Substrate processing device, substrate processing method and substrate processing program

Abstract

To reduce the consumption of chemical liquids.SOLUTION: A substrate processing device generates a third process liquid from a first process liquid and a second process liquid and processes a substrate using the third process liquid. The substrate processing device comprises: a discharge port OH; a first supply path connected to the discharge port OH; a plurality of second supply paths connected to the first supply path at a plurality of mixture positions with different channel lengths to the discharge port OH; a first supply section 23a which supplies the first process liquid to the first supply path; and a second supply section 23b which supplies the second process liquid to the first supply path via the plurality of second supply paths. The liquid in the first supply path and the second process liquid are successively mixed from the mixture position most separated from the discharge port OH to the mixture position most proximate to the discharge port OH in the plurality of mixture positions of the first supply path.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a substrate processing apparatus, a substrate processing method executed by the substrate processing apparatus, and a substrate processing program for causing a computer to execute the substrate processing method. [Background technology]

[0002] In a lithography process for manufacturing semiconductor devices and the like, a resist film is formed on the entire surface of a substrate to be processed. SPM processing is a method for removing the resist film. In SPM processing, a sulfuric acid hydrogen peroxide mixture (SPM) liquid is generated from sulfuric acid (H2SO4) and hydrogen peroxide (H2O2), and the SPM liquid is supplied to a substrate to remove the resist film formed on the substrate. The chemical reaction in which the SPM liquid is generated from sulfuric acid and hydrogen peroxide is an exothermic reaction. In general, in order to fully utilize the resist stripping ability of the SPM liquid, the temperature of the SPM supplied to the substrate needs to be 160°C or higher. A technology for adjusting the temperature of the SPM liquid is described in Patent Document 1.

[0003] Patent document 1 describes a substrate processing apparatus for supplying sulfuric acid / hydrogen peroxide solution to a surface of a substrate to peel off and remove resist from the surface of the substrate, the substrate processing apparatus including: a mixing section for mixing sulfuric acid and hydrogen peroxide solution to generate sulfuric acid / hydrogen peroxide solution; a discharge section for discharging the sulfuric acid / hydrogen peroxide solution generated in the mixing section and supplying the sulfuric acid / hydrogen peroxide solution to the surface of the substrate; a path length changing means for changing the path length of the supply path of the sulfuric acid / hydrogen peroxide solution from the mixing section to the discharge section; a liquid temperature detection means for detecting the liquid temperature of the sulfuric acid / hydrogen peroxide solution supplied from the mixing section to the discharge section; and a control means for controlling the path length changing means based on the liquid temperature detected by the liquid temperature detection means so that sulfuric acid / hydrogen peroxide solution having a liquid temperature equal to or higher than a predetermined reference temperature is supplied to the discharge section. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2008-4819 A Summary of the Invention [Problem to be solved by the invention]

[0005] When SPM liquid is produced from sulfuric acid and hydrogen peroxide solution, the progress of a first chemical reaction is promoted at a first temperature or higher. Meanwhile, the progress of a second chemical reaction in which hydrogen peroxide solution decomposes into water and oxygen is promoted at a temperature equal to or higher than a second temperature lower than the first temperature. As a result, the first chemical reaction and the second chemical reaction proceed simultaneously for each mixing of sulfuric acid and hydrogen peroxide solution. Therefore, it is necessary to use an amount of hydrogen peroxide solution sufficient to carry out the first chemical reaction with sulfuric acid while carrying out the second chemical reaction. Meanwhile, from the viewpoint of environmental conservation, it is desirable to reduce the consumption of chemical solutions used to produce SPM liquid.

[0006] An object of the present invention is to provide a substrate processing apparatus capable of reducing the consumption of chemical solutions. [Means for solving the problem]

[0007] A substrate processing apparatus according to one aspect of the present invention is a substrate processing apparatus that generates a third processing liquid from a first processing liquid and a second processing liquid and processes a substrate using the third processing liquid, and includes an outlet, a first supply path connected to the outlet, a plurality of second supply paths respectively connected to the first supply path at a plurality of mixing positions having different flow path lengths to the outlet, a first supply unit that supplies the first processing liquid to the first supply path, and a second supply unit that supplies the second processing liquid to the first supply path via the plurality of second supply paths, and at the plurality of mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed sequentially from the mixing position farthest from the outlet to the mixing position closest to the outlet.

[0008] A substrate processing method according to another aspect of the present invention is a substrate processing method that generates a third processing liquid from a first processing liquid and a second processing liquid, and processes a substrate using the third processing liquid, the substrate processing apparatus having an outlet, a first supply path connected to the outlet, and a plurality of second supply paths each connected to the first supply path at a plurality of mixing positions having different flow path lengths to the outlet, the method including the steps of supplying the first processing liquid to the first supply path, and supplying the second processing liquid to the first supply path via the plurality of second supply paths, and at the plurality of mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed sequentially from the mixing position farthest from the outlet to the mixing position closest to the outlet.

[0009] A substrate processing program according to another aspect of the present invention is a substrate processing program executed by a computer that controls a substrate processing apparatus that generates a third processing liquid from a first processing liquid and a second processing liquid and processes a substrate using the third processing liquid, the substrate processing apparatus having an outlet for discharging the third processing liquid, a first supply path connected to the outlet, and a plurality of second supply paths each connected to the first supply path at a plurality of mixing positions having different flow path lengths to the outlet, and the substrate processing apparatus causes the computer to execute a step of supplying the first processing liquid to the first supply path and a step of supplying the second processing liquid to the first supply path via the plurality of second supply paths, and at the plurality of mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed sequentially from the mixing position farthest from the outlet to the mixing position closest to the outlet. Effect of the Invention

[0010] According to the present invention, it is possible to reduce the consumption of chemical solutions used. [Brief description of the drawings]

[0011] [Figure 1] 1 is a side view showing an example of a configuration of a substrate processing apparatus; [Diagram 2]FIG. 2 is a plan view of the substrate processing apparatus. [Diagram 3] 5A and 5B are schematic diagrams for explaining the configuration of a nozzle arm. [Figure 4] FIG. 2 is an enlarged schematic diagram of a discharge nozzle. [Diagram 5] 5 is a cross-sectional view taken along line AA in FIG. 4. [Figure 6] FIG. 2 illustrates an example of the configuration of a control unit. [Figure 7] 2 is a block diagram showing an example of a functional configuration of a control unit. FIG. [Figure 8] 1 is a flowchart illustrating an example of a flow of substrate processing. [Figure 9] FIG. 4 is a schematic diagram for explaining a nozzle arm of a substrate processing unit used in a first comparative example. [Figure 10] FIG. 1 is a first diagram showing a first experimental result. [Figure 11] FIG. 2 is a second diagram showing the results of the first experiment. [Figure 12] 13 is a schematic diagram for explaining a nozzle arm of a substrate processing unit used in a second comparative example. FIG. [Figure 13] FIG. 13 is a diagram showing the results of a second experiment. [Figure 14] FIG. 11 is a first schematic view for explaining a nozzle arm of a substrate processing section according to a second modified example. [Figure 15] FIG. 13 is a second schematic view illustrating a nozzle arm of a substrate processing section according to a third modified example. [Figure 16] FIG. 11 is a block diagram showing an example of a functional configuration of a control unit in a second embodiment. [Figure 17] FIG. 13 is a diagram illustrating an example of the format of an allocation table. [Figure 18] 10 is a flowchart illustrating an example of a flow of substrate processing in the second embodiment. [Figure 19] FIG. 13 is a block diagram showing an example of a functional configuration of a control unit in a third embodiment. [Figure 20] FIG. 11 is a diagram illustrating an example of a format of history information. [Figure 21]13 is a flowchart illustrating an example of a flow of substrate processing in the third embodiment. [Figure 22] FIG. 13 is a block diagram showing an example of a functional configuration of a control unit in a fourth embodiment. [Diagram 23] FIG. 23 is a diagram showing an example of a format of history information in the fourth embodiment. [Figure 24] 13 is a flowchart showing an example of the flow of an allocation table generation process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A coating method and coating apparatus according to an embodiment of the present invention will be described below with reference to the drawings. In the following description, the term "substrate" refers to a substrate for a flat panel display (FPD) used in a liquid crystal display device or an organic electroluminescence (EL) display device, a semiconductor substrate, an optical disk substrate, a magnetic disk substrate, a magneto-optical disk substrate, a photomask substrate, a ceramic substrate, a solar cell substrate, or the like.

[0013] <First embodiment> (1) Overall configuration of substrate processing equipment FIG. 1 is a side view showing an example of the configuration of a substrate processing apparatus. FIG. 2 is a plan view of the substrate processing apparatus. In FIG. 1 and FIG. 2, mutually orthogonal X, Y and Z directions are defined to clarify the positional relationship. The X and Y directions are mutually orthogonal in a horizontal plane, and the Z direction corresponds to the up-down direction (vertical direction). As shown in FIG. 1 and FIG. 2, the substrate processing apparatus 100 includes a spin chuck (rotary holding unit) 10, a nozzle unit 20, a splash guard 40 and a control unit 50. The control unit 50 controls the operations of the spin chuck 10, the nozzle unit 20 and the splash guard 40.

[0014] The spin chuck 10, the nozzle unit 20 and the splash guard 40 are housed in a processing chamber. The processing chamber has four side sections, a ceiling section and a bottom section. A transfer opening (not shown) is formed in one side section of the processing chamber for transferring a substrate between the inside of the processing chamber and the outside of the processing chamber. In addition, an FFU (filter fan unit) is provided in the ceiling section of the processing chamber. The FFU generates a downward air current of clean air in the inside of the processing chamber.

[0015] The spin chuck 10 includes a spin base 11, a plurality of chuck pins 12, and a spin motor 13. The spin base 11 is attached to the upper end of the rotation shaft of the spin motor 13. The rotation force of the spin motor 13 is transmitted to the spin base 11, and the spin base 11 holding the substrate W rotates. In this embodiment, the rotation shaft of the spin motor 13 is set in the vertical direction. The spin base 11 has a holding surface perpendicular to the rotation shaft of the spin motor 13. A plurality of chuck pins 12 are arranged on the holding surface of the spin base 11. The plurality of chuck pins 12 are arranged at equal intervals on a concentric circle centered on the rotation shaft of the spin base 11. At least one of the plurality of chuck pins 12 is fixed to the spin base 11 so as to be rotatable about a rotation axis perpendicular to the holding surface, and can be changed between a state in which the outer peripheral edge of the substrate W is held and a state in which the outer peripheral edge of the substrate W is not held. During substrate processing, the substrate W is held on the spin base 11 in a horizontal position with the plurality of chuck pins 12 holding the substrate W.

[0016] The splash guard 40 surrounds the spin chuck 10 in a plan view. In a side view, the splash guard 40 can be moved in the vertical direction by a moving mechanism (not shown). During substrate processing, the splash guard 40 rises to a position where its upper end is above the substrate W held by the spin chuck 10. In this case, the splash guard 40 receives droplets scattered from the substrate W held and rotated by the spin base 11. The droplets received by the splash guard 40 are collected by a recovery unit (not shown). When the substrate W is loaded before the substrate processing operation and when the substrate W is unloaded after the substrate processing operation, the splash guard 40 descends to a position where its upper end is below the spin base 11 of the spin chuck 10. This allows the substrate W on the spin chuck 10 to be loaded and unloaded.

[0017] The nozzle unit 20 includes a nozzle arm 21, a holding arm 24, a linear guide LG, and a processing liquid supply unit 23. The nozzle arm 21 includes a discharge arm 21a and a discharge nozzle 21b. The discharge arm 21a has a rectangular parallelepiped shape that is long in the X direction. The discharge nozzle 21b is provided at one end of the lower surface of the discharge arm 21a in the longitudinal direction, and the other end is fixed to the holding arm 24. The discharge nozzle 21b has a discharge port OH. The discharge port OH is an opening that opens downward. The discharge arm 21a houses multiple tubes inside. As shown in FIG. 3, the multiple tubes include a first supply pipe 25 and a second supply pipe 26. The processing liquid supply unit 23 includes a first supply unit 23a and a second supply unit 23b. One end of the first supply pipe 25 and the second supply pipe 26 are connected to the first supply unit 23a and the second supply unit 23b, respectively. The other end of the first supply pipe 25 is connected to the discharge nozzle 21b, and the other end of the second supply pipe 26 is connected to the first supply pipe 25, respectively.

[0018] The linear guide LG includes a carriage CA, a rail RL, and a pulse motor. The rail RL of the linear guide LG is disposed outside the splash guard 40 in a plan view, and has a rod-like shape extending in the Y direction. The carriage CA is slidably connected to the rail RL. The pulse motor moves the carriage CA along the rail RL.

[0019] The holding arm 24 is a rod-shaped member extending in the vertical direction. The upper end of the holding arm 24 is fixed to the discharge arm 21a. The lower end of the holding arm 24 is fixed to the carriage CA. The length of the holding arm 24 in the longitudinal direction is set to a size that positions the discharge port OH of the discharge nozzle 21b a predetermined distance above the substrate W held by the spin chuck 10. As a result, the discharge port OH of the discharge nozzle 21b is held by the discharge arm 21a and the holding arm 24 at a position a predetermined distance above the substrate W held by the spin chuck 10.

[0020] When the carriage CA moves along the rail RL, the discharge arm 21a held by the holding arm 24 moves parallel to the Y direction. The longitudinal length of the discharge arm 21a is set to a size that allows the discharge port OH of the discharge nozzle 21b to pass through the center WO of the substrate W and along a moving line YL that is parallel to the Y direction. As a result, when the carriage CA moves along the linear guide LG, the discharge port OH of the discharge nozzle 21b moves along the moving line YL a predetermined distance above the substrate W held by the spin chuck 10.

[0021] When the discharge arm 21a moves, the processing liquid supplied from the processing liquid supply unit 23 is discharged from the discharge port OH of the discharge nozzle 21b. As a result, the processing liquid is supplied from the discharge port OH of the discharge nozzle 21b of the nozzle arm 21 to the upper surface of the substrate W held on the spin base 11 by the spin chuck 10. Hereinafter, this operation is referred to as the scanning operation of the discharge nozzle 21b. In this embodiment, the processing liquid supplied to the upper surface of the substrate W is SPM (Sulfuric Acid Hydrogen Peroxide Mixture) liquid. The SPM liquid is generated inside the nozzle arm 21.

[0022] (2) Configuration of nozzle arm 21 3 is a schematic diagram for explaining the configuration of the nozzle arm 21. The nozzle arm 21 houses a first supply pipe 25 and a second supply pipe 26. The first supply pipe 25 has two ends, one end of which is connected to a first supply unit 23a that supplies the first processing liquid, and the other end of which is connected to the discharge nozzle 21b. A flow path extending from the end of the first supply pipe 25 connected to the first supply unit 23a to the discharge port OH of the discharge nozzle 21b is an example of a first supply path.

[0023] The second supply pipe 26 includes a main pipe 26A and a plurality of branch pipes 26a-26d. The main pipe 26A has two ends, one end of which is connected to the second supply unit 23b and the other end of which is connected to the branch pipe 26d. Each of the plurality of branch pipes 26a-26d has one end connected to the main pipe 26A at a plurality of different branch points aA-dD of the main pipe 26A and the other end connected to the first supply pipe 25 at a plurality of first mixing positions AA-fourth mixing positions DD of the first supply pipe 25.

[0024] The branch pipe 26a has one end connected to the main pipe 26A at a branch point aA, and the other end connected to the first supply pipe 25 at a first mixing position AA. A first opening / closing valve Va and a first adjustment valve NVa are interposed in the branch pipe 26a. The first opening / closing valve Va is, for example, a ball valve. The first opening / closing valve Va can be switched between an open state in which the branch pipe 26a is opened and a closed state in which the branch pipe 26a is closed. When the first opening / closing valve Va is in an open state, the second treatment liquid flows in the branch pipe 26a, and the second treatment liquid is supplied to the first supply pipe 25 at the first mixing position AA. When the first opening / closing valve Va is in a closed state, the second treatment liquid does not flow in the branch pipe 26a. The first adjustment valve NVa can adjust the flow rate of the second treatment liquid flowing in the branch pipe 26a. The first adjustment valve NVa is, for example, a needle valve.

[0025] The branch pipe 26b has one end connected to the main pipe 26A at a branch point bB, and the other end connected to the first supply pipe 25 at a second mixing position BB. A second opening / closing valve Vb and a second adjustment valve NVb are interposed in the branch pipe 26b. The second opening / closing valve Vb is, for example, a ball valve. The second opening / closing valve Vb can be switched between an open state in which the branch pipe 26b is opened and a closed state in which the branch pipe 26b is closed. When the second opening / closing valve Vb is in an open state, the second treatment liquid flows in the branch pipe 26b, and the second treatment liquid is supplied to the first supply pipe 25 at the second mixing position BB. When the second opening / closing valve Vb is in a closed state, the second treatment liquid does not flow in the branch pipe 26b. The second adjustment valve NVb can adjust the flow rate of the second treatment liquid flowing in the branch pipe 26b. The second adjustment valve NVb is, for example, a needle valve.

[0026] The branch pipe 26c has one end connected to the main pipe 26A at a branch point cC, and the other end connected to the first supply pipe 25 at a third mixing position CC. A third opening / closing valve Vc and a third adjustment valve NVc are interposed in the branch pipe 26c. The third opening / closing valve Vc is, for example, a ball valve. The third opening / closing valve Vc can be switched between an open state in which the branch pipe 26c is opened and a closed state in which the branch pipe 26c is closed. When the third opening / closing valve Vc is in an open state, the second treatment liquid flows in the branch pipe 26c, and the second treatment liquid is supplied to the first supply pipe 25 at the third mixing position CC. When the third opening / closing valve Vc is in a closed state, the second treatment liquid does not flow in the branch pipe 26c. The third adjustment valve NVc can adjust the flow rate of the second treatment liquid flowing in the branch pipe 26c. The third adjustment valve NVc is, for example, a needle valve.

[0027] One end of the branch pipe 26d is connected to the main pipe 26A at a branch point dD, and the other end is connected to the discharge nozzle 21b at a fourth mixing position DD. A fourth opening / closing valve Vd and a fourth adjustment valve NVd are interposed in the branch pipe 26d. The fourth opening / closing valve Vd is, for example, a ball valve. The fourth opening / closing valve Vd can be switched between an open state in which the branch pipe 26d is opened and a closed state in which the branch pipe 26b is closed. When the fourth opening / closing valve Vd is in an open state, the second treatment liquid flows in the branch pipe 26d, and the second treatment liquid is supplied to the discharge nozzle 21b at the fourth mixing position DD. When the fourth opening / closing valve Vd is in a closed state, the second treatment liquid does not flow in the branch pipe 26d. The fourth adjustment valve NVd can adjust the flow rate of the second treatment liquid flowing in the branch pipe 26d. The fourth adjustment valve NVd is, for example, a needle valve.

[0028] The branch pipes 26a to 26d are an example of a plurality of second supply paths. The branch pipe 26d is an example of a final supply path. The second supply unit 23b and the first opening / closing valve Va to the fourth opening / closing valve Vd are an example of a second supply unit.

[0029] A main opening / closing valve V and a main adjustment valve NV are interposed in the first supply pipe 25. The main opening / closing valve V and the main adjustment valve NV are disposed between the first supply unit 23a and the first mixing position AA. The main opening / closing valve V can be switched between an open state in which the first supply pipe 25 is opened and a closed state in which the first supply pipe 25 is closed. The main opening / closing valve V is, for example, a ball valve. When the main opening / closing valve V is in an open state, the first processing liquid flows in the first supply pipe 25, and when the main opening / closing valve V is in a closed state, the first processing liquid does not flow in the first supply pipe 25. The main adjustment valve NV can adjust the flow rate of the first processing liquid flowing in the first supply pipe 25. The main adjustment valve NV is, for example, a needle valve. The first supply unit 23a and the main opening / closing valve V are examples of the first supply unit.

[0030] The flow path lengths from the discharge port OH to the first mixing position AA to the fourth mixing position DD are referred to as flow path lengths LA to LD, respectively. The flow path length LA from the discharge port OH to the first mixing position AA is the longest, and the flow path length LD from the discharge port OH to the fourth mixing position DD is the shortest. The flow path length LB from the discharge port OH to the second mixing position BB is shorter than the flow path length LA but longer than the flow path length LD. The flow path length LC from the discharge port OH to the third mixing position CC is shorter than the flow path length LB but longer than the flow path length LD.

[0031] In this embodiment, an agitator 27 is provided between the first mixing position AA and the second mixing position BB of the first supply pipe 25. For example, an in-line mixer may be used as the agitator 27. The agitator 27 is provided inside the first supply pipe 25. For example, the agitator 27 has a spiral shape centered on an axis parallel to the extension direction of the first supply pipe 25. The liquid flowing through the first supply pipe 25 changes its flow direction when it collides with the agitator 27, and is agitated. Note that another mixer having a drive mechanism may be used as the agitator 27.

[0032] The processing liquid supply unit 23 includes a first supply unit 23a and a second supply unit 23b. The first supply unit 23a includes a pump. The first supply unit 23a supplies the first processing liquid to the first supply pipe 25 at a predetermined pressure. The second supply unit 23b includes a pump. The second supply unit 23b supplies the second processing liquid to the second supply pipe 26 at a predetermined pressure.

[0033] Here, the SPM liquid supplied to the upper surface of the substrate W will be described. In this embodiment, the first processing liquid is sulfuric acid (H2SO4), and the second processing liquid is hydrogen peroxide (H2O2). The first supply unit 23a supplies sulfuric acid to the first supply pipe 25, and the second supply unit 23b supplies hydrogen peroxide to the second supply pipe 26. Caro's acid (H2SO5) is generated as the third processing liquid by mixing the sulfuric acid and the hydrogen peroxide in the nozzle arm 21. Therefore, the SPM liquid containing Caro's acid is discharged from the discharge nozzle 21b. Caro's acid is effective for peeling off the resist film. Caro's acid is generated by the following reaction formula (1) of the first chemical reaction. The first chemical reaction is an exothermic reaction. In addition, the first chemical reaction proceeds efficiently at a first temperature or higher. Therefore, Caro's acid can be efficiently generated by setting the temperature of the first processing liquid to the first temperature or higher. The first temperature is about 170°C.

[0034] H2SO4+H2O2→H2SO5+H2O···(1) 2H2O2 → 2H20 + O2 (2) On the other hand, when the hydrogen peroxide solution reaches a second temperature lower than the first temperature, the second chemical reaction shown in the above reaction formula (2) proceeds. The second temperature is about 140°C. The hydrogen peroxide solution is supplied from the branch pipe 26a to the first mixing position AA of the first supply pipe 25. In this case, a part of the hydrogen peroxide solution undergoes a first chemical reaction with sulfuric acid, another part of the hydrogen peroxide solution undergoes a second chemical reaction, and the remaining part of the hydrogen peroxide solution remains without undergoing the first chemical reaction or the second chemical reaction. Therefore, the liquid flowing between the first mixing position AA and the second mixing position BB of the first supply pipe 25 contains sulfuric acid, hydrogen peroxide solution, Caro's acid, and water. While the hydrogen peroxide solution flows between the first mixing position AA and the second mixing position BB of the first supply pipe 25, a part of the hydrogen peroxide solution undergoes a first chemical reaction with sulfuric acid, and all the remaining part of the hydrogen peroxide solution undergoes a second chemical reaction and is decomposed into water and oxygen. In this case, the liquid that reaches the second mixing position BB of the first supply pipe 25 does not contain hydrogen peroxide solution, but contains sulfuric acid, Caro's acid, and water.

[0035] The same applies to the liquid flowing between the second mixing position BB and the third mixing position CC of the first supply pipe 25, and the liquid flowing between the third mixing position CC and the fourth mixing position DD.

[0036] In this embodiment, hydrogen peroxide is supplied to the first supply pipe 25 at each of the first mixing position AA to the fourth mixing position DD. The hydrogen peroxide is supplied to each mixing position before the sulfuric acid flows. Therefore, by supplying sulfuric acid to the first supply pipe 25, the hydrogen peroxide is mixed with the hydrogen peroxide at each mixing position from the first mixing position AA, which is the furthest from the discharge port OH, to the fourth mixing position DD, which is the closest. A first chemical reaction progresses each time hydrogen peroxide is supplied to sulfuric acid. As described above, the first chemical reaction is an exothermic reaction. Therefore, the temperature of the liquid flowing through the first supply pipe 25 increases in the order of the time when the liquid passes through each of the first mixing position AA to the fourth mixing position DD. In other words, the temperature of the liquid passing through the first mixing position AA is the lowest, and the temperature of the liquid passing through the fourth mixing position DD is the highest.

[0037] There is a case where all of the sulfuric acid supplied from first supply unit 23a to first supply pipe 25 undergoes the first chemical reaction with hydrogen peroxide while flowing through first supply pipe 25. In this case, no sulfuric acid is supplied to discharge nozzle 21b, and an SPM liquid containing hydrogen peroxide, Caro's acid, and water is supplied. In addition, if the remaining portion of the hydrogen peroxide that has not undergone the first chemical reaction is decomposed by a second chemical reaction before being discharged from discharge port OH, no hydrogen peroxide is supplied to discharge nozzle 21b, and an SPM liquid containing Caro's acid and water is supplied.

[0038] Here, the details of the discharge nozzle 21b will be described. FIG. 4 is a schematic diagram of an enlarged discharge nozzle 21b. FIG. 5 is a cross-sectional view of the line AA in FIG. 4. The discharge nozzle 21b includes a mixing chamber 251. The mixing chamber 251 is a part of the first supply path. One end of the mixing chamber 251 is connected to the first supply pipe 25, and the other end reaches the discharge port OH of the discharge nozzle 21b. The mixing chamber 251 includes a cylindrical mixing space MSP and a connecting space LSP that connects the mixing space MSP to the discharge port OH from below. The connecting space LSP has a mortar-like truncated cone shape whose cross-sectional area gradually decreases from the mixing space MSP toward the discharge port OH. A branch pipe 26d is connected to the side of the mixing space MSP. A filter FT having a plurality of holes is provided at the connection portion between the branch pipe 26d and the mixing space MSP. The filter FT is, for example, a sintered filter. A predetermined pressure is applied to the hydrogen peroxide solution flowing through the branch pipe 26d. Therefore, the hydrogen peroxide solution is atomized when passing through the filter FT and supplied to the mixing space MSP. As a result, the hydrogen peroxide solution is atomized, and the surface area of ​​the hydrogen peroxide solution increases. As a result, the hydrogen peroxide solution and the sulfuric acid can be mixed efficiently, and the progress of the first chemical reaction is promoted.

[0039] (3) Substrate processing under the control of the control unit 50 Fig. 6 is a diagram showing an example of a configuration of control unit 50 in Fig. 3. Referring to Fig. 6, control unit 50 is configured with a CPU 511, a RAM 512, a ROM 513, a storage device 514, and an input / output I / F 517. CPU 511, RAM 512, ROM 513, storage device 514, and input / output I / F 517 are connected to a bus 518.

[0040] The RAM 512 is used as a working area for the CPU 511. The ROM 513 stores system programs. The storage device 514 includes a storage medium such as a hard disk or a semiconductor memory, and stores programs.

[0041] A CD-ROM 519 on which a program is recorded can be detachably attached to the storage device 514. The CPU 511 loads the program recorded on a hard disk, a semiconductor memory, or the CD-ROM 519 into the RAM 512 and executes it. The input / output I / F 517 is a communication interface, and can connect the CPU 511 to an external device.

[0042] The recording medium for storing the program executed by the CPU 511 is not limited to the CD-ROM 519, but may be an optical disk (MO (Magnetic Optical Disc) The program may be a medium such as a semiconductor memory, such as a digital video card (Digital Versatile Disc (DVD)), an IC card, an optical card, a mask ROM, or an erasable programmable ROM (EPROM). Furthermore, the CPU 511 may download the program from a computer connected to the network and store it in the storage device 514, or the computer connected to the network may write the program to the storage device 514, and the program stored in the storage device 514 may be loaded into the RAM 512 and executed by the CPU 511. The program here includes not only a program that can be directly executed by the CPU 511, but also a source program, a compressed program, an encrypted program, and the like.

[0043] Fig. 7 is a block diagram showing an example of the functional configuration of control unit 50. Control unit 50 includes a first supply control unit 501, a second supply control unit 502, an opening / closing control unit 503, a flow rate acquisition unit 504, and a flow rate control unit 505. In this embodiment, each component of control unit 50 is realized by CPU 511 of Fig. 6 executing a substrate processing program stored in CD-ROM 519.

[0044] The first supply control unit 501 controls the first supply unit 23a. Specifically, the first supply control unit 501 switches a pump (not shown) included in the first supply unit 23a between an off state and an on state. When the pump is switched from an off state to an on state, the sulfuric acid supplied to the first supply pipe 25 is pressurized. The second supply control unit 502 controls the second supply unit 23b. Specifically, the second supply control unit 502 switches a pump (not shown) included in the second supply unit 23b between an off state and an on state. When the pump is switched from an off state to an on state, the hydrogen peroxide solution supplied to the second supply pipe 26 is pressurized.

[0045] The opening / closing control unit 503 controls the main opening / closing valve V, the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd. The opening / closing control unit 503 switches the main opening / closing valve V between an open state and a closed state. When the main opening / closing valve V is switched from a closed state to an open state, sulfuric acid at a predetermined pressure is supplied to the first supply pipe 25. The opening / closing control unit 503 switches the first opening / closing valve Va between an open state and a closed state. When the first opening / closing valve Va is switched from a closed state to an open state, hydrogen peroxide solution is supplied to the first mixing position AA of the first supply pipe 25. The opening / closing control unit 503 switches the second opening / closing valve Vb between an open state and a closed state. When the second opening / closing valve Vb is switched from a closed state to an open state, hydrogen peroxide solution is supplied to the second mixing position BB of the first supply pipe 25. The opening / closing control unit 503 switches the third opening / closing valve Vc between an open state and a closed state. When the third on-off valve Vc is switched from a closed state to an open state, hydrogen peroxide solution is supplied to the third mixing position CC of the first supply pipe 25. The on-off control unit 503 switches the fourth on-off valve Vd between an open state and a closed state. When the fourth on-off valve Vd is switched from a closed state to an open state, hydrogen peroxide solution is supplied to the fourth mixing position DD of the discharge nozzle 21b. After switching the main on-off valve V from a closed state to an open state, the on-off control unit 503 simultaneously switches the first on-off valve Va to the fourth on-off valve Vd from a closed state to an open state.

[0046] The flow rate acquisition unit 504 acquires the flow rate of sulfuric acid to flow into the first supply pipe 25 and the flow rate of hydrogen peroxide solution to be supplied from each branch pipe to the first supply pipe 25 at each of the first mixing position AA to the fourth mixing position DD. In this embodiment, the flow rate of sulfuric acid to flow into the first supply pipe 25 and the flow rate of hydrogen peroxide solution to be supplied from each branch pipe to the first supply pipe 25 at each of the first mixing position AA to the fourth mixing position DD are determined in advance and stored in the storage device 514 of FIG. 6. The flow rate of sulfuric acid to flow into the first supply pipe 25 is the main flow rate. In addition, the flow rates of hydrogen peroxide solution to be supplied from the second supply pipe 26 to each mixing position are the first flow rate at the first mixing position AA, the second flow rate at the second mixing position BB, the third flow rate at the third mixing position CC, and the fourth flow rate at the fourth mixing position DD. The flow rate acquisition unit 504 acquires each flow rate stored in the storage device 514.

[0047] In this embodiment, the flow rate of hydrogen peroxide supplied to discharge nozzle 21b at fourth mixing position DD is greater than the flow rate of hydrogen peroxide supplied from branch pipe 26c to first supply pipe 25 at third mixing position CC, the flow rate of hydrogen peroxide supplied from branch pipe 26b to first supply pipe 25 at second mixing position BB, and the flow rate of hydrogen peroxide supplied from branch pipe 26a to first supply pipe 25 at first mixing position AA. In other words, the flow rate of hydrogen peroxide supplied to discharge nozzle 21b is greatest at fourth mixing position DD, where the flow path length from discharge port OH is shortest.

[0048] The flow rate control unit 505 controls the main adjustment valve NV, the first adjustment valve NVa, the second adjustment valve NVb, the third adjustment valve NVc, and the fourth adjustment valve NVd based on the flow rates acquired by the flow rate acquisition unit 504. Specifically, the flow rate control unit 505 controls the main adjustment valve NV to make the flow rate of sulfuric acid supplied to the first supply pipe 25 the same as the flow rate (main flow rate) acquired for the first supply pipe 25 by the flow rate acquisition unit 504. The flow rate control unit 505 controls the first adjustment valve NVa to make the flow rate of the hydrogen peroxide solution supplied to the first supply pipe 25 at the first mixing position AA the same as the flow rate (first flow rate) acquired for the first mixing position AA by the flow rate acquisition unit 504. The flow rate control unit 505 controls the second adjustment valve NVb to make the flow rate of the hydrogen peroxide solution supplied to the first supply pipe 25 at the second mixing position BB the same as the flow rate (second flow rate) acquired for the second mixing position BB by the flow rate acquisition unit 504. The flow rate control unit 505 controls the third adjustment valve NVc to make the flow rate of the hydrogen peroxide solution supplied to the first supply pipe 25 at the third mixing position CC the same as the flow rate (third flow rate) acquired for the third mixing position CC by the flow rate acquisition unit 504. The flow rate control unit 505 controls the fourth adjustment valve NVd to make the flow rate of the hydrogen peroxide solution supplied to the discharge nozzle 21b at the fourth mixing position DD the same as the flow rate (fourth flow rate) acquired for the fourth mixing position DD by the flow rate acquisition unit 504.

[0049] Also, for example, a flow rate sensor that detects the flow rate of the liquid flowing through the first supply pipe 25 may be provided downstream of the main adjustment valve NV of the first supply pipe 25. In this case, the flow rate control unit 505 feedback-controls the main adjustment valve NV based on the flow rate detected by the flow rate sensor after switching the main opening / closing valve V to an open state. The same applies to the first adjustment valve NVa, the second adjustment valve NVb, the third adjustment valve NVc, and the fourth adjustment valve NVd.

[0050] FIG. 8 is a flow chart for explaining an example of the flow of the substrate processing. The substrate processing is a process executed by the CPU 511 provided in the control unit 50 by the CPU 511 executing a substrate processing program stored in the RAM 512. Here, the substrate processing for one substrate W will be explained. The substrate processing here is a process of discharging the SPM liquid toward the substrate W held on the spin base 11 by the spin chuck 10 while the substrate W is rotating at a predetermined rotation speed. The time required for the substrate processing for one substrate W is called the processing time. The processing time is a predetermined time. The processing time is stored in the storage device 514 of FIG. 6. At the start of the substrate processing, the main opening / closing valve V, the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd are in a closed state. In addition, before the start of the substrate processing, the discharge arm 21a having the discharge nozzle 21b is placed in a standby position on the outer periphery of the splash guard 40.

[0051] 8, the CPU 511 included in the control unit 50 determines whether or not substrate processing has started (step S1). The time when the substrate W rotated by the spin chuck 10 reaches a predetermined rotation speed is detected as the start time of the substrate processing. The CPU 511 moves the discharge nozzle 21b from the standby position onto the substrate. The CPU 511 waits until it detects the start of the substrate processing, and when it detects the start of the substrate processing, it advances the process to step S2.

[0052] In step S2, the CPU 511 acquires the main flow rate, the first flow rate, the second flow rate, the third flow rate, and the fourth flow rate, and proceeds to step S3. Here, the main flow rate, the first flow rate, the second flow rate, the third flow rate, and the fourth flow rate stored in the storage device 514 are read out. In step S3, the CPU 511 provides the main adjustment valve NV with an electric signal indicating the main flow rate acquired in step S2, and proceeds to step S4. As a result, the main adjustment valve NV is adjusted to an opening degree such that the flow rate of sulfuric acid flowing from the first supply pipe 25 toward the discharge port OH becomes the main flow rate.

[0053] In step S4, CPU 511 provides an electrical signal indicating the first flow rate acquired in step S2 to first adjustment valve NVa, and proceeds to step S5. As a result, first adjustment valve NVa is adjusted to an opening degree such that the flow rate of hydrogen peroxide solution flowing from branch pipe 26a to first mixing position AA becomes the first flow rate.

[0054] In step S5, the CPU 511 provides the second adjustment valve NVb with an electrical signal indicating the second flow rate acquired in step S2, and the process proceeds to step S6. As a result, the second adjustment valve NVb is adjusted to an opening degree at which the flow rate of the hydrogen peroxide solution flowing from the branch pipe 26b toward the second mixing position BB is the second flow rate. In step S6, the CPU 511 provides the third adjustment valve NVc with an electrical signal indicating the third flow rate acquired in step S2, and the process proceeds to step S7. As a result, the third adjustment valve NVc is adjusted to an opening degree at which the flow rate of the hydrogen peroxide solution flowing from the branch pipe 26b toward the third mixing position CC is the third flow rate. In step S7, the CPU 511 provides the fourth adjustment valve NVd with an electrical signal indicating the fourth flow rate acquired in step S2, and the process proceeds to step S8. As a result, the fourth adjustment valve NVd is adjusted to an opening degree at which the flow rate of the hydrogen peroxide solution flowing from the branch pipe 26d toward the fourth mixing position DD is the fourth flow rate.

[0055] In step S8, the CPU 511 simultaneously opens the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd. In this case, hydrogen peroxide solution is supplied at a determined flow rate (first flow rate to fourth flow rate) from the first mixing position AA to the fourth mixing position DD of the first supply pipe 25. In step S9, the CPU 511 opens the main opening / closing valve V. Sulfuric acid is supplied at a determined flow rate (main flow rate) to the first supply pipe 25 to which hydrogen peroxide solution has been previously supplied. In this case, sulfuric acid is mixed with hydrogen peroxide solution in order from the first mixing position AA, which is the furthest from the discharge port OH, to the fourth mixing position DD, which is the closest from the discharge port OH. The main opening / closing valve V may be opened at any time after the second cleaning liquid in each branch pipe is supplied to each mixing position of the first supply pipe 25. In step S10, the CPU 511 starts a scanning operation of the discharge nozzle 21b. As a result, the discharge port OH of the discharge nozzle 21b moves above the substrate W on the movement line YL while the SPM liquid is discharged from the discharge port OH of the discharge nozzle 21b.

[0056] In step S11, the CPU 511 determines whether a predetermined processing time has elapsed since the start of the substrate processing. A standby state is entered until the processing time has elapsed, and once the processing time has elapsed, the processing proceeds to step S12. Until the processing time has elapsed, the discharge port OH of the discharge nozzle 21b moves in parallel in the horizontal direction above the substrate W while the SPM liquid is discharged from the discharge port OH of the discharge nozzle 21b. In step S12, the CPU 511 ends the substrate processing. Specifically, the CPU 511 stops the scanning operation of the discharge nozzle 21b, and simultaneously closes the main opening / closing valve V, the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd.

[0057] Here, the state of the liquid in first supply pipe 25 while substrate processing is being performed will be described. Sulfuric acid flowing through first supply pipe 25 from first supply unit 23a toward outlet OH is mixed with hydrogen peroxide solution supplied from branch pipe 26a at first mixing position AA. Then, between first mixing position AA and second mixing position BB of first supply pipe 25, a part of the sulfuric acid and the hydrogen peroxide solution undergo the first chemical reaction shown in formula (1) above, producing Caro's acid.

[0058] Stirring unit 27 is disposed between first mixing position AA and second mixing position BB of first supply pipe 25. At the inlet of stirring unit 27, the temperature of the sulfuric acid is 170°C, and the temperature of the hydrogen peroxide solution is room temperature. Therefore, the sulfuric acid and the hydrogen peroxide solution are in a liquid state. Therefore, the sulfuric acid and the hydrogen peroxide solution are efficiently stirred by stirring unit 27.

[0059] In addition, between the first mixing position AA and the second mixing position BB of the first supply pipe 25, the second chemical reaction shown in the above formula (2) proceeds simultaneously with the progress of the first chemical reaction shown in the above formula (1). As a result, water and oxygen are generated. The first chemical reaction shown in the above formula (1) is an exothermic reaction. Therefore, when the temperature of the liquid flowing between the first mixing position AA and the second mixing position BB becomes equal to or higher than the boiling point of water, the water contained in the liquid vaporizes. Therefore, the liquid and the gas are present in a mixed state between the first mixing position AA and the second mixing position BB.

[0060] Between the first mixing position AA and the second mixing position BB of the first supply pipe 25, sulfuric acid and Caro's acid that did not undergo the first chemical reaction with the hydrogen peroxide flow toward the second mixing position BB. At the second mixing position BB of the first supply pipe 25, the hydrogen peroxide supplied from the branch pipe 26b joins with the sulfuric acid and Caro's acid that did not undergo the first chemical reaction. In this case, between the second mixing position BB and the third mixing position CC of the first supply pipe 25, a portion of the sulfuric acid and the hydrogen peroxide undergo the first chemical reaction shown in the above formula (1), producing Caro's acid.

[0061] Next, between the second mixing position BB and the third mixing position CC of the first supply pipe 25, the sulfuric acid and Caro's acid that did not undergo the first chemical reaction with the hydrogen peroxide flow toward the third mixing position CC. At the third mixing position CC of the first supply pipe 25, the hydrogen peroxide supplied from the branch pipe 26c joins with the sulfuric acid and Caro's acid that did not undergo the first chemical reaction. In this case, between the third mixing position CC and the fourth mixing position DD of the first supply pipe 25, a part of the sulfuric acid and the hydrogen peroxide undergo the first chemical reaction shown in the above formula (1), producing Caro's acid.

[0062] Furthermore, between the third mixing position CC and the fourth mixing position DD of the first supply pipe 25, sulfuric acid and Caro's acid that have not undergone the first chemical reaction with the hydrogen peroxide solution flow toward the fourth mixing position DD. At the fourth mixing position DD of the discharge nozzle 21b, the hydrogen peroxide solution supplied from the branch pipe 26d joins with the sulfuric acid and Caro's acid that have not undergone the first chemical reaction. In this case, the sulfuric acid and the hydrogen peroxide solution are mixed in the mixing space MSP between the fourth mixing position DD of the discharge nozzle 21b and the discharge port OH. As a result, the sulfuric acid and the hydrogen peroxide solution undergo the first chemical reaction shown in the above formula (1), and Caro's acid is generated. Finally, the SPM liquid containing Caro's acid is supplied to the upper surface of the substrate W from the discharge port OH.

[0063] (4) Effects of the embodiment The first to fourth mixing positions AA to DD of the first supply pipe 25 have different flow path lengths to the discharge port OH. Since hydrogen peroxide is supplied to each of the first to fourth mixing positions AA to DD of the first supply pipe 25, hydrogen peroxide can be mixed with sulfuric acid flowing through the first supply pipe 25 at each mixing position at different times. In addition, the amount of hydrogen peroxide relative to the amount of sulfuric acid present at each of the first to fourth mixing positions AA to DD can be made equal to or greater than a predetermined ratio, and the first chemical reaction can proceed at different times. Therefore, the amount of hydrogen peroxide can be reduced while the first chemical reaction proceeds efficiently. As a result, a substrate processing apparatus capable of reducing the consumption of chemicals used can be provided.

[0064] Moreover, the hydrogen peroxide solution is supplied to the first supply pipe 25 at the maximum flow rate at the fourth mixing position DD, which is closest to the discharge port OH. As a result, the hydrogen peroxide solution is mixed with the sulfuric acid at the highest temperature at the maximum flow rate, so that Caro's acid can be efficiently produced.

[0065] The contact area between the sulfuric acid and the hydrogen peroxide solution in first supply pipe 25 can be increased by stirring the sulfuric acid and the hydrogen peroxide solution in stirrer 27. This makes it possible to accelerate the progress of the first chemical reaction between the sulfuric acid and the hydrogen peroxide solution at first mixing position AA.

[0066] (5) Examples and Comparative Examples Two experiments were carried out to compare the performance of stripping the resist film from the substrate W by the substrate processing apparatus 100 according to the present embodiment. Here, the first experiment will be described. In the embodiment, the substrate processing apparatus 100 having the nozzle arm 21 of FIG. 3 was used. FIG. 9 is a schematic diagram for explaining the nozzle arm 21Z of the substrate processing apparatus 100 used in the first comparative example. The nozzle arm 21 of FIG. 3 and the nozzle arm 21Z of FIG. 9 are different in the following respects. The second supply pipe 26 of the nozzle arm 21Z is not branched and is connected to the first supply pipe 25 at the fourth mixing position DD. The second supply pipe 26 includes a sub-opening / closing valve V1 and a sub-adjusting valve NV1. The functions of the sub-opening / closing valve V1 and the sub-adjusting valve NV1 are similar to those of the main opening / closing valve V and the main adjusting valve NV. In the nozzle arm 21Z of the first comparative example, hydrogen peroxide is mixed with sulfuric acid flowing through the first supply pipe 25 at one point.

[0067] In the first experiment, the resist film stripping performance of the embodiment and the first comparative example were compared. In the first experiment, the substrate was processed in a state where the nozzle arm 21 of the embodiment and the nozzle arm 21Z of the first comparative example were stopped on the upper surface of the substrate W on the spin chuck 10. The ratio of sulfuric acid flowing through the first supply pipe 25 and the hydrogen peroxide solution flowing through the second supply pipe 26 of each of the nozzle arm 21 of the embodiment and the nozzle arm 21Z of the first comparative example was adjusted to be 10:1. In addition, the rotation speed of the substrate W held by the spin chuck 10 was set to 200 rpm.

[0068] FIG. 10 is a first diagram showing the results of the first experiment, and FIG. 11 is a second diagram showing the results of the second experiment. FIG. 10 shows images of the surface of the substrate W after the substrate processing in the embodiment and the first comparative example. Here, an example in which the SPM liquid is supplied to the surface of the substrate W for 60 seconds, an example in which the SPM liquid is supplied to the surface of the substrate W for 120 seconds, and an example in which the SPM liquid is supplied to the surface of the substrate W for 180 seconds are shown. In the images of each substrate, the peeling state of the resist film on the substrate W is shown in shades of gray. Specifically, the part where the peeling of the resist film on the substrate W is completed is shown in black, and the part where the peeling of the resist film on the substrate W is progressing is shown in a light color with a lower density than black. The density is higher in the part where the peeling progresses. The numbers shown under the multiple images indicate the peeling rate. The peeling rate is the ratio of the total area of ​​the area where the peeling of the resist film is completed to the area of ​​the upper surface of the substrate W. FIG. 11 is a graph showing the peeling rate of each of the embodiment and the first comparative example of FIG. 10. The vertical axis of the graph in FIG. 11 indicates the stripping rate (%) of the resist film, and the horizontal axis indicates the processing time.

[0069] When the SPM liquid was supplied to the surface of the substrate W for 60 seconds, the peeling rate of the resist film was 2% in the example, whereas the peeling rate of the resist film was 1% in the first comparative example. When the SPM liquid was supplied to the surface of the substrate W for 120 seconds, the peeling rate of the resist film was 27% in the example, whereas the peeling rate of the resist film was 20% in the first comparative example. When the SPM liquid was supplied to the surface of the substrate W for 180 seconds, the peeling rate of the resist film was 71% in the example, whereas the peeling rate of the resist film was 53% in the first comparative example.

[0070] According to the experimental results, in both the embodiment and the first comparative example, the stripping rate increases as the processing time increases, but even with the same processing time, the stripping rate of the embodiment is greater than that of the first comparative example. In particular, when the SPM liquid is supplied to the surface of the substrate W for 180 seconds, it was found that the stripping rate of the resist film is 18% higher in the nozzle arm 21 of the embodiment than in the nozzle arm 21Z of the first comparative example. In this way, since the stripping rate of the resist film is higher in the nozzle arm 21 of the embodiment than in the nozzle arm 21Z of the first comparative example, the usefulness of the nozzle arm 21 in which hydrogen peroxide solution is mixed in multiple stages with the sulfuric acid flowing through the first supply pipe 25 is confirmed.

[0071] Next, a second experiment will be described. In the embodiment, a substrate processing apparatus 100 having the nozzle arm 21 of Fig. 3 was used. Fig. 12 is a schematic diagram for explaining a nozzle arm 21Y of the substrate processing apparatus 100 used in a second comparative example. The nozzle arm 21 of Fig. 3 differs from the nozzle arm 21Y of Fig. 9 in that the nozzle arm 21Y is not provided with an agitation unit 27.

[0072] In the second experiment, the amount of peeling of the resist film was compared between the embodiment and the second comparative example. In the second experiment, the substrate was processed in a state where the nozzle arm 21 of the embodiment and the nozzle arm 21Y of the second comparative example were stopped on the upper surface of the substrate W on the spin chuck 10. The ratio of sulfuric acid flowing through the first supply pipe 25 and the hydrogen peroxide solution flowing through the second supply pipe 26 of each of the nozzle arm 21 of the embodiment and the nozzle arm 21Y of the second comparative example was adjusted to be 4:1. The substrate W used had a diameter of 300 mm. In the second experiment, the SPM liquid was discharged from the discharge nozzle 21b in a state where the discharge nozzle 21b was fixed at a position above the center of the substrate W.

[0073] FIG. 13 is a diagram showing the results of the second experiment. The vertical axis of the graph in FIG. 13 indicates the amount of peeled resist film, and the horizontal axis indicates the radial position in one cross section of the substrate W. 0 mm on the horizontal axis indicates the center of the substrate, and -150 mm and 150 mm on the horizontal axis indicate both ends of the substrate in one cross section. In the graph in FIG. 13, the amount of peeled resist film at each of a plurality of radial positions in one cross section of the substrate W on which the substrate processing was performed in the embodiment and the second comparative example is plotted. Since the substrate processing was performed with the nozzle arm 21 of the embodiment and the nozzle arm 21Y of the second comparative example each stopped on the upper surface of the substrate W on the spin chuck 10, the part with the maximum amount of peeled is located near 0 mm on the horizontal axis. In the second experiment, as shown in FIG. 13, it was found that the amount of peeled resist film in the embodiment was generally larger than the amount of peeled resist film in the second comparative example. In this way, it was confirmed that the amount of peeled resist film was improved when the stirring unit 27 was provided in the first supply pipe 25 of the nozzle arm 21.

[0074] <First Modification> In the above embodiment, the main opening / closing valve V is opened after the second cleaning liquid in each branch pipe is supplied to each mixing position of the first supply pipe 25, but the present invention is not limited to this. The main opening / closing valve V and the opening / closing valves arranged in each branch pipe may be opened simultaneously. In this case, the length of the pipe from each opening / closing valve arranged in each branch pipe to each mixing position of the first supply pipe 25 is configured so that the second processing liquid is supplied from each branch pipe 26a to 26d to each mixing position AA to DD of the first supply pipe 25 earlier than the first processing liquid is supplied to each mixing position when the main opening / closing valve V and each opening / closing valve Va to Vd arranged in each branch pipe 26a to 26d are opened simultaneously. In this case, at the start of substrate processing, the second processing liquid is discharged before the SPM liquid is discharged from the discharge port OH.

[0075] In the above embodiment, the first processing liquid (sulfuric acid) is supplied to the second processing liquid (hydrogen peroxide solution) previously supplied to each mixing position of the first supply pipe 25, and the first processing liquid is mixed with the second processing liquid in sequence from the first mixing position AA, which is the furthest from the discharge port OH, to the fourth mixing position DD, which is the closest to the discharge port OH. However, the present invention is not limited to this. The second processing liquid may be sequentially supplied to the first processing liquid circulated through the first supply pipe 25 in a state in which the first processing liquid is supplied to each mixing position. The state in which the first processing liquid is supplied to each mixing position may be a state in which the first processing liquid is supplied to each mixing position first, or a state in which the first processing liquid and the second processing liquid are simultaneously supplied to each mixing position. In this case, at the start of the substrate processing, the first processing liquid is discharged before the SPM liquid is discharged from the discharge port OH.

[0076] As a configuration for adjusting the timing at which the second processing liquid is supplied to each mixing position, the first opening / closing valve Va to the fourth opening / closing valve Vd are opened at different times. In the first modified example, the CPU 511 first opens the main opening / closing valve V and supplies the first processing liquid to the first supply pipe 25. Next, the CPU 511 controls the first opening / closing valve Va to the fourth opening / closing valve Vd so that the second processing liquid is supplied to each mixing position while the first processing liquid is being supplied to each mixing position. In other words, the first opening / closing valve Va to the fourth opening / closing valve Vd are opened in sequence from the first mixing position AA, which is the furthest from the discharge port OH, to the fourth mixing position DD, which is the closest. According to this configuration, the second processing liquid is mixed with the first processing liquid sequentially at each mixing position.

[0077] <Second Modification> In addition, a second modified example, which is another configuration for adjusting the timing at which the second processing liquid is supplied to each mixing position, is configured to vary the distance from the opening and closing valves arranged in each branch pipe to each mixing position of the first supply pipe 25, and to open each opening and closing valve simultaneously. Fig. 14 is a first schematic diagram for explaining a nozzle arm of a substrate processing unit of the second modified example. More specifically, the length of the pipe from each opening and closing valve arranged in each branch pipe to each mixing position is shortened in order of the length of the pipe from the discharge port OH to each mixing position so that the second processing liquid is supplied to each mixing position while the first processing liquid circulated in the first supply pipe 25 is supplied to each mixing position. As shown in Fig. 14, the flow path length from the first on-off valve Va of the branch pipe 26a to the first mixing position AA, the flow path length from the second on-off valve Vb of the branch pipe 26b to the second mixing position BB, the flow path length from the third on-off valve Vc of the branch pipe 26c to the third mixing position CC, and the flow path length from the fourth on-off valve Vd of the branch pipe 26d to the fourth mixing position DD are different from one another, and are longer in this order. According to this configuration, when the CPU 511 controls the main on-off valve V and the first on-off valve Va to the fourth on-off valve Vd to be simultaneously opened, the first processing liquid circulated through the first supply pipe 25 is supplied to each mixing position, and the second processing liquid is supplied to each mixing position. Therefore, the second processing liquid is mixed with the first processing liquid sequentially at each mixing position.

[0078] According to the two modified examples described above, hydrogen peroxide solution can be mixed with the sulfuric acid flowing through first supply pipe 25 at each mixing position at different times. Also, the amount of hydrogen peroxide solution relative to the amount of sulfuric acid present at each of first mixing position AA to fourth mixing position DD can be made equal to or greater than a predetermined ratio, and the first chemical reaction can proceed at different times. Therefore, the amount of hydrogen peroxide solution used can be reduced while the first chemical reaction proceeds efficiently. As a result, a substrate processing apparatus capable of reducing the consumption of chemicals used can be provided.

[0079] <Third Modification> FIG. 15 is a second schematic diagram for explaining a nozzle arm of a substrate processing unit of a third modified example. In the nozzle arm 21 of FIG. 15, the first to fourth opening and closing valves Va to Vd are not provided in the branch pipes 26a to 26d, respectively. The main pipe 26A of the second supply pipe 26 includes a connection path 26Aa. The connection path 26Aa is provided between the second supply unit 23b and each of the branch pipes 26a to 26d. The connection path 26Aa is provided with a switching valve Vv. The switching valve Vv switches between supplying and stopping the supply of the second processing liquid from the second supply unit 23b to each of the branch pipes 26a to 26d. The flow path length from the switching valve Vv to the first mixing position AA is the shortest, the flow path length from the switching valve Vv to the second mixing position BB is the next shortest, the flow path length from the switching valve Vv to the third mixing position CC is the next shortest, and the flow path length from the switching valve Vv to the fourth mixing position DD is the longest. In this case, when the CPU 511 switches the switching valve Vv to an open state in which the second processing liquid is supplied from the second supply unit 23b to each of the branch pipes 26a to 26d, the second processing liquid reaches the first mixing position AA, the second mixing position BB, the third mixing position CC, and the fourth mixing position DD in this order. In this way, the time it takes for the second processing liquid to reach each mixing position can be made different.

[0080] <Fourth modified example> In the first modified example, an example in which either the first processing liquid or the second processing liquid arrives at a plurality of mixing positions first at the start of substrate processing has been shown, but the first processing liquid and the second processing liquid may arrive at a plurality of mixing positions simultaneously. The timing at which the first processing liquid and the second processing liquid arrive at a plurality of mixing positions may be adjusted by varying the timing of opening and closing of the main opening and closing valve V and the first opening and closing valves Va to Vd as in the first modified example, or by varying the distance from each of the main opening and closing valve V and the first opening and closing valves Va to Vd to each mixing position of the first supply pipe 25 as in the second modified example. In this case, the SPM liquid can be discharged from the discharge port OH at the start of substrate processing. As a result, the first processing liquid and the second processing liquid can be efficiently mixed, and the consumption of the first processing liquid and the second processing liquid can be suppressed.

[0081] <Fifth modified example> In the above embodiment, an example was shown in which the first treatment liquid is sulfuric acid and the second treatment liquid is hydrogen peroxide, but the present invention is not limited thereto. The first treatment liquid may be hydrogen peroxide solution and the second treatment liquid may be sulfuric acid. In addition, the combination of the first treatment liquid and the second treatment liquid is a combination of sulfuric acid and hydrogen peroxide solution, but the present invention is not limited thereto. Any combination of the first treatment liquid and the second treatment liquid may be used as long as at least one of the first treatment liquid and the second treatment liquid has a property of undergoing a chemical reaction in which the first treatment liquid and the second treatment liquid are decomposed at a predetermined temperature or higher and satisfies the condition that the chemical reaction proceeding by mixing the first treatment liquid and the second treatment liquid becomes an exothermic reaction.

[0082] <Second embodiment> The substrate processing apparatus 100 in the second embodiment supplies hydrogen peroxide solution to the first supply pipe 25 from two or more selected branch pipes selected from the branch pipes 26a to 26d. Moreover, the substrate processing apparatus 100 in the second embodiment does not supply hydrogen peroxide solution to the first supply pipe 25 from one or more selected branch pipes not selected from the branch pipes 26a to 26d. As described above, the distance between each of the branch pipes 26a to 26d and the discharge port OH is different. Therefore, when two or more selected from the branch pipes 26a to 26d are different, the concentration of Caro's acid in the SPM liquid discharged from the discharge port OH is different. The substrate processing apparatus 100 in the second embodiment adjusts the concentration of Caro's acid in the SPM liquid discharged from the discharge port OH.

[0083] The configuration of the substrate processing apparatus 100 in the second embodiment is basically the same as the configuration of the substrate processing apparatus 100 in the first embodiment. The following describes the substrate processing apparatus 100 in the second embodiment, focusing mainly on the differences from the substrate processing apparatus 100 in the first embodiment.

[0084] Fig. 16 is a block diagram showing an example of a functional configuration of a control unit in the second embodiment. Referring to Fig. 16, the functions of control unit 50 shown in Fig. 7 are different in that opening / closing control unit 503 is changed to opening / closing control unit 503A, and in that a processing condition acquisition unit 601 and a selection unit 603 are added. The other functions are the same as those shown in Fig. 7, and therefore description thereof will not be repeated here.

[0085] The processing condition acquisition unit 601 receives processing conditions for the substrate W. When processing the substrate W, the required concentration of Caro's acid in the SPM liquid may differ depending on the processing content. The processing condition acquisition unit 601 acquires the processing conditions for the substrate W received from the outside by the input / output I / F 517. The processing condition acquisition unit 601 outputs the acquired processing conditions to the selection unit 603. The substrate processing apparatus 100 executes a process to strip the resist film. The processing conditions include information about the resist film formed on the substrate W. The information about the resist film includes, for example, the type, thickness, etc. of the resist film.

[0086] The selection unit 603 selects two or more selected branch pipes from among the plurality of branch pipes 26a to 26d with reference to the allocation table stored in the storage device 514. The allocation table associates processing conditions with two or more selected branch pipes.

[0087] FIG. 17 is a diagram showing an example of the format of the allocation table. Referring to FIG. 17, the allocation table stores one or more allocation records. The allocation record associates a branch pipe to be used among the branch pipes 26a to 26d with a processing condition. The allocation record includes a field for the processing condition and a field for the selected branch pipe. The field for the selected branch pipe includes four fields for the first branch pipe to the fourth branch pipe. The field for the first branch pipe corresponds to the branch pipe 26a. The field for the second branch pipe corresponds to the branch pipe 26b. The field for the third branch pipe corresponds to the branch pipe 26c. The field for the fourth branch pipe corresponds to the branch pipe 26d.

[0088] A processing condition is set in the processing condition field of the allocation record. A mark indicating which of the branches 26a to 26d is to be used is set in the selected branch pipe field of the allocation record. Specifically, a mark indicating that branch pipe 26a is to be used is set in the first branch pipe field of the allocation record. A mark indicating that branch pipe 26b is to be used is set in the second branch pipe field of the allocation record. A mark indicating that branch pipe 26c is to be used is set in the third branch pipe field of the allocation record. A mark indicating that branch pipe 26d is to be used is set in the fourth branch pipe field of the allocation record.

[0089] In the second embodiment, a mark indicating that the branch pipe 26d is used is set in the field of the fourth branch pipe of each of the multiple allocation records included in the allocation table. Also, a mark indicating that the branch pipe corresponding to one or more of the negative fields of the first branch pipe to the third branch pipe of each of the multiple allocation records is used is set in each of the multiple allocation records. Therefore, each of the multiple allocation records specifies that two or more selected branch pipes are used.

[0090] 16, in response to the processing condition input from the processing condition acquisition unit 601, the selection unit 603 refers to the allocation table and selects one allocation record corresponding to the processing condition. The selection unit 603 identifies two or more selected branch pipes defined in the selected branch pipe field of the selected allocation record. The selection unit 603 outputs identification information for identifying each of the identified two or more selected branch pipes to the opening and closing control unit 503A.

[0091] The selection unit 603 specifies the branch pipe 26a as the selected branch pipe when a mark indicating that the branch pipe 26a is used is set in the field of the first branch pipe of the allocation record, but does not specify the branch pipe 26a as the selected branch pipe when a mark indicating that the branch pipe 26a is used is not set in the field of the first branch pipe. The selection unit 603 specifies the branch pipe 26b as the selected branch pipe when a mark indicating that the branch pipe 26b is used is set in the field of the first branch pipe of the allocation record, but does not specify the branch pipe 26b as the selected branch pipe when a mark indicating that the branch pipe 26c is used is set in the field of the first branch pipe of the allocation record, but does not specify the branch pipe 26c as the selected branch pipe when a mark indicating that the branch pipe 26c is used is not set in the field of the first branch pipe of the allocation record. The selection unit 603 identifies the branch pipe 26d as the selected branch pipe if a mark indicating that the branch pipe 26d is used is set in the field of the first branch pipe in the allocation record, but does not identify the branch pipe 26d as the selected branch pipe if a mark indicating that the branch pipe 26d is used is not set in the field of the first branch pipe in the allocation record.

[0092] The opening / closing control unit 503A controls the main opening / closing valve V, the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd. The opening / closing control unit 503A switches the main opening / closing valve V between an open state and a closed state. When the main opening / closing valve V switches from a closed state to an open state, sulfuric acid at a predetermined pressure is supplied to the first supply pipe 25. The opening / closing control unit 503A switches each of the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd between an open state and a closed state. When the first opening / closing valve Va switches from a closed state to an open state, hydrogen peroxide is supplied to the first mixing position AA of the first supply pipe 25. When the second opening / closing valve Vb switches from a closed state to an open state, hydrogen peroxide is supplied to the second mixing position BB of the first supply pipe 25. When the third on-off valve Vc switches from a closed state to an open state, hydrogen peroxide solution is supplied to the third mixing position CC of the first supply pipe 25. When the fourth on-off valve Vd switches from a closed state to an open state, hydrogen peroxide solution is supplied to the fourth mixing position DD of the discharge nozzle 21b.

[0093] The opening / closing control unit 503A receives two or more pieces of identification information from the selection unit 603. The opening / closing control unit 503A identifies an opening / closing valve provided corresponding to the selected branch pipe identified by the identification information. When the identification information identifies the branch pipe 26a, the first opening / closing valve Va provided in the branch pipe 26a is identified. When the identification information identifies the branch pipe 26b, the second opening / closing valve Vb provided in the branch pipe 26b is identified. When the identification information identifies the branch pipe 26c, the third opening / closing valve Vc provided in the branch pipe 26c is identified. When the identification information identifies the branch pipe 26d, the fourth opening / closing valve Vd provided in the branch pipe 26d is identified.

[0094] Hereinafter, an on-off valve provided corresponding to a selection branch pipe is referred to as a selection valve. On the basis of two or more pieces of identification information input from the selection unit 603, the on-off control unit 503A switches two or more selection valves identified from the first to fourth on-off valves Va to Vd to an open state, and switches on-off valves other than the two or more selection valves to a closed state. When the on-off control unit 503A identifies all of the first to fourth on-off valves Va to Vd, it switches all of the first to fourth on-off valves Va to Vd to an open state. Therefore, hydrogen peroxide is supplied to the first supply pipe 25 at two or more of the first mixing position AA to the fourth mixing position DD.

[0095] Fig. 18 is a flow chart for explaining an example of a flow of substrate processing in the second embodiment. Referring to Fig. 18, the CPU 511 included in the control unit 50 determines whether or not substrate processing has started (step S21). The time when the substrate W rotated by the spin chuck 10 reaches a predetermined rotation speed is detected as the start time of the substrate processing. The CPU 511 moves the discharge nozzle 21b from the standby position onto the substrate. The CPU 511 waits until it detects the start of the substrate processing, and when it detects the start of the substrate processing, it advances the process to step S22.

[0096] In step S22, processing conditions for the substrate W are acquired, and the process proceeds to step S23. Processing conditions input from the outside are acquired. In step S23, a selected branch pipe is identified from the allocation table, and the process proceeds to step S24. One allocation record corresponding to the processing conditions acquired in step S22 is selected from among a plurality of allocation records included in the allocation table stored in the storage device 514. Then, two or more selected branch pipes determined to be used in the selected allocation record are identified.

[0097] In step S24, the flow rates corresponding to the first supply pipe 25 and the two or more selected branch pipes are adjusted, and the process proceeds to step S25. The main flow rate, the first flow rate, the second flow rate, the third flow rate, and the fourth flow rate stored in the storage device 514 are read out. The main flow rate is the flow rate of sulfuric acid corresponding to the first supply pipe 25. The CPU 511 provides an electrical signal indicating the main flow rate to the main adjustment valve NV. The main adjustment valve NV adjusts the flow rate of sulfuric acid flowing from the first supply pipe 25 toward the discharge port OH to an opening that becomes the main flow rate.

[0098] The first flow rate is the flow rate of hydrogen peroxide solution corresponding to branch pipe 26a. CPU 511 provides an electrical signal indicative of the first flow rate to first adjustment valve NVa. The first adjustment valve NVa adjusts the opening so that the flow rate of hydrogen peroxide solution flowing from branch pipe 26a toward first mixing position AA becomes the first flow rate. The second flow rate is the flow rate of hydrogen peroxide solution corresponding to branch pipe 26b. CPU 511 provides an electrical signal indicative of the second flow rate to second adjustment valve NVb. The second adjustment valve NVb adjusts the opening so that the flow rate of hydrogen peroxide solution flowing from branch pipe 26b toward second mixing position BB becomes the second flow rate.

[0099] The third flow rate is the flow rate of hydrogen peroxide solution corresponding to branch pipe 26c. CPU 511 provides an electrical signal indicative of the third flow rate to third adjustment valve NVc. The third adjustment valve NVc adjusts the opening so that the flow rate of hydrogen peroxide solution flowing from branch pipe 26c toward third mixing position CC becomes the third flow rate. The fourth flow rate is the flow rate of hydrogen peroxide solution corresponding to branch pipe 26d. CPU 511 provides an electrical signal indicative of the fourth flow rate to fourth adjustment valve NVd. The fourth adjustment valve NVd adjusts the opening so that the flow rate of hydrogen peroxide solution flowing from branch pipe 26d toward fourth mixing position DD becomes the fourth flow rate.

[0100] In step S25, the selected valves among the first on-off valve Va, the second on-off valve Vb, the third on-off valve Vc, and the fourth on-off valve Vd are simultaneously opened. The selected valves correspond to the selected branch pipes identified in step S23. The first on-off valve Va corresponds to the branch pipe 26a, the second on-off valve Vb corresponds to the branch pipe 26b, the third on-off valve Vc corresponds to the branch pipe 26c, and the fourth on-off valve Vd corresponds to the branch pipe 26d.

[0101] For example, when the branch pipe 26a and the branch pipe 26d are specified as the selected branch pipes, the first opening / closing valve Va and the fourth opening / closing valve Vd are simultaneously opened. In this case, hydrogen peroxide solution is supplied from the first mixing position AA and the fourth mixing position DD of the first supply pipe 25, respectively. Also, for example, when the branch pipe 26a, the branch pipe 26b, and the branch pipe 26d are specified as the selected branch pipes, the first opening / closing valve Va, the second opening / closing valve Vb, and the fourth opening / closing valve Vd are simultaneously opened. In this case, hydrogen peroxide solution is supplied from the first mixing position AA, the second mixing position BB, and the fourth mixing position DD of the first supply pipe 25, respectively. Also, for example, when the branch pipe 26a, the branch pipe 26b, the branch pipe 26c, and the branch pipe 26d are all specified as the selected branch pipes, the first opening / closing valve Va, the second opening / closing valve Vb, the third opening / closing valve Vc, and the fourth opening / closing valve Vd are all simultaneously opened. In this case, hydrogen peroxide solution is supplied from the first mixing position AA, the second mixing position BB, the third mixing position CC, and the fourth mixing position DD of the first supply pipe 25, respectively.

[0102] The processing in steps S26 to S29 is the same as the processing in steps S9 to S12 shown in Fig. 8. Therefore, the description will not be repeated here.

[0103] The substrate processing apparatus 100 in the second embodiment selects at least two of the four mixing positions AA, BB, CC, and DD, and in the at least two mixing positions, the sulfuric acid and the hydrogen peroxide solution are mixed in sequence within the first supply pipe 25 from the mixing position farthest from the discharge port OH to the mixing position closest to the discharge port OH. Therefore, by changing the combination of the at least two mixing positions selected, the concentration of Caro's acid in the SPM liquid can be changed.

[0104] Furthermore, at least two mixing positions are selected based on the processing conditions for processing the substrate W. Therefore, the concentration of Caro's acid in the SPM liquid can be adjusted in accordance with the processing conditions.

[0105] <Third embodiment> The substrate processing apparatus 100 in the third embodiment supplies hydrogen peroxide solution to the first supply pipe 25 from two or more selected branch pipes selected from the branch pipes 26a to 26d, similarly to the substrate processing apparatus 100 in the second embodiment. The substrate processing apparatus 100 in the third embodiment changes the two or more selected branch pipes selected from the branch pipes 26a to 26d based on the processing result obtained by processing the substrate W. The configuration of the substrate processing apparatus 100 in the third embodiment is basically the same as that of the substrate processing apparatus 100 in the second embodiment. The following will mainly describe the differences between the substrate processing apparatus 100 in the third embodiment and the substrate processing apparatus 100 in the second embodiment.

[0106] Fig. 19 is a block diagram showing an example of a functional configuration of a control unit in the third embodiment. Referring to Fig. 19, the functions of control unit 50 shown in Fig. 16 are different in that processing condition acquisition unit 601 is deleted, selection unit 603 is changed to selection unit 603A, and processing result acquisition unit 605, history generation unit 607 and change unit 609 are added. The other functions are the same as those shown in Fig. 16, and therefore description thereof will not be repeated here.

[0107] At the start-up of the substrate processing apparatus 100, the selection unit 603 selects two or more selected branch pipes from among the branch pipes 26a to 26d that have the lowest concentration of Caro's acid. The selection unit 603A outputs identification information for identifying each of the selected two or more selected branch pipes to the opening / closing control unit 503A and the processing result acquisition unit 605. Here, an example will be described in which the branch pipes 26a and 26d are selected. In this case, the identification information for each of the branch pipes 26a and 26d is output to the processing result acquisition unit 605.

[0108] After the substrate processing apparatus 100 processes the substrate W, the processing result acquisition unit 605 acquires the processing result for the substrate W. The processing result acquisition unit 605 outputs the processing result to the history generation unit 607 together with the identification information input from the selection unit 603. The substrate processing apparatus 100 executes a process of stripping the resist film formed on the surface of the substrate W. The processing result is an index for evaluating this process. Here, an example will be described in which a stripping rate is used as the index. The stripping rate can be found by image processing an image obtained by capturing an image of the substrate W with a camera.

[0109] The history generating unit 607 generates history information including the processing results input from the processing result acquiring unit 605. The history information associates the processing results with a selected branch pipe from among the branch pipes 26a to 26d. The history generating unit 607 outputs the history information to the changing unit 609.

[0110] Fig. 20 is a diagram showing an example of a format of the history information. Referring to Fig. 17, the history information includes four fields for the first branch pipe to the fourth branch pipe, and a field for a processing result. The field for the first branch pipe corresponds to branch pipe 26a. The field for the second branch pipe corresponds to branch pipe 26b. The field for the third branch pipe corresponds to branch pipe 26c. The field for the fourth branch pipe corresponds to branch pipe 26d.

[0111] In the field of the processing result of the history information, the peeling rate, which is the processing result input from the processing result acquisition unit 605, is set. In each of the four fields of the first branch pipe to the fourth branch pipe of the allocation record, a mark indicating that it is a selected branch pipe is set. Specifically, when the identification information input from the processing result acquisition unit 605 specifies the branch pipe 26a, a mark indicating that the branch pipe 26a is the selected branch pipe is set. When the identification information input from the processing result acquisition unit 605 specifies the branch pipe 26a, a mark indicating that the branch pipe 26a is the selected branch pipe is set. When the identification information input from the processing result acquisition unit 605 specifies the branch pipe 26b, a mark indicating that the branch pipe 26b is the selected branch pipe is set. When the identification information input from the processing result acquisition unit 605 specifies the branch pipe 26c, a mark indicating that the branch pipe 26c is the selected branch pipe is set. When the identification information input from the processing result acquisition unit 605 specifies the branch pipe 26d, a mark indicating that the branch pipe 26d is the selected branch pipe is set.

[0112] Returning to FIG. 19, the change unit 609 changes the two or more selected branch pipes based on the history information. The change unit 609 changes the two or more selected branch pipes when the difference between the processing result included in the history information and the target value exceeds a predetermined range. The change unit 609 changes the set of two or more selected branch pipes so that the concentration of Caro's acid contained in the SPM liquid increases. Among the first to fourth mixing positions AA, BB, CC, and DD, the concentration of Caro's acid tends to be higher at the position closer to the discharge port OH. For this reason, the change unit 609 changes the selected branch pipe that is the furthest away from the discharge port OH among the currently selected branch pipes to a branch pipe that is closer to the discharge port OH. The change unit 609 outputs two or more pieces of identification information for identifying each of the two or more selected branch pipes after the change to the selection unit 603A.

[0113] The selection unit 603A selects two or more selected branch pipes, each identified by the two or more pieces of identification information, from among the branch pipes 26a to 26d in response to the two or more pieces of identification information input from the change unit 609. The selection unit 603A outputs the identification information for identifying each of the two or more selected branch pipes to the opening / closing control unit 503A and the processing result acquisition unit 605.

[0114] Fig. 21 is a flow chart for explaining an example of a flow of substrate processing in the third embodiment. Referring to Fig. 21, the substrate processing in the third embodiment is different from that in the second embodiment shown in Fig. 18 in that step S22 is deleted, step S23 is changed to step S23A, and steps S30 to S32 are added. Since the other steps are the same as those shown in Fig. 18, the description will not be repeated here.

[0115] When it is determined in step S21 that the processing of the substrate has started, the process proceeds to step S23A. In step S23A, two or more branch pipes are selected, and the process proceeds to step S24. The two or more branch pipes selected in step S23A are determined in advance. Here, the branch pipe 26a and the branch pipe 26d in which the concentration of Caro's acid is the lowest are selected.

[0116] In step S29, when the scanning operation and the discharge of the SPM liquid are stopped, the process proceeds to step S30. In step S30, a processing result is acquired, and the process proceeds to step S31. The processing result is an index by which the substrate processing apparatus 100 can evaluate the processing of stripping the resist film formed on the surface of the substrate W. Here, a stripping rate is used as the index.

[0117] In step S31, it is determined whether or not there is a substrate to be processed next. If there is a substrate to be processed, the process proceeds to step S32, but if there is not, the process ends. In step S32, the selection branch pipe is changed based on the processing result, and the process returns to step S24. The selection branch pipe is changed to two or more new selection branch pipes so that the Caro's acid concentration is higher than that of the current two or more selection branch pipes. Therefore, hydrogen peroxide solution is supplied from the new two or more selection branch pipes while the following steps S24 to S30 are being performed.

[0118] The substrate processing apparatus 100 in the third embodiment selects at least two of the four mixing positions AA, BB, CC, and DD, obtains processing results of a substrate W processed using the at least two selected mixing positions, and changes the set of at least two mixing positions to be selected for a substrate W to be processed next based on the processing results. Therefore, the processing results of the substrate W are fed back to the processing of the substrate W to be processed next, so that a set of at least two mixing positions can be appropriately determined while a plurality of substrates W are processed in sequence.

[0119] <Fourth embodiment> The substrate processing apparatus 100 in the fourth embodiment generates an allocation table used in the substrate processing apparatus 100 in the second embodiment based on history information. The configuration of the substrate processing apparatus 100 in the fourth embodiment is basically the same as the configuration of the substrate processing apparatus 100 in the second embodiment. The following describes the substrate processing apparatus 100 in the second embodiment, focusing mainly on the differences from the substrate processing apparatus 100 in the second embodiment.

[0120] Fig. 22 is a block diagram showing an example of a functional configuration of a control unit in the fourth embodiment. Referring to Fig. 22, the function differs from that of control unit 50 shown in Fig. 16 in that a processing result acquisition unit 605, a history generation unit 607A, and an update unit 611 are added. The other functions are the same as those shown in Fig. 16, and therefore description thereof will not be repeated here.

[0121] In the fourth embodiment, four branch pipes 26a to 26d are used. The two or more selection branch pipes include the branch pipe 26d and one or more of the other three branch pipes 26b to 26d. Therefore, there are a total of seven combinations of two or more selection branch pipes: three combinations of two selection branch pipes, three combinations of three selection branch pipes, and one combination of four selection branch pipes.

[0122] After the substrate processing apparatus 100 processes the substrate W, the processing result acquisition unit 605 acquires the processing result for the substrate W. The processing result acquisition unit 605 outputs the processing result to the history generation unit 607A. The substrate processing apparatus 100 executes a process of stripping the resist film formed on the surface of the substrate W. The processing result is an index for evaluating this process. Here, an example will be described in which a stripping rate is used as the index. The stripping rate can be found by image processing an image obtained by capturing an image of the substrate W with a camera.

[0123] History generating unit 607A generates history information including the processing results input from processing result acquiring unit 605. The history information associates the processing conditions, the selected branch pipe among branch pipes 26a to 26d, and the processing results. History generating unit 607A stores the history information in storage device 514.

[0124] Fig. 23 is a diagram showing an example of a format of history information in the fourth embodiment. Referring to Fig. 23, a processing condition field is added to the history information shown in Fig. 20. Processing conditions are set in the processing condition field of the history information.

[0125] Returning to Fig. 22, the update unit 611 updates the allocation table after the history generation unit 607A generates history information for each of the 10 combinations of two or more selected branch pipes. For example, the update unit 611 reads out a plurality of pieces of history information stored in the storage device 514 by the history generation unit 607A, and determines optimal values ​​for the two or more selected branch pipes by statistically processing the plurality of pieces of history information. Specifically, the update unit 611 determines, for the same processing conditions, the combination of two or more selected branch pipes for which the value obtained by statistically processing the processing results is optimal, as the optimal value.

[0126] Fig. 24 is a flowchart showing an example of the flow of an allocation table generating process. Referring to Fig. 24, CPU 511 included in control unit 50 acquires a process result (step S41), and advances the process to step S42.

[0127] In step S42, history information is generated based on the processing result, and the process proceeds to step S43. History information in the format shown in Fig. 23 is generated. The history information includes processing conditions, whether each of the first to fourth branch pipes 26a to 26d can be used, and the processing result. The history information is stored in the storage device 514.

[0128] In step S43, the history information is classified into processing condition groups, and the process proceeds to step S44. The processing condition groups include history information with the same processing conditions. Therefore, there are as many processing condition groups as the number of processing conditions. The history information is classified into processing condition groups with the same processing conditions as the processing conditions included in the history information. In step S44, the history information is classified into branch pipe groups, and the process proceeds to step S45. The branch pipe groups include history information with the same branch pipes (selected branch pipes) used. Therefore, there are as many branch pipe groups as the number of selected divided pipes (four in this example), which are two or more. Of the multiple branch pipe groups included in the processing condition group, the history information is classified into a branch pipe group of a set of two or more selected branch pipes that is the same as the set of two or more selected branch pipes specified in the first to fourth branch pipe fields included in the history information.

[0129] In step S45, the average value of the branch pipe group is calculated, and the process proceeds to step S46. The average value of the processing results is calculated for the multiple pieces of history information included in the branch pipe group into which the history information has been classified.

[0130] In step S46, the allocation table is updated and the process ends. The split pipe group with the largest average value is selected from among the multiple split pipe groups that include the same processing conditions as the processing conditions included in the history information. Then, from among the multiple allocation records included in the allocation table, an allocation record that includes the same processing conditions as the processing conditions included in the history information is identified. Furthermore, the selected branch pipe field of the identified allocation record is updated with a value indicating that two or more selected branch pipes corresponding to the split pipe group with the largest average value are used.

[0131] The substrate processing apparatus 100 in the fourth embodiment acquires processing results of the substrate W, generates history information that associates at least two mixing positions with the processing results, and determines an optimal value of a set of at least two mixing positions for the processing conditions based on the history information. Therefore, it is possible to determine a set of at least two mixing positions for the processing conditions without measuring the concentration of Caro's acid in the SPM liquid. In addition, since an allocation table is generated by processing the substrate W, it is possible to generate an allocation table suitable for the substrate processing apparatus 100.

[0132] <Correspondence between each component of the claims and each part of the embodiment> The outlet OH is an example of an outlet, the first supply pipe 25 is an example of a first supply path, the mixing positions AA to DD are examples of mixing positions, the branch pipes 26a to 26d are examples of multiple second supply paths, the first supply unit 23a is an example of a first supply unit, the second supply unit 23b is an example of a second supply unit, and Caro's acid, water, sulfuric acid, and hydrogen peroxide are examples of liquids. In addition, the control unit 50 is an example of a control unit, the first to fourth opening and closing valves Va to Vd are examples of multiple first switching units, the connection path 26Aa is an example of a connection path, the switching valve Vv is an example of a second switching unit, and the stirring unit 27 is an example of a stirring unit. The control unit 50 is an example of a control unit, the processing condition acquisition unit 601 is an example of a processing condition acquisition unit, the selection units 603 and 603A are examples of a selection unit, the processing result acquisition units 605 and 605A are examples of a processing result acquisition unit, the history generation unit 607 is an example of a history generation unit, the change unit 609 is an example of a change unit, and the update unit 611 is an example of a determination unit.

[0133] <Summary of the embodiment> (Item 1) A substrate processing apparatus according to one aspect includes: A substrate processing apparatus that generates a third processing liquid from a first processing liquid and a second processing liquid, and processes a substrate using the third processing liquid, A discharge port; A first supply path connected to the discharge port; a plurality of second supply paths connected to the first supply path at a plurality of mixing positions each having a different flow path length to the discharge port; a first supply unit that supplies the first processing liquid to the first supply path; a second supply unit that supplies the second processing liquid to the first supply path via a plurality of the second supply paths; At the multiple mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0134] In the substrate processing apparatus described in paragraph 1, the first processing liquid and the second processing liquid are mixed at each of the multiple mixing positions. The first processing liquid and the second processing liquid undergo a first chemical reaction to generate a third processing liquid. In the case where the first chemical reaction is an exothermic reaction, the progress of the first chemical reaction is promoted at a predetermined temperature or higher, and a second chemical reaction in which the second processing liquid decomposes into two or more substances at a temperature lower than the predetermined temperature or higher may proceed. In this case, the first chemical reaction and the second chemical reaction proceed simultaneously for each mixing of the first processing liquid and the second processing liquid. Therefore, at a temperature higher than the predetermined temperature, the first chemical reaction proceeds and the second chemical reaction proceeds. The second processing liquid is reduced due to the progress of the second chemical reaction, so the first chemical reaction is inhibited. In the multiple mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port. This allows the amount of the second processing liquid to be equal to or greater than a predetermined ratio relative to the amount of the first processing liquid present in the first supply path at each of the multiple mixing positions, allowing the first chemical reaction to continue. This allows the first chemical reaction to proceed efficiently while reducing the amount of the second processing liquid used. As a result, it is possible to provide a substrate processing apparatus that can reduce the consumption of chemicals used.

[0135] (2) The substrate processing apparatus according to the first aspect of the present invention comprises: A control unit that controls the first supply unit and the second supply unit is further provided. The control unit may control the second supply unit to supply the second treatment liquid to the plurality of mixing positions in the first supply path, and then control the first supply unit to supply the first treatment liquid to the first supply path.

[0136] According to the substrate processing apparatus described in paragraph 2, the first processing liquid is supplied after the second processing liquid is supplied to each of the plurality of mixing positions in the first supply path. In this case, the third processing liquid can be generated by simple control of the first supply unit and the second supply unit.

[0137] (Item 3) The substrate processing apparatus according to item 1, A control unit that controls the first supply unit and the second supply unit is further provided. The control unit may control the first supply unit and the second supply unit to supply the second processing liquid to the plurality of mixing positions in a state in which the first processing liquid is supplied to the plurality of mixing positions.

[0138] According to the substrate processing apparatus described in the third aspect, the second processing liquid is supplied in a state where the first processing liquid is supplied to each of the multiple mixing positions in the first supply path. Therefore, the second processing liquid is mixed with the liquid in the first supply path in sequence. Therefore, it is possible to reduce the amount of the second processing liquid used while efficiently progressing the first chemical reaction.

[0139] (4) The substrate processing apparatus according to the first aspect of the present invention comprises: a plurality of first switching units each arranged in the plurality of second supply paths and configured to switch between supply and stop of the second processing liquid from the second supply paths to the first supply path; The flow path length from the first switching portion to the mixing position in each of the plurality of second supply paths may be shorter as the flow path length between the mixing position where the second supply path is connected to the first supply path and the discharge outlet is longer.

[0140] According to the substrate processing apparatus described in the fourth aspect, when the timings at which the first switching units are switched from a stopped state to a state for supplying the second processing liquid are simultaneous, the second processing liquid is supplied in the order of the mixing position with the longest flow path length to the discharge port to the mixing position with the shortest flow path length to the discharge port. Therefore, the time it takes for the second processing liquid to reach each mixing position can be made different. By determining the timing for switching the state of the first switching unit according to the timing at which the first processing liquid is supplied, the second processing liquid can arrive at the same time as the first processing liquid arrives at each of the multiple mixing positions. As a result, the first processing liquid and the second processing liquid can be efficiently mixed, and the consumption of the first processing liquid and the second processing liquid can be suppressed.

[0141] (Item 5) The substrate processing apparatus according to item 1, a single connection path provided between the second supply unit and the second supply paths; a second switching unit provided in the connection path and configured to switch between supply and stop of the second treatment liquid from the second supply unit to the second supply paths, A flow path length between the mixing position and the second switching portion in each of the plurality of mixing positions may be shorter as a flow path length between the mixing position and the discharge port is longer.

[0142] According to the substrate processing apparatus described in the fifth aspect, the second processing liquid is supplied in the order of a mixing position having a long flow path length to the discharge port to a mixing position having a short flow path length to the discharge port. Therefore, it is possible to make the time until the second processing liquid reaches each mixing position different. By determining the timing for switching the state of the switching unit according to the timing at which the first processing liquid is supplied, it is possible to make the second processing liquid arrive at the same time as the first processing liquid arrives at each of the multiple mixing positions. As a result, it is possible to suppress the consumption of the first processing liquid and the second processing liquid.

[0143] (Item 6) In the substrate processing apparatus according to any one of items 1 to 5, The second supply unit may set a flow rate of the second processing liquid flowing into a final supply path among the multiple second supply paths that is connected to the first supply path at the mixing position where the flow path length from the outlet is shortest, greater than a flow rate of the second processing liquid flowing into one or more other second supply paths.

[0144] According to the substrate processing apparatus described in paragraph 6, the second processing liquid is supplied to the first supply path at a large flow rate at a position closest to the discharge port, whereby the amount of the second processing liquid mixed with the first processing liquid becomes maximum when the temperature of the first processing liquid is at its highest, and therefore the third processing liquid can be efficiently generated.

[0145] (Item 7) In the substrate processing apparatus according to any one of items 1 to 6, The liquid supply device may further include an agitator provided in the first supply path and configured to agitate the liquid flowing through the first supply path.

[0146] In the substrate processing apparatus described in paragraph 7, the first processing liquid and the second processing liquid mixed in the first supply path are stirred by the stirring unit, which promotes mixing of the first processing liquid and the second processing liquid, thereby making it possible to increase the amount of the first processing liquid that is the target of the first chemical reaction.

[0147] (Item 8) In the substrate processing apparatus according to item 7, The stirring section may be provided at a position where a flow path length from a first mixing position, which has the longest flow path length from the outlet, among the plurality of mixing positions, is equal to or less than a flow path length between the first mixing position and a second mixing position, which has the second longest flow path length from the outlet.

[0148] In the substrate processing apparatus described in item 8, the first processing liquid and the second processing liquid can be mixed before gas is generated in the first supply path, thereby accelerating the first chemical reaction.

[0149] (Item 9) In the substrate processing apparatus according to any one of items 1 to 8, One of the first processing liquid and the second processing liquid may be sulfuric acid, and the other may be hydrogen peroxide.

[0150] According to the substrate processing apparatus described in item 9, the first chemical reaction is H2SO4+H2O2→H2SO5+H2O, and the second chemical reaction is 2H2O2→2H20+O2. Therefore, Caro's acid contained in the SPM liquid can be efficiently produced.

[0151] (Item 10) In the substrate processing apparatus according to item 9, The first treatment liquid may be sulfuric acid, and the second treatment liquid may be hydrogen peroxide.

[0152] According to the substrate processing apparatus described in paragraph 10, hydrogen peroxide is supplied to the first supply path in multiple stages. The first chemical reaction is H2SO4+H2O2→H2SO5+H2O, and the second chemical reaction is 2H2O2→2H20+O2. Therefore, Caro's acid contained in the SPM liquid can be efficiently produced, and the consumption of hydrogen peroxide can be reduced.

[0153] (Item 11) In the substrate processing apparatus according to any one of items 1 to 10, A control unit is further provided for controlling opening and closing of each of the second supply paths, the plurality of mixing locations is at least three; The control unit includes a selection unit that selects at least two of the at least three mixing positions, At least two of the selected mixing positions are controlled so that the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0154] According to the substrate processing apparatus described in paragraph 11, at least two of the at least three mixing positions are selected. Therefore, in the at least two mixing positions, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port. Therefore, by varying the at least two combinations selected, the concentration of the third processing liquid can be changed.

[0155] (Item 12) In the substrate processing apparatus according to item 11, The control unit further includes a processing condition acquisition unit that acquires processing conditions for processing the substrate, The selection unit selects at least two of the mixing positions based on the processing conditions.

[0156] According to the substrate processing apparatus described in item 12, at least two mixing positions are selected based on processing conditions for processing the substrate, so that the concentration of the third processing liquid can be adjusted in accordance with the processing conditions.

[0157] (Item 13) In the substrate processing apparatus according to item 12, The control unit includes a processing result acquisition unit that acquires a processing result of the substrate; a history generating unit that generates history information that associates the at least two mixing positions selected by the selecting unit with the processing result; and a determination unit that determines optimal values ​​of a set of at least two of the mixing positions for the processing conditions based on the generated history information.

[0158] According to the substrate processing apparatus described in paragraph 13, a processing result of the substrate is acquired, history information that associates the at least two mixing positions with the processing result is generated, and an optimal value of a set of at least two mixing positions for the processing condition is determined based on the history information. Since the set of at least two mixing positions for the processing condition is determined based on the processing result, it is possible to determine the set of at least two mixing positions for the processing condition without measuring the concentration of the third processing liquid.

[0159] (Item 14) In the substrate processing apparatus according to any one of items 1 to 10, A control unit is further provided for controlling opening and closing of each of the second supply paths, the plurality of mixing locations is at least three; The control unit includes a selection unit that selects at least two of the at least three mixing positions; a processing result acquisition unit that acquires processing results of the substrate processed using the at least two mixing positions selected by the selection unit; and a change unit that changes the set of at least two of the mixing positions selected by the selection unit based on the processing result.

[0160] According to this aspect, a processing result of processing a substrate using at least two mixing positions selected from at least three mixing positions is obtained, and the set of at least two mixing positions is changed based on the processing result. Since the processing result is fed back, the set of at least two mixing positions can be appropriately determined.

[0161] (Item 15) A substrate processing method according to another aspect includes: 1. A substrate processing method comprising: generating a third processing liquid from a first processing liquid and a second processing liquid; and causing a substrate processing apparatus to process a substrate using the third processing liquid, the method comprising: The substrate processing apparatus includes: A discharge port; A first supply path connected to the discharge port; a plurality of second supply paths connected to the first supply path at a plurality of mixing positions each having a different flow path length to the discharge port; supplying the first processing liquid to the first supply path; supplying the second processing liquid to the first supply path via a plurality of the second supply paths; At the multiple mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0162] According to the substrate processing method described in paragraph 11, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port at multiple mixing positions in the first supply path, so that the amount of the second processing liquid relative to the amount of the first processing liquid present in the first supply path at each of the multiple mixing positions can be made equal to or greater than a predetermined ratio, and the first chemical reaction can be continued. Therefore, the amount of the second processing liquid used can be reduced while the first chemical reaction is efficiently progressed. As a result, a substrate processing apparatus capable of reducing the consumption of the chemical liquid used can be provided.

[0163] (Item 16) A substrate processing program according to another aspect of the present invention includes: A substrate processing program executed by a computer that controls a substrate processing apparatus that generates a third processing liquid from a first processing liquid and a second processing liquid and processes a substrate using the third processing liquid, The substrate processing apparatus includes: a discharge port for discharging the third treatment liquid; A first supply path connected to the discharge port; a plurality of second supply paths connected to the first supply path at a plurality of mixing positions each having a different flow path length to the discharge port; supplying the first processing liquid to the first supply path; supplying the second processing liquid to the first supply path via a plurality of the second supply paths; At the multiple mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0164] According to the substrate processing program described in paragraph 12, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port at multiple mixing positions in the first supply path, so that the amount of the second processing liquid relative to the amount of the first processing liquid present in the first supply path at each of the multiple mixing positions can be made equal to or greater than a predetermined ratio, and the first chemical reaction can be continued. Therefore, the amount of the second processing liquid used can be reduced while the first chemical reaction is efficiently progressed. As a result, a substrate processing apparatus capable of reducing the consumption of the chemical liquid used can be provided. [Explanation of symbols]

[0165] 10... spin chuck, 11... spin base, 12... chuck pin, 13... spin motor, 20... nozzle unit, 21... nozzle arm, 21Y... nozzle arm, 21Z... nozzle arm, 21a... discharge arm, 21b... discharge nozzle, 23... processing liquid supply section, 23a... first supply section, 23b... second supply section, 24... holding arm, 25... first supply pipe, 26... second supply pipe, 26A... main Pipe, 26a... branch pipe, 26a... branch pipe, 26b... branch pipe, 26c... branch pipe, 26d... branch pipe, 27... mixing unit, 40... splash guard, 50... control unit, 100... substrate processing apparatus, 251... mixing chamber, 501... first supply control unit, 502... second supply control unit, 503... opening / closing control unit, 504... flow rate acquisition unit, 505... flow rate control unit, 511... CPU, 512... RAM, 513... ROM, 514...storage device, 517...input / output I / F, 518...bus, 519...CD-ROM, 601...processing condition acquisition unit, 603, 603A...selection unit, 605, 605A...processing result acquisition unit, 607...history generation unit, 609...change unit, 611...update unit, Aa...connection path, AA...first mixing position, BB...second mixing position, CC...third mixing position, DD...fourth mixing position, LA...flow path length, LB...flow path length, LC...flow path length, LD...flow path length, NV...main adjustment valve, NV1...secondary adjustment valve, NVa...first adjustment valve, NVb...second adjustment valve, NVc...third adjustment valve, NVd...fourth adjustment valve, OH...discharge port, V...main opening / closing valve, V1...secondary opening / closing valve, Va...first opening / closing valve, Vb...second opening / closing valve, Vc...third opening / closing valve, Vd...fourth opening / closing valve, Vv...switching valve, W...substrate

Claims

1. A substrate processing apparatus that generates a third processing liquid from a first processing liquid and a second processing liquid, and processes a substrate using the third processing liquid, A discharge port; A first supply passage connected to the discharge port; a plurality of second supply paths connected to the first supply path at a plurality of mixing positions each having a different flow path length to the discharge port; a first supply unit that supplies the first processing liquid to the first supply path; a second supply unit that supplies the second processing liquid to the first supply path through a plurality of the second supply paths, A substrate processing apparatus, wherein at the multiple mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed sequentially from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

2. A control unit that controls the first supply unit and the second supply unit is further provided.

2. The substrate processing apparatus of claim 1, wherein the control unit controls the second supply unit to supply the second processing liquid to a plurality of the mixing positions in the first supply path, and then controls the first supply unit to supply the first processing liquid to the first supply path.

3. A control unit that controls the first supply unit and the second supply unit is further provided. The substrate processing apparatus according to claim 1 , wherein the control unit controls the first supply unit and the second supply unit to supply the second processing liquid while the first processing liquid is being supplied to the plurality of mixing positions.

4. a plurality of first switching units each arranged in the plurality of second supply paths and configured to switch between supply and stop of the second processing liquid from the second supply paths to the first supply path; 2. The substrate processing apparatus according to claim 1, wherein a flow path length from the first switching portion to the mixing position in each of the plurality of second supply paths is shorter as a flow path length between the mixing position where the second supply path is connected to the first supply path and the discharge port is longer.

5. a single connection path provided between the second supply unit and the second supply paths; a second switching unit provided in the connection path and configured to switch between supply and stop of the second treatment liquid from the second supply unit to the second supply paths, The substrate processing apparatus according to claim 1 , wherein a flow path length between the mixing position and the second switching unit in each of the plurality of mixing positions is shorter as a flow path length between the mixing position and the discharge port is longer.

6. The substrate processing apparatus of any one of claims 1 to 5, wherein the second supply unit makes a flow rate of the second processing liquid flowing into a final supply path among the plurality of second supply paths that is connected to the first supply path at the mixing position where the flow path length from the outlet is shortest, greater than a flow rate of the second processing liquid flowing into one or more other second supply paths.

7. 6. The substrate processing apparatus according to claim 1, further comprising an agitator provided in the first supply path for agitating the liquid flowing through the first supply path.

8. 8. The substrate processing apparatus according to claim 7, wherein the mixing unit is provided at a position where a flow path length from a first mixing position, which has the longest flow path length from the discharge port among the plurality of mixing positions, is equal to or less than a flow path length between the first mixing position and a second mixing position, which has the second longest flow path length from the discharge port.

9. 6. The substrate processing apparatus according to claim 1, wherein one of the first processing liquid and the second processing liquid is sulfuric acid, and the other is hydrogen peroxide.

10. The substrate processing apparatus according to claim 9 , wherein the first processing liquid is sulfuric acid, and the second processing liquid is hydrogen peroxide.

11. A control unit that controls opening and closing of each of the second supply paths is further provided. the plurality of mixing locations is at least three; The control unit includes a selection unit that selects at least two of the at least three mixing positions, 2. The substrate processing apparatus of claim 1, wherein the second supply unit is controlled so that, at at least two selected mixing positions, the liquid in the first supply path and the second processing liquid are mixed in sequence from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

12. The control unit further includes a processing condition acquisition unit that acquires processing conditions for processing the substrate, The substrate processing apparatus according to claim 11 , wherein the selection unit selects at least two of the mixing positions based on the processing conditions.

13. The control unit includes a processing result acquisition unit that acquires a processing result of the substrate; a history generating unit that generates history information that associates the at least two mixing positions selected by the selecting unit with the processing result; The substrate processing apparatus according to claim 12 , further comprising: a determination unit that determines optimal values ​​of a set of at least two of the mixing positions for the processing conditions based on the generated history information.

14. A control unit that controls opening and closing of each of the second supply paths is further provided. the plurality of mixing locations is at least three; The control unit includes a selection unit that selects at least two of the at least three mixing positions; a processing result acquisition unit that acquires processing results of the substrate processed using the at least two mixing positions selected by the selection unit; The substrate processing apparatus according to claim 1 , further comprising: a change unit that changes the set of at least two mixing positions selected by the selection unit based on the processing result.

15. 1. A substrate processing method comprising: generating a third processing liquid from a first processing liquid and a second processing liquid; and causing a substrate processing apparatus to process a substrate using the third processing liquid, the method comprising: The substrate processing apparatus includes: A discharge port; A first supply passage connected to the discharge port; a plurality of second supply paths connected to the first supply path at a plurality of mixing positions each having a different flow path length to the discharge port; supplying the first processing liquid to the first supply path; supplying the second processing liquid to the first supply path via a plurality of the second supply paths; a mixing position for mixing the liquid in the first supply path with the second processing liquid in a direction parallel to the discharge port, the mixing position being arranged to mix ...

16. A substrate processing program executed by a computer that controls a substrate processing apparatus that generates a third processing liquid from a first processing liquid and a second processing liquid and processes a substrate using the third processing liquid, The substrate processing apparatus includes: a discharge port for discharging the third processing liquid; A first supply passage connected to the discharge port; a plurality of second supply paths connected to the first supply path at a plurality of mixing positions each having a different flow path length to the discharge port; supplying the first processing liquid to the first supply path; supplying the second processing liquid to the first supply path via a plurality of the second supply paths; A substrate processing program, wherein at the multiple mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are mixed sequentially from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

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