Substrate processing apparatus and substrate processing method

Abstract

The present invention treats a substrate while suppressing a decrease in oxidizing power of electrolyzed sulfuric acid. The substrate processing apparatus includes: a substrate processing unit configured to process a substrate using a processing liquid containing electrolytic sulfuric acid; a supply tank for storing the processing liquid supplied to the substrate processing unit; a temperature raising unit for raising the temperature of the processing liquid by mixing and applying water to the processing liquid supplied from the supply tank in the substrate processing unit; a generation unit for generating a processing liquid by electrolysis and supplying the generated processing liquid to the supply tank; and a recovery unit that recovers a post-treatment liquid, which is the treatment liquid used in the substrate treatment unit, and supplies the post-treatment liquid to the generation unit.

Description

Technical Field

[0001] The technology disclosed in this specification relates to substrate processing technology. The substrates to be processed include, for example, semiconductor wafers, glass substrates for liquid crystal displays (LCDs), substrates for flat panel displays (FPDs) such as organic EL (electroluminescence) displays, substrates for optical disks, magnetic disks, magneto-optical disks, glass substrates for photomasks, ceramic substrates, substrates for field emission displays (FEDs), and substrates for solar cells. Background Art

[0002] Previously, a mixed solution of sulfuric acid and hydrogen peroxide solution (SPM) has been used as a processing liquid in substrate processing (for example, see Patent Document 1). SPM is a processing liquid generated by mixing hydrogen peroxide solution with sulfuric acid to generate oxidizing power, and is mainly used for substrate processing such as removing resist formed on the upper surface of the substrate.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2018-163977 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] On the other hand, electrolytic sulfuric acid may be used as a processing liquid for substrate processing instead of using SPM that generates a large amount of drainage as a processing liquid.

[0008] However, if the electrolytic sulfuric acid is maintained at a high temperature for a long time for use in substrate processing, there is a problem that the oxidizing power of the electrolytic sulfuric acid decreases due to self-decomposition.

[0009] The technology disclosed in this specification has been accomplished in view of the above-described problems, and is a technology for performing substrate processing while suppressing a decrease in the oxidizing power of electrolytic sulfuric acid.

[0010] [Technical means to solve the problem]

[0011] The first mode of the technology disclosed in the specification of this case comprises: a substrate processing unit for processing a substrate using a processing liquid containing electrolytic sulfuric acid; a supply tank for storing the processing liquid supplied to the substrate processing unit; a temperature rising unit for heating the processing liquid supplied from the supply tank in the substrate processing unit by mixing it with water; a generating unit for generating the processing liquid by electrolysis and supplying the generated processing liquid to the supply tank; and a recovery unit for recovering the processing liquid used in the substrate processing unit, i.e., post-processing liquid, and supplying it to the generating unit.

[0012] The second mode of substrate processing apparatus of the technology disclosed in the specification of this case is associated with the first mode of substrate processing apparatus, and is further provided with a first circulation path for returning the processing liquid supplied from the above-mentioned supply tank to the above-mentioned supply tank, the above-mentioned substrate processing portion is provided with a spray nozzle branched from the above-mentioned first circulation path for spraying the supplied processing liquid toward the above-mentioned substrate, the above-mentioned spray nozzle is provided with a spray path for spraying the supplied processing liquid toward the above-mentioned substrate, and a second circulation path branched from the above-mentioned spray path for returning the above-mentioned processing liquid to the above-mentioned supply tank, the above-mentioned temperature rising portion is located in the above-mentioned spray path further downstream than the branch point with the above-mentioned second circulation path, and mixes the above-mentioned imparting water with the above-mentioned processing liquid.

[0013] The third mode of substrate processing apparatus of the technology disclosed in the specification of this case is related to the second mode of substrate processing apparatus, and is also provided with a second temperature adjustment unit, which is used to adjust the temperature of the above-mentioned processing liquid in the above-mentioned first circulation path to a temperature used to generate the above-mentioned processing liquid by electrolysis, namely, an electrolysis temperature.

[0014] The substrate processing apparatus of the fourth mode of the technology disclosed in the specification of this case is associated with the substrate processing apparatus of any one of the first to third modes, and the above-mentioned generating section comprises a first electrolysis section and a second electrolysis section for generating the above-mentioned processing liquid by electrolysis. While the above-mentioned first electrolysis section supplies the above-mentioned processing liquid to the above-mentioned supply tank, the above-mentioned second electrolysis section electrolyzes the above-mentioned processed liquid recovered by the above-mentioned recovery section to generate the above-mentioned processing liquid.

[0015] The substrate processing device of the fifth mode of the technology disclosed in the specification of this case is associated with the substrate processing device of any one of the first to fourth modes, and the above-mentioned generation unit has a first temperature adjustment unit, which is used to adjust the temperature of the above-mentioned post-processing liquid and the temperature of the above-mentioned processing liquid generated to the temperature used to generate the above-mentioned processing liquid by electrolysis, that is, the electrolysis temperature.

[0016] The substrate processing device of the 6th mode of the technology disclosed in the specification of this case is associated with the substrate processing device of any one of the 1st to 5th modes, and the above-mentioned generating section comprises: a 1st replenishing section, which is used to replenish the above-mentioned imparted water to the above-mentioned electrolyzed processing liquid; and a 2nd replenishing section, which is used to replenish sulfuric acid to the above-mentioned electrolyzed processing liquid.

[0017] The seventh mode of the substrate processing method of the technology disclosed in the specification of this case is used to process a substrate using a processing liquid containing electrolytic sulfuric acid, and comprises the following steps: storing the above-mentioned processing liquid supplied to a substrate processing part in a supply tank; in the above-mentioned substrate processing part, heating the above-mentioned processing liquid by mixing the above-mentioned processing liquid supplied from the above-mentioned supply tank with water; in the above-mentioned substrate processing part, processing the above-mentioned substrate using the above-mentioned processing liquid mixed with the above-mentioned water; recovering the above-mentioned processing liquid used for processing in the above-mentioned substrate processing part, i.e., treated liquid, and supplying it to a generating part; and generating the above-mentioned processing liquid from the liquid containing the above-mentioned treated liquid by electrolysis in the above-mentioned generating part, and supplying the generated above-mentioned processing liquid to the above-mentioned supply tank.

[0018] Effects of the Invention

[0019] According to at least the first and seventh aspects of the technology disclosed in the present specification, by heating the electrolytic sulfuric acid contained in the processing liquid immediately before it is used for substrate processing in the substrate processing unit, substrate processing can be performed while suppressing the reduction in the oxidizing power of the electrolytic sulfuric acid.

[0020] In addition, the objects, features, aspects, and advantages of the technology disclosed in this specification will become more apparent from the following detailed description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a diagram showing a configuration example of a substrate processing apparatus according to an embodiment.

[0022] Figure 2 It is conceptually expressed Figure 1 A diagram showing an example of the configuration of a control unit shown in the example.

[0023] Figure 3 This is a diagram schematically showing a processing unit and a related configuration example in a substrate processing apparatus according to an embodiment.

[0024] Figure 4 It is a cross-sectional view showing an example of the internal structure of the ejection nozzle.

[0025] Figure 5 This is a diagram showing a configuration example of a substrate processing apparatus in a circulation state of a discharge nozzle.

[0026] Figure 6This is a diagram showing a configuration example of a substrate processing apparatus in a discharge state of a discharge nozzle. DETAILED DESCRIPTION

[0027] The following embodiments will be described with reference to the accompanying drawings. Although detailed features and the like are shown in the following embodiments for the purpose of explaining the technology, these are merely examples and not all of them are necessarily essential features in order to implement the embodiments.

[0028] Furthermore, the drawings are schematic representations, and for the sake of convenience, some components may be omitted or simplified as appropriate. Furthermore, the sizes and positions of components shown in the various drawings are not necessarily accurately depicted and may be modified as appropriate. Furthermore, in drawings such as top views that are not cross-sectional views, hatching may be used to facilitate understanding of the embodiments.

[0029] In the following description, the same components are denoted by the same reference numerals and are illustrated in the figures. Their names and functions are also the same, and therefore, detailed descriptions thereof may be omitted to avoid redundancy.

[0030] In addition, in the description recorded in the specification of the present case, when it is described as "having", "including" or "having" a certain component, unless otherwise specified, it is not an exclusive description that excludes the existence of other components.

[0031] In addition, in the descriptions recorded in the specification of this case, even if there are cases where ordinal numbers such as "1st" or "2nd" are used, these terms are used expediently to facilitate understanding of the content of the implementation method, and the content of the implementation method is not limited to the order generated by these ordinal numbers.

[0032] In addition, even if there are cases in the descriptions recorded in the specification of this case where terms are used that imply specific positions or directions such as "up", "down", "left", "right", "side", "bottom", "front" or "back", these terms are used expediently to facilitate understanding of the content of the implementation method and have nothing to do with the position or direction when the implementation method is actually implemented.

[0033] Furthermore, in the description of this application, when the description refers to "the upper surface of..." or "the lower surface of...", this includes not only the upper surface or lower surface of the component in question, but also states where other components are formed on the upper or lower surface of the component in question. That is, for example, when the description refers to "B disposed on the upper surface of A," another component "C" may be disposed between A and B.

[0034] <Implementation Method>

[0035] Hereinafter, a substrate processing apparatus and a substrate processing method according to this embodiment will be described.

[0036] <About the Configuration of the Substrate Processing Apparatus>

[0037] Figure 1 1 is a diagram showing an example of the structure of a substrate processing apparatus related to this embodiment. Figure 1 As shown in the example, the substrate processing apparatus 1 includes a plurality of processing units 600 , a supply tank 10 , generation tanks 20A and 20B, electrolytic cells 21A and 21B, a recovery tank 30 , a drain tank 40 for draining a processing liquid, and a control unit 90 .

[0038] The processing unit 600 processes the substrate using the supplied processing liquid. The detailed structure of the processing unit 600 will be described below. Figure 1 The number shown.

[0039] The supply tank 10 stores the treatment liquid supplied from the generation tank 20A or the generation tank 20B via the supply piping 100. Furthermore, the supply tank 10 supplies the treatment liquid to the processing unit 600. Furthermore, pure water (DIW), hydrogen peroxide solution, or ozone water is supplied to the supply tank 10 from a pure water supply source 12. The flow rate of pure water, etc., supplied from the pure water supply source 12 can be adjusted by controlling a valve 12A using the control unit 90. Furthermore, the pure water supply source 12 may not be provided.

[0040] The piping for supplying the treatment liquid from the supply tank 10 includes: a circulation piping 102, which is connected to the supply tank 10 and circulates the treatment liquid through the supply tank 10; a measuring piping 104, which branches off from the circulation piping 102 and returns the treatment liquid to the supply tank 10; a supply piping 106, which branches off from the circulation piping 102 and supplies the treatment liquid to each treatment unit 600; a return piping 108, which branches off at the end on the downstream side of each supply piping 106 and returns the treatment liquid to the supply tank 10 side; and a circulation piping 110, which returns the treatment liquid merged from each return piping 108 to the supply tank 10.

[0041] On the upstream side of the circulation piping 102, beyond the point where it branches off from the measuring piping 104, are installed a flow meter 112 for measuring the flow rate of the treatment liquid, a pump 114 for circulating the treatment liquid, a heater 116 for heating the treatment liquid, a thermometer 117 for measuring the temperature of the treatment liquid, and an electrolytic cell 118 for electrolyzing the treatment liquid. Furthermore, the electrolytic cell 118 may not be provided if the self-decomposition of the treatment liquid is sufficiently suppressed. Furthermore, the heater may be replaced with a mechanism capable of adjusting the temperature, including cooling, and is not limited to heating. This also applies to the heaters described below.

[0042] The measurement piping 104 is provided with a concentration meter 120 for measuring the concentration of the treatment liquid flowing through the measurement piping 104. If the concentration of the treatment liquid measured by the concentration meter 120 is higher than the desired concentration, the concentration of the treatment liquid can be reduced by supplying pure water or the like from the pure water supply source 12 to the supply tank 10 under the control of the control unit 90. Furthermore, if the concentration of the treatment liquid measured by the concentration meter 120 is lower than the desired concentration, the treatment liquid is electrolyzed in the electrolytic cell 118 under the control of the control unit 90, and water is also electrolyzed at the same time, thereby increasing the concentration of the treatment liquid. Furthermore, the water generated by the electrolysis can also be used as the feed water.

[0043] On the downstream side of the circulation piping 102 from the position where it branches off from the measuring piping 104, there are provided a filter 119 for removing particles etc. in the treatment liquid, and a valve 102A for adjusting the flow rate of the treatment liquid circulating in the circulation piping 102 by control by the control unit 90.

[0044] The supply pipe 106 is provided with a valve 106A that can adjust the flow rate of the processing liquid flowing in the supply pipe 106 by control by the controller 90. The flow rate of a portion of the processing liquid flowing in the circulation pipe 102 flows in the supply pipe 106.

[0045] The return pipe 108 is provided with a valve 108A that can adjust the flow rate of the processing liquid flowing through the return pipe 108 through control by the control unit 90 .

[0046] Furthermore, the portion where the return pipe 108 branches off from the supply pipe 106 is provided in the discharge nozzle 106B in the treatment unit 600. Furthermore, the discharge nozzle 106B is connected to a mixing pipe 200 for mixing a supply water such as pure water (DIW), hydrogen peroxide solution, or ozone water with the treatment liquid in the supply pipe 106. The mixing pipe 200 is provided with a valve 200A that can be controlled by the control unit 90 to adjust the flow rate of the supply water flowing in the mixing pipe 200.

[0047] Furthermore, the applied water supplied to the mixing pipe 200 may be supplied from the pure water supply source 12 or from a separately prepared supply source.

[0048] The piping for recovering the processing liquid from the processing unit 600 includes: a drain piping 122, which is connected to each processing unit 600 and discharges the processing liquid (processed liquid) used for substrate processing; a recovery piping 124, which supplies the processed liquid merged from each drain piping 122 to the recovery tank 30; a recovery piping 126, which is connected to the recovery tank 30 and supplies the processed liquid to the generating tank 20A or the generating tank 20B; a circulation piping 128, which circulates the processing liquid between the generating tank 20A and the electrolytic tank 21A; a circulation piping 130, which circulates the processing liquid between the generating tank 20B and the electrolytic tank 21B; a supply piping 132, which allows the processing liquid to merge from the generating tank 20A to the supply piping 100; and a supply piping 134, which allows the processing liquid to merge from the generating tank 20B to the supply piping 100. The drain pipe 122 is provided with a valve 122A that adjusts the flow rate of the drain from the processing unit 600 under the control of the control unit 90 .

[0049] Here, a plurality of recovery tanks 30 may be provided in parallel. That is, the treated liquid from the recovery pipe 124 can be selectively supplied to a plurality of recovery tanks, thereby lengthening the time until the treated liquid is supplied from the recovery tank to the generation tank.

[0050] The recovery piping 126 is provided with: a pump 136 for transporting the treated liquid stored in the recovery tank 30 to the generation tank 20A or the generation tank 20B; a valve 126A, which can adjust the flow rate of the treated liquid transported to the generation tank 20A by controlling the control unit 90; and a valve 126B, which can adjust the flow rate of the treated liquid transported to the generation tank 20B by controlling the control unit 90.

[0051] The circulation piping 128 is provided with: a valve 128A, which is used to adjust the flow rate of the treatment liquid flowing in the circulation piping 128 by controlling the control unit 90; a concentration meter 138, which is used to measure the concentration of the treatment liquid flowing in the circulation piping 128; a pump 140, which is used to transport the treatment liquid flowing in the circulation piping 128; a heater 142, which heats the treatment liquid; and a filter 144, which removes particles and the like in the treatment liquid.

[0052] The circulation piping 130 is provided with: a valve 130A, which is used to adjust the flow rate of the treatment liquid flowing in the circulation piping 130 by controlling the control unit 90; a concentration meter 146, which is used to measure the concentration of the treatment liquid flowing in the circulation piping 130; a pump 148, which is used to transport the treatment liquid flowing in the circulation piping 130; a heater 150, which heats the treatment liquid; and a filter 152, which removes particles and the like in the treatment liquid.

[0053] The supply pipe 132 is provided with a valve 132A that adjusts the flow rate of the processing liquid flowing through the supply pipe 132 under control by the control unit 90 .

[0054] The supply pipe 134 is provided with a valve 134A that adjusts the flow rate of the processing liquid flowing through the supply pipe 134 under control by the control unit 90 .

[0055] The supply piping 100 is provided with: a pump 154 for transporting the treatment liquid flowing in the supply piping 100; a heater 156 for heating the treatment liquid; a filter 158 for removing particles and the like in the treatment liquid; and a valve 100A for adjusting the flow rate of the treatment liquid flowing in the supply piping 100 by controlling the control unit 90.

[0056] Furthermore, pure water (DIW), hydrogen peroxide solution, or ozone water is supplied from the pure water supply source 14 to the generation tank 20A and the generation tank 20B. The flow rate of the pure water, etc. supplied from the pure water supply source 14 to the generation tank 20A can be adjusted by controlling the valve 14A using the control unit 90. Furthermore, the flow rate of the pure water, etc. supplied from the pure water supply source 14 to the generation tank 20B can be adjusted by controlling the valve 14B using the control unit 90. Furthermore, the pure water supply source 14 may not be provided.

[0057] Furthermore, sulfuric acid (H2SO4) is supplied to the generation tank 20A and the generation tank 20B from the sulfuric acid supply source 16. The flow rate of sulfuric acid supplied from the sulfuric acid supply source 16 to the generation tank 20A can be adjusted by controlling valve 16A using the control unit 90. Furthermore, the flow rate of sulfuric acid supplied from the sulfuric acid supply source 16 to the generation tank 20B can be adjusted by controlling valve 16B using the control unit 90. Furthermore, the sulfuric acid supply source 16 may not be provided.

[0058] The pipes for draining the processing liquid and the post-processed liquid include a drain pipe 160 for draining the post-processed liquid from each processing unit 600 to the drain tank 40; a drain pipe 162 for draining the processing liquid from the supply tank 10 to the drain tank 40; and a drain pipe 164 for draining the processing liquid or the post-processed liquid from the generation tank 20A, the generation tank 20B, and the recovery tank 30 to the drain tank 40. The drain pipe 160 is provided with a valve 160A for adjusting the flow rate of the drain from the processing unit 600 under the control of the control unit 90. The drain pipe 162 is provided with a valve 162A for adjusting the flow rate of the drain from the supply tank 10 under the control of the control unit 90. The drainage piping 164 is provided with: a valve 164A, which adjusts the flow rate of the drainage from the generation tank 20A under the control of the control unit 90; a valve 164B, which adjusts the flow rate of the drainage from the generation tank 20B under the control of the control unit 90; and a valve 164C, which adjusts the flow rate of the drainage from the recovery tank 30 under the control of the control unit 90.

[0059] Figure 2 It is conceptually expressed Figure 1 The diagram shows an example of the configuration of the control unit 90 shown in FIG. The control unit 90 can be formed by a general computer having circuits. Specifically, the control unit 90 includes a central processing unit (CPU) 91, a read-only memory (ROM) 92, a random access memory (RAM) 93, a storage device 94, an input unit 96, a display unit 97, and a communication unit 98, and a bus line 95 interconnecting these.

[0060] ROM 92 stores basic programs. RAM 93 serves as a work area for CPU 91 when performing predetermined processing. Storage device 94 is comprised of a non-volatile storage device such as a flash memory or a hard disk drive. Input unit 96 is comprised of various switches or a touch panel, and receives input and setting instructions such as processing procedures from the operator. Display unit 97 is comprised of, for example, a liquid crystal display device and a lamp, and displays various information under the control of CPU 91. Communication unit 98 has a data communication function via a local area network (LAN), etc.

[0061] The storage device 94 is pre-set with respect to Figure 1 The processing program 94P is executed by the CPU 91 to select one of the aforementioned modes and control each component of the substrate processing apparatus 1. Furthermore, the processing program 94P may be stored on a recording medium. Using this recording medium, the processing program 94P can be installed in the control unit 90. Furthermore, some or all of the functions performed by the control unit 90 do not necessarily need to be implemented by software and may be implemented by hardware such as dedicated logic circuits.

[0062] Figure 3 1 is a diagram schematically showing an example of a processing unit 600 and related configurations in a substrate processing apparatus according to this embodiment. Figure 3 In the figure, it is shown that the configuration Figure 1 The configuration of the processing unit 600 downstream of a certain supply pipe 106 is similar to the configuration of the processing unit 600 downstream of the other supply pipes 106. Figure 3 The same is true for the situation shown in the example.

[0063] like Figure 3As shown in the example, the processing unit 600 includes: a box-shaped chamber 80 having an internal space; a rotating chuck 251, which holds a substrate W in a horizontal position in the chamber 80 and rotates the substrate W around a vertical rotation axis Z1 passing through the center of the substrate W; and a cylindrical processing shield 511, which surrounds the rotating chuck 251 around the rotation axis Z1 of the substrate W.

[0064] The chamber 80 is surrounded by a box-shaped wall 250A. The wall 250A has an opening 250B formed therein for carrying a substrate W into or out of the chamber 80 .

[0065] The opening 250B is opened and closed by the shutter 250C. The shutter 250C is moved to a closed position (in a position where the shutter 250C covers the opening 250B) by a shutter lifting mechanism (not shown). Figure 3 Indicated by a two-dot chain line in the figure), and the opening position where the opening 250B is opened (indicated by a two-dot chain line in the figure) Figure 3 The solid line in the middle indicates the rise and fall of the

[0066] like Figure 3 As shown in the example, the rotary chuck 251 includes: a circular plate-shaped rotary base 251A, which is arranged opposite to the horizontally positioned substrate W; a plurality of chuck pins 251B, which protrude upward from the outer peripheral portion of the upper surface of the rotary base 251A and clamp the peripheral portion of the substrate W; a rotary shaft 251C, which extends downward from the central portion of the rotary base 251A; and a rotary motor 251D, which rotates the substrate W adsorbed on the rotary base 251A by rotating the rotary shaft 251C.

[0067] Furthermore, the rotary chuck 251 is not limited to Figure 3 In the case of the clamping type chuck shown in the example, for example, a vacuum adsorption type chuck including a spin base for vacuum adsorbing the lower surface of the substrate W may be used.

[0068] The processing unit 600 may also be connected to a nozzle for spraying liquid for other purposes (for example, a nozzle for spraying other liquid chemicals or a nozzle for spraying a rinse liquid, etc.).

[0069] In addition, if Figure 3 As shown in the middle example, a discharge nozzle 106B for discharging the processing liquid is connected to the front end of the supply pipe 106 connected to the processing unit 600. The discharge nozzle 106B discharges the processing liquid toward a predetermined location inside the chamber 80 (for example, the spin base 251A).

[0070] The processing shield 511 is disposed so as to surround the spin chuck 251 and is vertically raised and lowered by a lifting mechanism (not shown) (e.g., a motor or cylinder). The upper portion of the processing shield 511 is raised and lowered between an upper position, where its upper end is above the substrate W held on the spin base 251A, and a lower position, where its upper end is below the substrate W.

[0071] The processing liquid scattered outward from the upper surface of the substrate W is caught by the inner side surface of the processing shield 511. The processing liquid caught by the processing shield 511 is then appropriately drained to the outside of the chamber 80 via the drain pipe 122 and the drain pipe 160 provided at the bottom of the chamber 80 and inside the processing shield 511. Furthermore, the atmosphere within the processing shield 511 is exhausted by a shield exhaust mechanism (not shown).

[0072] Furthermore, an exhaust port 515 is provided on a side portion of the chamber 80 , so that the atmosphere in the chamber 80 is appropriately exhausted to the outside of the chamber 80 through the exhaust port 515 .

[0073] Figure 4 It is a cross-sectional view showing an example of the internal structure of the discharge nozzle 106B.

[0074] The ejection nozzle 106B comprises: a main body 36, which forms a flow path 35 for guiding the treatment liquid; a valve body 37, which opens and closes the flow path 35; a pneumatic actuator 38, which causes the valve body 37 to move forward and backward in the axial direction X1 to open and close the flow path 35; a mixing pipe 200, which merges at a position (flow path 35c) in the flow path 35 that is further downstream than the valve body 37; and a ejection port 31.

[0075] The main body 36 includes: a cylinder 39, which constitutes a pneumatic actuator 38; a valve chamber 40A, which moves the valve body 37 forward and backward; a flow path 35a, which is connected to the supply piping 106 and reaches the valve chamber 40A; a flow path 35b, which is connected to the flow path 35a at a position upstream of the valve chamber 40A and is connected to the return piping 108; and a flow path 35c, which reaches the ejection port 31 from the valve chamber 40A.

[0076] Cylinder 39 and valve chamber 40A are aligned in the axial direction X1. Cylinder 39 and valve chamber 40A are separated by partition wall 41. Flow paths 35a and 35c correspond to portions of supply piping 106, which guides the treatment liquid supplied from supply tank 10 toward discharge port 31. Flow path 35b corresponds to a portion of return piping 108, which returns the treatment liquid to supply tank 10.

[0077] The pneumatic actuator 38 includes a cylinder 39, a piston 42, a spring 43, and a rod 44. The cylinder 39 is partitioned by the piston 42 into a front chamber on the side of the partition wall 41 and a rear chamber located on the opposite side of the piston 42 in the axial direction X1. Connectors 47 for connecting pipes that transmit air pressure to the front and rear chambers of the cylinder 39 are connected to the main body 36. Air pressure is transmitted to either the front or rear chamber of the cylinder 39 via the pipes and the joint 47, causing the piston 42 to advance and retract within the cylinder 39 along the axial direction X1.

[0078] The spring 43 is installed between the piston 42 and the body 36 on the rear chamber side of the cylinder 39 , and presses the piston 42 toward the partition wall 41 .

[0079] The base of the rod 44 is connected to the piston 42, and the front end thereof extends through the partition wall 41 and projects into the valve chamber 40A. The valve body 37 is connected to the front end of the rod 44 that projects into the valve chamber 40A. The valve body 37 is formed into a disc shape, with the radial direction perpendicular to the axial direction X1, and is connected to the front end of the rod 44. When the piston 42 advances and retreats along the axial direction X1 within the cylinder 39, the valve body 37 advances and retreats along the axial direction X1 within the valve chamber 40A via the rod 44.

[0080] The valve chamber 40A includes an annular valve seat surface 46 that faces the partition wall 41 and is perpendicular to the axial direction X1. The flow path 35a opens concentrically at the center of the valve seat surface 46. The flow path 35c opens laterally of the valve chamber 40A in the direction of advance and retreat of the valve body 37 (axial direction X1).

[0081] The main body 36 includes a cylindrical portion 49 having a discharge port 31 formed at its front end and protruding downward from the lower surface of the nozzle head 26. A mixing pipe 200 is inserted from the side of the cylindrical portion 49 and connected to the flow path 35c at a position downstream of the valve chamber 40A.

[0082] When air pressure is not applied to any of the front and rear chambers of the cylinder 39 and the pneumatic actuator 38 is not actuated, the piston 42 is held in the cylinder 39 by the spring 43 to the forward position. Figure 4 As shown in the middle example, the valve body 37 is pressed toward a position close to the partition wall 41 , whereby the valve body 37 contacts the valve seat surface 46 in the valve chamber 40A, thereby closing the opening of the flow path 35 a .

[0083] Therefore, the passage 35a and the passage 35c are closed, and the processing liquid supplied from the supply tank 10 through the supply pipe 106 and the passage 35a returns to the supply tank 10 through the passage 35b and the return pipe 108 (circulation state).

[0084] When air pressure is transmitted to the front chamber of cylinder 39 in this circulation state, piston 42 retreats toward the rear chamber of cylinder 39 against the pressing force of spring 43. Then, valve body 37 separates from valve seat surface 46 within valve chamber 40A, and the opening of flow path 35a opens in valve chamber 40A. Consequently, flow paths 35a and 35c are connected via valve chamber 40A, and the treatment liquid supplied from supply tank 10 through supply pipe 106 and flow path 35a passes through flow path 35c and is discharged from discharge port 31 (discharge state).

[0085] When the air pressure is discontinued from the front chamber of cylinder 39 during this ejection phase and instead transmitted to the rear chamber of cylinder 39, piston 42, under the pressure of spring 43, advances toward the front chamber of cylinder 39, i.e., toward partition wall 41. Within valve chamber 40A, valve element 37 contacts valve seat surface 46, closing the opening of flow path 35a. Consequently, the flow paths 35a and 35c are closed, and the treatment liquid supplied from supply tank 10 via supply pipe 106 and flow path 35a returns to the circulation state of supply tank 10 via flow path 35b and return pipe 108.

[0086] When valve 200A is opened in the above-described ejection state and water is mixed into the treatment liquid from mixing pipe 200, the temperature of the treatment liquid containing electrolytic sulfuric acid rises due to the heat of reaction. Specifically, the temperature of the treatment liquid rises to a temperature suitable for substrate treatment (treatment temperature).

[0087] <About Operation of Substrate Processing Apparatus>

[0088] Next, the operation of the substrate processing apparatus will be described. The substrate processing method of the substrate processing apparatus according to this embodiment includes the following steps: spraying a processing liquid onto a substrate W being transported to the processing unit 600 to perform substrate processing; cleaning the substrate W after the processing; rotating the cleaned substrate W to dry it; and unloading the dried substrate W from the processing unit 600.

[0089] Below, refer to Figure 5 and Figure 6 , the substrate processing included in the operation of the above-mentioned substrate processing device is described. Here, Figure 5 106B is a diagram showing an example of the configuration of a substrate processing apparatus in a circulation state of the ejection nozzle 106B. Figure 6 106B is a diagram showing an example of the configuration of a substrate processing apparatus in a discharge state of the discharge nozzle 106B. Figure 5 and Figure 6 The following operations are performed by controlling the operations of the various components (pumps, heaters, valves, rotary motors, etc.) in the substrate processing apparatus 1 using the control unit 90 .

[0090] First, sulfuric acid (H2SO4) circulates between the generation tank 20A and the electrolytic cell 21A via circulation piping 128 to generate a treatment solution containing electrolytic sulfuric acid. Here, electrolytic sulfuric acid refers to persulfuric acid (peroxydisulfuric acid, H2S2O8) generated by electrolyzing sulfuric acid. Persulfuric acid has a stronger oxidizing power than peroxodisulfuric acid (H2SO5) at the same temperature.

[0091] Sulfuric acid is appropriately supplied from the sulfuric acid supply source 16 to the generation tank 20A under the control of valve 16A by the controller 90. Furthermore, pure water (DIW) and the like are appropriately supplied from the pure water supply source 14 under the control of valve 14A by the controller 90. Furthermore, as described below, treated liquid is supplied from the recovery tank 30 to the generation tank 20A under the control of valve 126A by the controller 90.

[0092] The treated liquid stored in generation tank 20A is cooled to, for example, 60°C or below by heater 142 in circulation piping 128, with valve 128A open. Particles and the like are removed as appropriate by filter 144, and then pumped to electrolytic cell 21A by pump 140. By adjusting the treated liquid temperature to 60°C or below (electrolysis temperature), the production rate of electrolytic sulfuric acid during sulfuric acid electrolysis is increased. Furthermore, by adjusting the treated liquid temperature to 60°C or below, the self-decomposition of electrolytic sulfuric acid into carboxylic acid (H2SO5) and OH radicals is suppressed.

[0093] Then, the temperature-adjusted sulfuric acid is electrolyzed in the electrolytic tank 21A to generate a treatment solution containing electrolytic sulfuric acid and sulfuric acid. Here, when the sulfuric acid is electrolyzed, the water molecules in the treatment solution are also electrolyzed, so the concentration of the treatment solution increases with the electrolysis. The concentration of the treatment solution containing electrolytic sulfuric acid is measured using a concentration meter 138, and the control unit 90 controls the flow rate of the treatment solution delivered to the electrolytic tank 21A based on the measured concentration (that is, by opening and closing the control valve 128A, the flow rate of the treatment solution is increased when the measured concentration is low, and the flow rate of the treatment solution is reduced when the measured concentration is high). Furthermore, if the concentration of the electrolytic sulfuric acid is reduced, the efficiency of generating persulfuric acid increases.

[0094] The generation tank 20A and the generation tank 20B are redundantly configured. Therefore, similarly to the generation tank 20A, sulfuric acid (H2SO4) circulates between the generation tank 20B and the electrolytic cell 21B via the circulation pipe 130 to generate a treatment solution containing electrolytic sulfuric acid.

[0095] Sulfuric acid is appropriately supplied from the sulfuric acid supply source 16 to the generation tank 20B under the control of valve 16B by the control unit 90. Furthermore, pure water (DIW) and the like are appropriately supplied from the pure water supply source 14 under the control of valve 14B by the control unit 90. Furthermore, as described below, treated liquid is supplied from the recovery tank 30 to the generation tank 20B under the control of valve 126B by the control unit 90.

[0096] When valve 130A is open, the temperature of the treated liquid stored in the generation tank 20B is adjusted to the electrolysis temperature (for example, below 60°C) using the heater 150 in the circulation piping 130, and particles are appropriately removed using the filter 152, and then transported to the electrolytic cell 21B using the pump 148.

[0097] Then, the temperature-controlled sulfuric acid is electrolyzed in electrolytic cell 21B to generate a treatment solution containing electrolytic sulfuric acid and sulfuric acid. The concentration of the treatment solution containing electrolytic sulfuric acid is measured by concentration meter 146. Based on the measured concentration, control unit 90 adjusts the flow rate of the treatment solution supplied to electrolytic cell 21B by opening and closing control valve 130A.

[0098] The generation tank 20A and the generation tank 20B can switchably supply the treatment liquid to the supply tank 10. For example Figure 5 As shown in the example, valve 128A may be opened to circulate the treated liquid in circulation piping 128, and valve 132A may be opened to supply the treated liquid from generation tank 20A to supply tank 10. During this period, valves 130A and 134A may be closed to store the treated liquid from recovery tank 30 in generation tank 20B. Alternatively, if the concentration of the electrolytic sulfuric acid stored in generation tank 20A does not reach the desired concentration, valve 128A may be opened and valve 132A closed to continue circulating the treated liquid in circulation piping 128. The concentration of the treated liquid may be increased by electrolysis of sulfuric acid. Meanwhile, valves 130A and 134A may be opened to supply the treated liquid circulating in circulation piping 130, which has reached the desired concentration, from generation tank 20B to supply tank 10. In other words, even while the treated liquid is being generated in one generation tank (electrolytic cell), the treated liquid can be continuously supplied from the other generation tanks.

[0099] The processing liquid supplied from one (or both) generation tanks is temperature-controlled to, for example, 60° C. or less by the heater 156 in the supply piping 100 , particles are removed as appropriate by the filter 158 , and is then delivered to the supply tank 10 by the pump 154 through the open valve 100A.

[0100] The supply tank 10 stores the treatment liquid supplied from the generation tank via the supply pipe 100. In addition, pure water (DIW) or the like is appropriately supplied from the pure water supply source 12 to the supply tank 10 to adjust the concentration of the treatment liquid.

[0101] The processing liquid transported from the supply tank 10 through the circulation pipe 102 is temperature-controlled by a heater 116 so that the temperature measured by a thermometer 117 in the circulation pipe 102 is, for example, 60°C or lower. Particles are removed as appropriate by a filter 119, and the liquid is then transported back to the supply tank 10 by a pump 114. The control unit 90 monitors the substrate processing being performed in the processing unit 600 by referring to the processing schedule, and adjusts the flow rate of the processing liquid circulating in the circulation pipe 102 by opening and closing a valve 102A, etc., so that the flow rate of the processing liquid measured by a flow meter 112 is sufficient for the substrate processing.

[0102] The measuring pipe 104 branching from the circulation pipe 102 is provided with a valve 104A for adjusting the flow rate under the control of the control unit 90, and a concentration meter 120. The control unit 90 refers to the concentration of the treatment liquid measured by the concentration meter 120 and controls the opening of the valve 12A to supply pure water from the pure water supply source 12 to the supply tank 10, or to increase the concentration of the treatment liquid by electrolyzing the treatment liquid in the electrolytic cell 118.

[0103] On the downstream side of the circulation pipe 102 , a supply pipe 106 branching to each processing unit 600 is provided. By opening the corresponding valve 106A under the control of the controller 90 , the processing liquid can be appropriately supplied to the processing unit 600 .

[0104] In the circulation state of the ejection nozzle 106B ( Figure 4 In a state where the valve body 37 of the valve body 37 contacts the valve seat surface 46, valves 106A and 108A are opened, and the process liquid supplied from the circulation pipe 102 to the supply pipe 106 and then to the return pipe 108 merges in the circulation pipe 110 and then returns to the supply tank 10. In this way, the process liquid flows into the discharge nozzle 106B of the supply pipe 106 and circulates. This can suppress temperature changes of the process liquid caused by the temperature difference between the pipe and the process liquid when the process liquid is discharged to process the substrate. Furthermore, it is ideal to suppress the process liquid supplied through the return pipe 108 in the circulating state to the minimum flow rate required to maintain the temperature of the pipe.

[0105] In the ejection state of the ejection nozzle 106B ( Figure 4 With the valve body 37 separated from the valve seat surface 46, the valve 106A is opened and the valve 108A is closed, and the processing liquid is ejected from the ejection port 31 of the ejection nozzle 106B toward the upper surface of the substrate W. Then, the substrate is processed.

[0106] Here, water is added to the treatment liquid in the flow path 35c from the mixing pipe 200 with the valve 200A opened just before the treatment liquid is ejected from the ejection port 31. When pure water or other water is added to the treatment liquid containing electrolytic sulfuric acid, the temperature of the treatment liquid rises due to the heat of reaction, for example, to approximately 90°C.

[0107] By increasing the temperature of electrolytic sulfuric acid using the supplied water, the oxidizing power of the electrolytic sulfuric acid is increased, and even without using a heater or the like to increase the temperature, substrate processing (e.g., resist stripping) can be efficiently performed using the processing liquid. Furthermore, when ozone water is mixed into the electrolytic sulfuric acid as the supplied water, the oxidizing power of the ozone water itself may be increased, resulting in a processing liquid with even stronger oxidizing power.

[0108] Furthermore, since both persulfuric acid and peroxodic acid are contained in electrolytic sulfuric acid, the treatment liquid can exhibit a higher oxidizing power than when substrates are treated using peroxodic acid alone at the same temperature.

[0109] The treatment liquid ejected onto the substrate W and used for substrate treatment flows into the drain pipe 122 through the valve 122A in the open state as a post-treatment liquid. The post-treatment liquid contains sulfate ions (SO4 2－ Then, the treated liquid merges in the recovery pipe 124 and is recovered in the recovery tank 30.

[0110] Electrolytic sulfuric acid can be recovered and electrolyzed again for use in substrate processing. Therefore, by using a processing liquid containing electrolytic sulfuric acid for substrate processing, it is possible to reduce the amount of liquid discharged during substrate processing.

[0111] The treated liquid stored in the recovery tank 30 is selectively sent to the generation tank 20A or to the generation tank 20B by opening the valve 126A or the valve 126B via the recovery pipe 126 by the pump 136 (ie, sent to one or both of them).

[0112] <Effects Produced by the Embodiments Described Above>

[0113] Next, examples of the effects produced by the above-described embodiments are described. Furthermore, in the following description, the effects are described based on the specific configurations exemplified in the above-described embodiments. However, within the scope of producing the same effects, these effects can be replaced with other specific configurations exemplified in the present specification. That is, for convenience, only one of the corresponding specific configurations may be described as a representative, but the specific configuration described as a representative may also be replaced with another corresponding specific configuration.

[0114] According to the embodiment described above, the substrate processing apparatus includes a substrate processing section, a supply box 10, a temperature rising section, a generating section, and a recovery section. Here, the substrate processing section corresponds to, for example, the processing unit 600 including the ejection nozzle 106B. In addition, the temperature rising section corresponds to, for example, the mixing pipe 200 for mixing water. In addition, the generating section corresponds to, for example, the generating box 20A (or generating box 20B) connected to the electrolytic tank. In addition, the recovery section corresponds to, for example, the recovery pipe 124 connected to the recovery tank 30. The substrate processing section uses a processing liquid containing electrolytic sulfuric acid to process the substrate W. The supply box 10 stores the processing liquid supplied to the substrate processing section. The mixing pipe 200 mixes the processing liquid supplied from the supply box 10 with water in the substrate processing section. Thus, the mixing pipe 200 heats up the processing liquid. The generating section generates the processing liquid by electrolysis in the electrolytic tank. Then, the generating section supplies the generated processing liquid from the generating box to the supply box 10. The recovery pipe 124 recovers the processing liquid used in the substrate processing unit, that is, the processed liquid, and supplies the processed liquid to the generating unit.

[0115] According to this configuration, by increasing the temperature of the electrolytic sulfuric acid contained in the processing liquid immediately before being used for substrate processing in the processing unit 600 , substrate processing can be performed while suppressing a decrease in the oxidizing power of the electrolytic sulfuric acid.

[0116] Furthermore, even when other structures shown as examples in the specification of this case are appropriately added to the above-mentioned structures, that is, when other structures in the specification of this case that are not mentioned as the above-mentioned structures are appropriately added, the same effect can be produced.

[0117] In addition, according to the embodiment described above, the substrate processing apparatus includes a first circulation path for returning the processing liquid supplied from the supply tank 10 to the supply tank 10. Here, the first circulation path corresponds to, for example, the circulation piping 102. Moreover, the substrate processing portion includes a spray nozzle 106B branching from the circulation piping 102 for spraying the supplied processing liquid toward the substrate W. The spray nozzle 106B includes a spray path for spraying the supplied processing liquid toward the substrate W, and a second circulation path branching from the spray path for returning the processing liquid to the supply tank 10. Here, the spray path corresponds to, for example, the flow path 35a and the flow path 35c of the spray nozzle 106B, which correspond to a part of the supply piping 106. In addition, the second circulation path corresponds to, for example, the flow path 35b of the spray nozzle 106B, which corresponds to a part of the return piping 108. Moreover, the mixing piping 200 is located at a branch point (for example, Figure 4 Water is added to the process liquid mixture further downstream of the valve chamber 40A in the discharge nozzle 106B. This configuration increases the temperature of the electrolytic sulfuric acid further downstream of the valve chamber 40A in the discharge nozzle 106B, thereby extending the time the electrolytic sulfuric acid is maintained at a temperature below 60°C. This allows substrate processing to be performed while suppressing a decrease in the oxidizing power of the electrolytic sulfuric acid.

[0118] Furthermore, according to the embodiment described above, a second temperature adjustment unit is provided in the circulation piping 102 for adjusting the temperature of the treatment liquid to the electrolysis temperature (e.g., 60°C or less), which is the temperature required to generate the treatment liquid through electrolysis. The second temperature adjustment unit corresponds to, for example, the heater 116. With this configuration, by adjusting the temperature of the treatment liquid to the electrolysis temperature (60°C or less) in the supply tank 10, the self-decomposition of electrolytic sulfuric acid can be suppressed.

[0119] Furthermore, according to the embodiment described above, the generation unit includes a first electrolysis unit and a second electrolysis unit for generating a treatment liquid through electrolysis. Here, the first electrolysis unit corresponds to, for example, the electrolytic cell 21A. Furthermore, the second electrolysis unit corresponds to, for example, the electrolytic cell 21B. Furthermore, while the electrolytic cell 21A is supplying the treatment liquid to the supply tank 10, the electrolytic cell 21B electrolyzes the treated liquid recovered via the recovery pipe 124 to generate the treatment liquid. With this configuration, even while the treatment liquid is being generated in one generation tank (electrolytic cell), the treatment liquid can be continuously supplied from the other generation tank.

[0120] Furthermore, according to the embodiment described above, the generation unit includes a first temperature adjustment unit for adjusting the temperature of the treated liquid and the temperature of the generated treated liquid to the electrolysis temperature (e.g., 60°C or less) required to generate the treated liquid through electrolysis. Here, the first temperature adjustment unit corresponds to, for example, heater 142 or heater 150. With this configuration, by adjusting the treated liquid temperature to the electrolysis temperature (60°C or less) in the generation tank and electrolytic cell, the generation rate of electrolytic sulfuric acid can be increased when electrolyzing sulfuric acid. Furthermore, the self-decomposition of the electrolytic sulfuric acid can be suppressed.

[0121] Furthermore, according to the embodiment described above, the generation unit includes a first replenishing unit for replenishing water to the electrolyzed treatment liquid, and a second replenishing unit for replenishing sulfuric acid to the electrolyzed treatment liquid. Here, the first replenishing unit corresponds to, for example, the pure water supply source 14. Furthermore, the second replenishing unit corresponds to, for example, the sulfuric acid supply source 16. With this configuration, when the concentration of the electrolyzed sulfuric acid is higher than the desired concentration, the concentration can be lowered by adding pure water, etc., and when the concentration of the electrolyzed sulfuric acid is lower than the desired concentration, the concentration can be increased by adding sulfuric acid.

[0122] According to the embodiment described above, in the substrate processing method, a processing liquid is stored in the supply tank 10 for supply to the substrate processing section. In the substrate processing section, the processing liquid supplied from the supply tank 10 is mixed with water to increase its temperature. Substrates W are then processed using the processing liquid. Furthermore, the processing liquid used in the substrate processing section, i.e., the post-processing liquid, is recovered and supplied to the generation section. Furthermore, in the generation section, the processing liquid containing the post-processing liquid is generated from the liquid by electrolysis, and the generated processing liquid is supplied to the supply tank 10.

[0123] According to this configuration, by increasing the temperature of the electrolytic sulfuric acid contained in the processing liquid immediately before being used for substrate processing in the processing unit 600 , substrate processing can be performed while suppressing a decrease in the oxidizing power of the electrolytic sulfuric acid.

[0124] Furthermore, unless otherwise specified, the order in which the processes are performed may be changed.

[0125] Furthermore, even when other configurations shown as examples in the present specification are appropriately added to the above configurations, that is, when other configurations in the present specification that are not mentioned as the above configurations are appropriately added, the same effects can be produced.

[0126] <Regarding Modifications of the Embodiments Described Above>

[0127] In the above-described embodiments, the materials, dimensions, shapes, relative arrangement relationships, and implementation conditions of each component are sometimes described, but these are merely examples in all aspects and are not restrictive.

[0128] Therefore, numerous variations and equivalents not shown in the examples are possible within the technical scope disclosed in this specification. For example, when at least one component is modified, additions or omissions are included.

[0129] In at least one embodiment described above, when a material name or the like is described without being particularly specified, the material may include other additives, such as alloys, unless there is any inconsistency.

[0130] [Description of Reference Numerals]

[0131] 1: Substrate processing equipment

[0132] 10: Supply Box

[0133] 106B: Spray nozzle

Claims

1. A substrate processing device, wherein: have: a substrate processing unit for processing a substrate using a processing solution containing electrolytic sulfuric acid; a supply tank for storing the processing liquid supplied to the substrate processing part; a temperature increasing unit configured to increase the temperature of the processing liquid in the substrate processing unit by mixing the processing liquid supplied from the supply tank with water; a generating unit configured to generate the treatment liquid by electrolysis and supply the generated treatment liquid to the supply tank; and The recovery unit is used to recover the processing liquid used in the substrate processing unit, that is, the post-processing liquid, and supply the processed liquid to the generating unit.

2. The substrate processing apparatus according to claim 1, wherein: The device further comprises a first circulation path for returning the treatment liquid supplied from the supply tank to the supply tank. The substrate processing section includes a discharge nozzle branched from the first circulation path for discharging the supplied processing liquid toward the substrate. The discharge nozzle includes a discharge path for discharging the supplied processing liquid toward the substrate, and a second circulation path branching from the discharge path to return the processing liquid to the supply tank. The temperature rising unit mixes the application water with the treatment liquid at a position downstream of a branch point with the second circulation path in the discharge path.

3. The substrate processing apparatus according to claim 2, wherein: The invention further includes a second temperature adjustment unit for adjusting the temperature of the treatment liquid in the first circulation path to an electrolysis temperature, which is a temperature for generating the treatment liquid by electrolysis.

4. The substrate processing apparatus according to any one of claims 1 to 3, wherein: The generating unit includes a first electrolysis unit and a second electrolysis unit for generating the treatment solution by electrolysis. While the first electrolysis unit supplies the treatment liquid to the supply tank, the second electrolysis unit electrolyzes the treated liquid recovered by the recovery unit to generate the treatment liquid.

5. The substrate processing apparatus according to any one of claims 1 to 4, wherein: The generating unit includes a first temperature adjusting unit for adjusting the temperature of the treated liquid and the temperature of the generated treating liquid to an electrolysis temperature, which is a temperature for generating the treating liquid by electrolysis.

6. The substrate processing apparatus according to any one of claims 1 to 5, wherein: The generating unit includes: a first replenishing portion for replenishing the electrolyzed treatment solution with the applied water; and The second replenishing part is used to replenish sulfuric acid to the electrolyzed treatment solution.

7. A substrate processing method for processing a substrate using a processing solution containing electrolytic sulfuric acid, wherein: The following steps are required: The processing liquid supplied to the substrate processing part is stored in the supply tank; In the substrate processing unit, the processing liquid supplied from the supply tank is mixed with water to increase the temperature of the processing liquid. In the substrate processing unit, the substrate is processed using the processing liquid mixed with the applied water; recovering the processing liquid that has been used for processing in the substrate processing unit, that is, the processed liquid, and supplying it to the generating unit; and The processing liquid is generated from the liquid containing the processed liquid by electrolysis in the generating unit, and the generated processing liquid is supplied to the supply tank.

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