary circulation path 25b may be applied.

Furthermore, in the above-described embodiment, the chemical solution mixing device 10 is connected to the single-wafer type substrate processing apparatus 1, and the mixed chemical solution necessary for removing the resist on one substrate is mixed with the chemical solution by the substrate processing device 1. Although the case of generating in the apparatus 10 has been described, the present invention is not limited to this, and the chemical liquid mixing apparatus 10 may be applied to a substrate processing apparatus that removes resist for a plurality of substrates at once. You may make it produce | generate the mixed chemical | medical solution used for the resist removal of several board | substrates once with the chemical | medical solution mixing apparatus 10. FIG.

Furthermore, in the above-described embodiment, when the sulfuric acid is being pumped from the quantitative storage pipe 33 to the junction 105 as a metering pump that injects the hydrogen peroxide solution less than sulfuric acid into a certain minute amount and injects it into the junction, The case where the metering pump 38 that intermittently injects the hydrogen peroxide solution less than sulfuric acid into the joining part in a constant minute amount has been described, but the present invention is not limited to this, and the metering storage pipe 33 to the joining part 105 When sulfuric acid is being supplied, a metering pump that injects a certain small amount of hydrogen peroxide solution into the junction only once without injecting hydrogen peroxide solution intermittently may be applied. The supply pressure that can achieve a stable hydrogen peroxide flow rate that does not fluctuate in the hydrogen peroxide solution flow rate, and that does not affect the pumping in the quantitative storage pipe 33, and overoxidizes the junction 105. Quantitative pump that can inject hydrogen water It is sufficient.

In this case, as a metering pump that continuously injects a constant and small amount of hydrogen peroxide solution into the junction 105 like the metering pump 38 of the above-described embodiment, for example, an electromagnetically driven piston metering pump, a syringe pump, Various other metering pumps such as a rotary displacement type uniaxial eccentric screw pump may be applied. Here, the syringe pump has a configuration in which a certain minute amount of hydrogen peroxide solution is continuously injected to the junction 105 by pushing the syringe at a predetermined speed by the driving force of the motor. In addition, the rotary positive displacement single-shaft eccentric screw pump has a single-shaft structure in which a single-threaded male screw rotor rotates while performing eccentric motion in a double-threaded female screw stator, and rotates the rotor inscribed in the stator. In this configuration, the hydrogen peroxide solution that fills the gap between the stator and the rotor is sent in the axial direction so that a small amount of the hydrogen peroxide solution is continuously injected to the junction 105. is there.

Claims

A chemical liquid mixing apparatus that mixes sulfuric acid and hydrogen peroxide water to generate a mixed chemical liquid, and supplies the mixed chemical liquid to a substrate processing apparatus that performs resist removal of the substrate using the mixed chemical liquid,
Pressurizing means for pressurizing the sulfuric acid with an inert gas, and pumping the sulfuric acid to the joining portion;
A metering pump for injecting the hydrogen peroxide solution, which is less than the sulfuric acid, into a certain minute amount and injecting it into the merging section;
A chemical liquid mixing apparatus, comprising: a mixed chemical liquid supply unit configured to supply the mixed chemical liquid generated by mixing the hydrogen peroxide solution and the sulfuric acid at the merging portion to the substrate processing apparatus.
The chemical liquid mixing apparatus according to claim 1, wherein the metering pump continuously injects the fixed minute amount of hydrogen peroxide solution to the junction.
A circulation path for returning the sulfuric acid discharged from the sulfuric acid storage tank back to the sulfuric acid storage tank;
The chemical liquid mixing apparatus according to claim 1, further comprising: a heating unit that is provided in the circulation path and preheats the sulfuric acid before being supplied to the substrate processing apparatus.
Separately from the sulfuric acid storage tank, the substrate processing apparatus comprises a quantitative storage means for storing a used amount of sulfuric acid used for one resist removal operation of the substrate,
The chemical solution mixing apparatus according to claim 3, wherein the sulfuric acid in the quantitative storage means is pressurized with an inert gas from the pressure feeding means, and the sulfuric acid is supplied to the junction.
Separately from the circulation path, an auxiliary circulation path in which the sulfuric acid heated by the heating means returns to the sulfuric acid storage tank, and
Path switching means for flowing the sulfuric acid supplied from the sulfuric acid storage tank to one of the circulation path and the auxiliary circulation path;
The quantitative storage means is arranged in the circulation path,
The path switching means controls the sulfuric acid supply path so as to store the sulfuric acid in the quantitative storage means and to store sulfuric acid in the auxiliary circulation path in a state where the sulfuric acid is stored in the quantitative storage means. It circulates. The chemical | medical solution mixing apparatus of Claim 4 characterized by the above-mentioned.