Substrate processing apparatus, substrate processing method, and substrate processing program

Abstract

The invention provides a substrate processing apparatus, a substrate processing method, and a substrate processing program. A substrate processing apparatus 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 including: a discharge port; a first supply path connected to the discharge port; a plurality of second supply paths connected to the first supply paths at a plurality of mixing positions having different flow path lengths to the discharge port; 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 that mixes the second processing liquid to the first supply path at the plurality of mixing positions in the first supply path. The liquid in the first supply path and the second processing liquid are sequentially mixed from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

Description

Technical Field

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

[0002] In the photolithography process in the manufacture of semiconductor devices, etc., a resist film is formed on the entire processed surface of the substrate. As a method for removing the resist film, there is an SPM treatment. In the SPM treatment, an SPM (Sulfuric Acid Hydrogen Peroxide Mixture) liquid is generated from sulfuric acid (H2SO4) and hydrogen peroxide (H2O2), and the resist film formed on the substrate is removed by supplying the SPM liquid to the substrate. The chemical reaction in the case of generating the SPM liquid from sulfuric acid and hydrogen peroxide is an exothermic reaction. Generally, in order to give full play to the resistance of the SPM liquid to reagent stripping, the temperature of the SPM supplied to the substrate needs to be set to above 160°C. The technology for adjusting the temperature of the SPM liquid is described in Japanese Patent Gazette No. 2008-4819.

[0003] Japanese Patent Publication No. 2008-4819 describes a substrate processing device for supplying sulfuric acid and hydrogen peroxide to the surface of a substrate to strip and remove an anti-reagent from the surface of the substrate, and is characterized in that it includes: a mixing section for mixing sulfuric acid and hydrogen peroxide to generate sulfuric acid and hydrogen peroxide; a spraying section for spraying the hydrogen peroxide generated by the mixing section and supplying the hydrogen peroxide to the surface of the substrate; a path length changing mechanism for changing the path length of the supply path of the hydrogen peroxide from the mixing section to the spraying section; a liquid temperature detecting mechanism for detecting the liquid temperature of the hydrogen peroxide supplied from the mixing section to the spraying section; and a control mechanism for controlling the path length changing mechanism based on the liquid temperature detected by the liquid temperature detecting mechanism so that the hydrogen peroxide having a liquid temperature above a predetermined reference temperature is supplied to the spraying section. Summary of the invention

[0004] The progress of the first chemical reaction in the case of generating SPM liquid from sulfuric acid and hydrogen peroxide is promoted at a temperature above the first temperature. On the other hand, the progress of the second chemical reaction in which hydrogen peroxide is decomposed into water and oxygen is promoted at a temperature above the second temperature which is lower than the first temperature. Thus, for each mixing of sulfuric acid and hydrogen peroxide, the first chemical reaction and the second chemical reaction proceed simultaneously. Therefore, it is necessary to use a sufficient amount of hydrogen peroxide for performing the first chemical reaction with sulfuric acid while performing the second chemical reaction. On the other hand, from the perspective of environmental protection, it is desirable to reduce the consumption of the chemical solution used to generate the SPM liquid.

[0005] An object of the present invention is to provide a substrate processing apparatus capable of reducing the consumption of a chemical solution used.

[0006] According to one aspect of the present invention, a substrate processing device generates a third processing liquid from a first processing liquid and a second processing liquid, and uses the third processing liquid to process a substrate, and the substrate processing device comprises: a nozzle; a first supply path connected to the nozzle; a plurality of second supply paths respectively connected to the first supply path at a plurality of mixing positions with different flow path lengths to the nozzle; 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 in sequence from the mixing position farthest from the nozzle to the mixing position closest to the nozzle.

[0007] According to another aspect of the present invention, a substrate processing method is a substrate processing method performed by a substrate processing device, wherein the substrate processing device generates a third processing liquid from a first processing liquid and a second processing liquid, and uses the third processing liquid to process a substrate, the substrate processing device comprising: a nozzle; a first supply path connected to the nozzle; and a plurality of second supply paths, which are respectively connected to the first supply path at a plurality of mixing positions having different flow path lengths to the nozzle, the substrate processing method comprising: 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, wherein 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 in sequence from the mixing position farthest from the nozzle to the mixing position closest to the nozzle.

[0008] According to another aspect of the present invention, a substrate processing program is executed by a computer that controls a substrate processing device, wherein the substrate processing device generates a third processing liquid from a first processing liquid and a second processing liquid, and uses the third processing liquid to process a substrate, and the substrate processing device comprises: a nozzle that sprays the third processing liquid; a first supply path that is connected to the nozzle; and a plurality of second supply paths that are respectively connected to the first supply path at a plurality of mixing positions with different flow path lengths to the nozzle, the substrate processing program causes the computer to execute the following steps: 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, 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 in sequence from the mixing position farthest from the nozzle to the mixing position closest to the nozzle.

[0009] According to the present invention, the consumption of the used chemical solution can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 It is a side view showing an example of the structure of a substrate processing apparatus.

[0011] Figure 2 It is a top view of the substrate processing apparatus.

[0012] Figure 3 It is a schematic diagram for explaining the structure of the nozzle arm.

[0013] Figure 4 This is a schematic diagram showing an enlarged view of the ejection nozzle.

[0014] Figure 5 yes Figure 4 AA line section view.

[0015] Figure 6 It is a diagram showing an example of the configuration of a control unit.

[0016] Figure 7 This is a block diagram showing an example of the functional structure of the control unit.

[0017] Figure 8 This is a flowchart for explaining an example of a flow of substrate processing.

[0018] Fig. 9 It is a schematic diagram for explaining the nozzle arm of the substrate processing unit used in the first comparative example.

[0019] Fig.10 This is the first figure showing the results of the first experiment.

[0020] Fig.11The second figure shows the results of the first experiment.

[0021] Fig.12 It is a schematic diagram for explaining the nozzle arm of the substrate processing unit used in the second comparative example.

[0022] Fig.13 It is a figure which shows the result of the 2nd experiment.

[0023] Fig.14 This is a first schematic diagram for explaining the nozzle arm of the substrate processing unit according to the second modified example.

[0024] Fig.15 This is a second schematic diagram for explaining the nozzle arm of the substrate processing unit according to the third modified example.

[0025] Fig.16 This is a block diagram showing an example of the functional configuration of the control unit in the second embodiment.

[0026] Fig.17 This is a diagram showing an example of the format of the allocation table.

[0027] Fig.18 This is a flowchart for explaining an example of the flow of substrate processing in the second embodiment.

[0028] Fig.19 This is a block diagram showing an example of the functional configuration of a control unit in the third embodiment.

[0029] Fig. 20 This is a diagram showing an example of the format of history information.

[0030] Fig.21 This is a flowchart for explaining an example of the flow of substrate processing in the third embodiment.

[0031] Fig. 22 This is a block diagram showing an example of the functional configuration of a control unit in the fourth embodiment.

[0032] Fig.23 This is a diagram showing an example of the format of history information in the fourth embodiment.

[0033] Fig.24 This is a flowchart showing an example of the flow of allocation table creation processing. DETAILED DESCRIPTION

[0034] Below, while referring to the attached Figure 1A substrate processing device and a substrate processing method according to an embodiment of the present invention are described. In the following description, the substrate refers to a FPD (Flat Panel Display) substrate, a semiconductor substrate, an optical disk substrate, a magnetic disk substrate, an optical magneto-magnetic disk substrate, a photomask substrate, a ceramic substrate, or a solar cell substrate used in a liquid crystal display device or an organic EL (Electro Luminescence) display device.

[0035] <First embodiment>

[0036] (1) Overall structure of substrate processing device

[0037] Figure 1 It is a side view showing an example of the structure of a substrate processing apparatus. Figure 2 FIG. 1 is a top view of the substrate processing device. Figure 1 and Figure 2 In order to clarify the positional relationship, mutually orthogonal X, Y, and Z directions are defined. The X and Y directions are mutually orthogonal in the horizontal plane, and the Z direction is equivalent to the up and down direction (vertical direction). Figure 1 and Figure 2 As shown, the substrate processing apparatus 100 includes a spin chuck (spin holding unit) 10, a nozzle unit 20, a protection plate 40, and a control unit 50. The control unit 50 controls the operations of the spin chuck 10, the nozzle unit 20, and the protection plate 40.

[0038] The spin chuck 10, the nozzle unit 20 and the protection plate 40 are accommodated in the processing chamber. The processing chamber has four side parts, a top wall part and a bottom part. A transport opening (not shown) for transporting a substrate between the inside of the processing chamber and the outside of the processing chamber is formed on one side part of the processing chamber. In addition, a FFU (filter fan unit) is provided on the top wall part of the processing chamber. The FFU generates a descending airflow of clean air inside the processing chamber.

[0039] The rotary chuck 10 includes a rotary base 11, a plurality of chuck pins 12, and a rotary motor 13. The rotary base 11 is mounted on the upper end of the rotary shaft of the rotary motor 13. With respect to the rotary base 11, the rotary force of the rotary motor 13 is transmitted to the rotary base 11, and the rotary base 11 holding the substrate W rotates. In the present embodiment, the rotary shaft of the rotary motor 13 is set in a vertical direction. The rotary base 11 has a holding surface orthogonal to the rotary shaft of the rotary motor 13. A plurality of chuck pins 12 are arranged on the holding surface of the rotary base 11. The plurality of chuck pins 12 are arranged at equal intervals on concentric circles centered on the rotary shaft of the rotary base 11. At least one of the plurality of chuck pins 12 can be rotatably fixed to the rotary base 11 around a rotation axis orthogonal to the holding surface, and can change the state to a state in which the outer peripheral end of the substrate W is held and a state in which the outer peripheral end of the substrate W is not held. During substrate processing, the substrate W is held on the spin base 11 in a horizontal posture while being held by the plurality of chuck pins 12 .

[0040] The protective plate 40 surrounds the rotary chuck 10 when viewed from the side. When viewed from the side, the protective plate 40 can be moved in the vertical direction by a moving mechanism not shown in the figure. When processing the substrate, the protective plate 40 rises to a position where its upper end is located above the substrate W held on the rotary chuck 10. In this case, the protective plate 40 receives droplets scattered from the substrate W held and rotated by the rotary base 11. The droplets received by the protective plate 40 are recovered by a recovery unit (not shown). When the substrate W is moved in before the substrate processing action and when the substrate W is moved out after the substrate processing action, the protective plate 40 is lowered to a position where its upper end is lower than the rotary base 11 of the rotary chuck 10. In this way, the substrate W on the rotary chuck 10 can be moved in and out.

[0041] 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 spray arm 21a and a spray nozzle 21b. The spray arm 21a has a rectangular parallelepiped shape that is long in the X direction. The spray nozzle 21b is provided at one end in the length direction of the lower surface of the spray arm 21a, and the other end is fixed to the holding arm 24. The spray nozzle 21b has a spray port OH. The spray port OH is an opening that opens downward. The spray arm 21a accommodates a plurality of tubes inside. Figure 3 As shown, the plurality of pipes include a first supply pipe 25 and a second supply pipe 26. The treatment 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 ejection nozzle 21b, and the other end of the second supply pipe 26 is connected to the first supply pipe 25.

[0042] The linear guide LG includes a carriage CA, a track RL, and a pulse motor. The track RL of the linear guide LG is arranged outside the protection plate 40 in a plan view and is a rod-shaped shape extending in the Y direction. The carriage CA is slidably connected to the track RL. The pulse motor moves the carriage CA along the track RL.

[0043] 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 ejection 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 the ejection port OH of the ejection nozzle 21b is located above the substrate W held on the spin chuck 10 at a predetermined distance. Thus, the ejection port OH of the ejection nozzle 21b is held by the ejection arm 21a and the holding arm 24 at a position above the substrate W held on the spin chuck 10 at a predetermined distance.

[0044] When the carriage CA moves along the rail RL, the ejection arm 21a held by the holding arm 24 moves parallel to the Y direction. The length of the ejection arm 21a in the longitudinal direction is set to a size that the ejection port OH of the ejection nozzle 21b passes through the moving line YL, which passes through the center WO of the substrate W and is parallel to the Y direction. Therefore, when the carriage CA moves along the linear guide LG, the ejection port OH of the ejection nozzle 21b moves on the moving line YL above the substrate W held by the spin chuck 10 at a predetermined distance.

[0045] When the ejection arm 21a moves, the processing liquid supplied from the processing liquid supply unit 23 is ejected from the ejection port OH of the ejection nozzle 21b. Thus, the processing liquid is supplied from the ejection port OH of the ejection 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 action is referred to as the scanning action of the ejection nozzle 21b. The processing liquid supplied to the upper surface of the substrate W in this embodiment is SPM (Sulfuric Acid Hydrogen Peroxide Mixture) liquid. The SPM liquid is generated in the nozzle arm 21.

[0046] (2) Structure of nozzle arm 21

[0047] Figure 3 2 is a schematic diagram for explaining the structure of the nozzle arm 21. The nozzle arm 21 accommodates the first supply pipe 25 and the second supply pipe 26. The first supply pipe 25 has two ends, one end of which is connected to the first supply part 23a for supplying the first processing liquid, and the other end of which is connected to the ejection nozzle 21b. The flow path of the first supply pipe 25 extending from the end connected to the first supply part 23a to the ejection port OH of the ejection nozzle 21b is an example of the first supply path.

[0048] The second supply pipe 26 includes a main pipe 26A and a plurality of branch pipes 26a to 26d. The main pipe 26A has two ends, one end of which is connected to the second supply portion 23b, and the other end of which is connected to the branch pipe 26d. One end of each of the plurality of branch pipes 26a to 26d is connected to the main pipe 26A at a plurality of different branch points aA to dD of the main pipe 26A, and the other end is connected to the first supply pipe 25 at a plurality of first mixing positions AA to fourth mixing positions DD of the first supply pipe 25.

[0049] One end of the branch pipe 26a is connected to the main pipe 26A at the branch point aA, and the other end is connected to the first supply pipe 25 at the first mixing position AA. The first opening and closing valve Va and the first regulating valve NVa are inserted in the branch pipe 26a. The first opening and closing valve Va is, for example, a ball valve. The first opening and closing valve Va can be switched to an open state in which the branch pipe 26a is opened and a closed state in which the branch pipe 26a is blocked. When the first opening and closing valve Va is in an open state, the second processing liquid flows in the branch pipe 26a, and the second processing liquid is supplied to the first supply pipe 25 at the first mixing position AA. When the first opening and closing valve Va is in a closed state, the second processing liquid does not flow in the branch pipe 26a. The first regulating valve NVa can adjust the flow rate of the second processing liquid flowing in the branch pipe 26a. The first regulating valve NVa is, for example, a needle valve.

[0050] One end of the branch pipe 26b is connected to the main pipe 26A at the branch point bB, and the other end is connected to the first supply pipe 25 at the second mixing position BB. The second opening and closing valve Vb and the second regulating valve NVb are inserted in the branch pipe 26b. The second opening and closing valve Vb is, for example, a ball valve. The second opening and closing valve Vb can be switched to an open state in which the branch pipe 26b is opened and a closed state in which the branch pipe 26b is blocked. When the second opening and closing valve Vb is in an open state, the second processing liquid flows in the branch pipe 26b, and the second processing liquid is supplied to the first supply pipe 25 at the second mixing position BB. When the second opening and closing valve Vb is in a closed state, the second processing liquid does not flow in the branch pipe 26b. The second regulating valve NVb can adjust the flow rate of the second processing liquid flowing in the branch pipe 26b. The second regulating valve NVb is, for example, a needle valve.

[0051] One end of the branch pipe 26c is connected to the main pipe 26A at the branch point cC, and the other end is connected to the first supply pipe 25 at the third mixing position CC. The third opening and closing valve Vc and the third regulating valve NVc are inserted in the branch pipe 26c. The third opening and closing valve Vc is, for example, a ball valve. The third opening and closing valve Vc can be switched to an open state in which the branch pipe 26c is opened and a closed state in which the branch pipe 26c is blocked. When the third opening and closing valve Vc is in an open state, the second processing liquid flows in the branch pipe 26c, and the second processing liquid is supplied to the first supply pipe 25 at the third mixing position CC. When the third opening and closing valve Vc is in a closed state, the second processing liquid does not flow in the branch pipe 26c. The third regulating valve NVc can adjust the flow rate of the second processing liquid flowing in the branch pipe 26c. The third regulating valve NVc is, for example, a needle valve.

[0052] One end of the branch pipe 26d is connected to the main pipe 26A at the branch point dD, and the other end is connected to the ejection nozzle 21b at the 4th mixing position DD. The 4th opening and closing valve Vd and the 4th regulating valve NVd are inserted in the branch pipe 26d. The 4th opening and closing valve Vd is, for example, a ball valve. The 4th opening and closing valve Vd can be switched to an open state in which the branch pipe 26d is opened and a closed state in which the branch pipe 26d is blocked. When the 4th opening and closing valve Vd is in an open state, the 2nd processing liquid flows in the branch pipe 26d, and the 2nd processing liquid is supplied to the ejection nozzle 21b at the 4th mixing position DD. When the 4th opening and closing valve Vd is in a closed state, the 2nd processing liquid does not flow in the branch pipe 26d. The 4th regulating valve NVd can adjust the flow rate of the 2nd processing liquid flowing in the branch pipe 26d. The 4th regulating valve NVd is, for example, a needle valve.

[0053] The plurality of branch pipes 26a to 26d are examples 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 to fourth opening and closing valves Va to Vd are examples of a second supply unit.

[0054] A main opening and closing valve V and a main regulating valve NV are inserted in the first supply pipe 25. The main opening and closing valve V and the main regulating valve NV are arranged between the first supply part 23a and the first mixing position AA. The main opening and closing valve V can be switched to an open state in which the first supply pipe 25 is opened and a closed state in which the first supply pipe 25 is blocked. The main opening and closing valve V is, for example, a ball valve. When the main opening and closing valve V is in an open state, the first processing liquid flows in the first supply pipe 25, and when the main opening and closing valve V is in a closed state, the first processing liquid does not flow in the first supply pipe 25. The main regulating valve NV can adjust the flow rate of the first processing liquid flowing in the first supply pipe 25. The main regulating valve NV is, for example, a needle valve. The first supply part 23a and the main opening and closing valve V are examples of the first supply part.

[0055] The flow path lengths from the ejection port OH to the first mixing position AA to the fourth mixing position DD are respectively set as flow path lengths LA to LD. The flow path length LA from the ejection port OH to the first mixing position AA is the largest, and the flow path length LD from the ejection port OH to the fourth mixing position DD is the smallest. In addition, the flow path length LB from the ejection port OH to the second mixing position BB is shorter than the flow path length LA and longer than the flow path length LD. The flow path length LC from the ejection port OH to the third mixing position CC is shorter than the flow path length LB and longer than the flow path length LD.

[0056] In the present embodiment, a stirring portion 27 is provided between the first mixing position AA and the second mixing position BB of the first supply pipe 25. The stirring portion 27 may be, for example, an in-line mixer. The stirring portion 27 is provided in the first supply pipe 25. For example, the stirring portion 27 has a spiral shape centered on an axis parallel to the extension direction of the first supply pipe 25. The liquid flowing in the first supply pipe 25 changes its flow direction when colliding with the stirring portion 27, thereby being stirred. In addition, other stirrers having a driving mechanism may also be used as the stirring portion 27.

[0057] 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.

[0058] Here, the SPM liquid supplied to the upper surface of the substrate W is described. In the present 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. In the nozzle arm 21, permonosulfuric acid (H2SO5) as the third processing liquid is generated by mixing sulfuric acid and hydrogen peroxide. Therefore, the SPM liquid containing permonosulfuric acid is ejected from the ejection nozzle 21b. Permonosulfuric acid is effective for stripping of the resist film. Permonosulfuric acid is generated according to the following reaction formula (1) of the first chemical reaction. The first chemical reaction is an exothermic reaction. In addition, the first chemical reaction is efficiently carried out above the first temperature. Therefore, if the temperature of the first processing liquid is set to above the first temperature, permonosulfuric acid can be efficiently generated. The first temperature is about 170°C.

[0059] H2SO4+H2O2→H2SO5+H2O···(1)

[0060] 2H2O2→2H2O+O2· · · (2)

[0061] On the other hand, if the hydrogen peroxide reaches a second temperature lower than the first temperature or higher, the second chemical reaction shown in the above reaction formula (2) proceeds. The second temperature is about 140°C. Hydrogen peroxide is supplied from the branch pipe 26a at the first mixing position AA of the first supply pipe 25. In this case, a portion of the hydrogen peroxide undergoes a first chemical reaction with sulfuric acid, another portion of the hydrogen peroxide undergoes a second chemical reaction, and the remaining portion of the hydrogen peroxide does not undergo the first chemical reaction and the second chemical reaction and remains. 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, permonosulfuric acid, and water. During the flow of hydrogen peroxide between the first mixing position AA and the second mixing position BB of the first supply pipe 25, there is a case where a portion of the hydrogen peroxide undergoes a first chemical reaction with sulfuric acid, and all the remaining portions of the hydrogen peroxide undergo a second chemical reaction and decompose into water and oxygen. In this case, the liquid reaching the second mixing position BB of the first supply pipe 25 does not contain hydrogen peroxide, but contains sulfuric acid, permonosulfuric acid, and water.

[0062] 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.

[0063] In the present embodiment, hydrogen peroxide is supplied to the first supply pipe 25 at the first mixing position AA to the fourth mixing position DD. At each mixing position, hydrogen peroxide is supplied before sulfuric acid is circulated. Therefore, by supplying sulfuric acid to the first supply pipe 25, sulfuric acid is sequentially mixed with hydrogen peroxide at each mixing position, from the first mixing position AA farthest from the nozzle OH to the fourth mixing position DD closest to the nozzle OH. Each time hydrogen peroxide is supplied to sulfuric acid, the first chemical reaction proceeds. As mentioned above, the first chemical reaction is an exothermic reaction. Therefore, the temperature of the liquid flowing in the first supply pipe 25 increases in the order of the time points of passing through 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.

[0064] In addition, there is a case where all the sulfuric acid supplied from the first supply unit 23a to the first supply pipe 25 undergoes the first chemical reaction with the hydrogen peroxide solution while flowing through the first supply pipe 25. In this case, sulfuric acid is not supplied to the ejection nozzle 21b, but an SPM liquid containing hydrogen peroxide solution, permonosulfuric acid, and water is supplied. In addition, when the remaining portion of the hydrogen peroxide solution that has not undergone the first chemical reaction is decomposed by the second chemical reaction before being ejected from the ejection port OH, hydrogen peroxide solution is not supplied to the ejection nozzle 21b, but an SPM liquid containing permonosulfuric acid and water is supplied.

[0065] Here, the details of the discharge nozzle 21b will be described. Figure 4 It is a schematic diagram which enlarges the discharge nozzle 21b. Figure 5 yes Figure 4 AA line cross-sectional view. The ejection 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 ejection outlet OH of the ejection nozzle 21b. The mixing chamber 251 includes a cylindrical mixing space MSP and a connecting space LSP connected to the ejection outlet OH from the bottom of the mixing space MSP. The connecting space LSP is a mortar-shaped truncated cone whose cross-sectional area gradually decreases from the mixing space MSP toward the ejection outlet OH. A branch pipe 26d is connected to the side of the mixing space MSP. At the connecting portion of the branch pipe 26d and the mixing space MSP, a filter FT formed with a plurality of holes is provided. The filter FT is, for example, a sintered filter. A predetermined pressure is applied to the hydrogen peroxide flowing in the branch pipe 26d. Therefore, the hydrogen peroxide becomes mist when passing through the filter FT and is supplied to the mixing space MSP. As a result, since the hydrogen peroxide becomes mist, the surface area of ​​the hydrogen peroxide increases. As a result, the hydrogen peroxide solution and the sulfuric acid can be mixed efficiently, thereby promoting the progress of the first chemical reaction.

[0066] (3) Substrate processing based on control of the control unit 50

[0067] Figure 6 Yes means Figure 3 FIG. 5 is a diagram showing an example of the structure of the control unit 50. Figure 6 The control unit 50 is composed of a CPU 511 , a RAM 512 , a ROM 513 , a storage device 514 , and an input / output I / F 517 . The CPU 511 , the RAM 512 , the ROM 513 , the storage device 514 , and the input / output I / F 517 are connected to a bus 518 .

[0068] RAM 512 is used as a work area of ​​CPU 511. System programs are stored in ROM 513. Storage device 514 includes a storage medium such as a hard disk or a semiconductor memory, and stores programs.

[0069] The CD-ROM 519 storing the program is removable from the storage device 514. The CPU 511 downloads the program stored in the hard disk, semiconductor memory or CD-ROM 519 to the RAM 512 and executes it. The input / output I / F 517 is a communication interface that can connect the CPU 511 to an external device.

[0070] In addition, the recording medium for storing the program executed by CPU511 is not limited to CD-ROM519, and may also be a medium such as an optical disk (MO (Magnetic Optical Disc) / MD (Mini Disc) / DVD (Digital Versatile Disc)), an IC card, an optical card, a MASK ROM, an EPROM (Erasable Programmable ROM) or other semiconductor memory. Furthermore, CPU511 may download the program from a computer connected to the network and store it in storage device 514, or a computer connected to the network may write the program to storage device 514, download the program stored in storage device 514 to RAM512 and execute it by CPU511. The program mentioned here includes not only programs that can be directly executed by CPU511, but also source programs, compressed programs, encrypted programs, etc.

[0071] Figure 7 50 is a block diagram showing an example of the functional structure of the control unit 50. The control unit 50 includes a first supply control unit 501, a second supply control unit 502, an opening and closing control unit 503, a flow acquisition unit 504, and a flow control unit 505. In this embodiment, the components of the control unit 50 are controlled by Figure 6 This is achieved by the CPU 511 executing the substrate processing program stored in the CD-ROM 519 .

[0072] The first supply control unit 501 controls the first supply unit 23a. Specifically, the first supply control unit 501 switches the pump (not shown) included in the first supply unit 23a between the closed state and the open state. When the pump is switched from the closed state to the open 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 the pump (not shown) included in the second supply unit 23b between the closed state and the open state. When the pump is switched from the closed state to the open state, the hydrogen peroxide supplied to the second supply pipe 26 is pressurized.

[0073] The opening and closing control unit 503 controls the main opening and closing valve V, the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc, and the fourth opening and closing valve Vd. The opening and closing control unit 503 switches the main opening and closing valve V between an open state and a closed state. When the closed state is switched to an open state, sulfuric acid of a predetermined pressure is supplied to the first supply pipe 25. The opening and closing control unit 503 switches the first opening and closing valve Va between an open state and a closed state. When the first opening and closing valve Va is switched from a closed state to an open state, hydrogen peroxide is supplied to the first mixing position AA of the first supply pipe 25. The opening and closing control unit 503 switches the second opening and closing valve Vb between an open state and a closed state. When the second opening and closing valve Vb is switched from a closed state to an open state, hydrogen peroxide is supplied to the second mixing position BB of the first supply pipe 25. The opening and closing control unit 503 switches the third opening and 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 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 is supplied to the fourth mixing position DD of the ejection nozzle 21b. After switching the main on-off valve V from a closed state to an open state, the on-off control unit 503 switches the first on-off valve Va to the fourth on-off valve Vd from a closed state to an open state at the same time.

[0074] The flow rate acquisition unit 504 acquires the flow rate of sulfuric acid to be flowed to the first supply pipe 25 and the flow rate of hydrogen peroxide to be supplied from each branch pipe to the first supply pipe 25 at the first mixing position AA to the fourth mixing position DD. In the present embodiment, the flow rate of sulfuric acid to be flowed to the first supply pipe 25 and the flow rate of hydrogen peroxide to be supplied from each branch pipe to the first supply pipe 25 at the first mixing position AA to the fourth mixing position DD are predetermined and stored in Figure 6 The flow rate of sulfuric acid to be supplied to the first supply pipe 25 is the main flow rate. In addition, the flow rate of hydrogen peroxide to be supplied from the second supply pipe 26 at each mixing position is 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.

[0075] In the present embodiment, the flow rate of hydrogen peroxide supplied to the ejection nozzle 21b at the fourth mixing position DD is greater than the flow rate of hydrogen peroxide supplied from the branch pipe 26c to the first supply pipe 25 at the third mixing position CC, the flow rate of hydrogen peroxide supplied from the branch pipe 26b to the first supply pipe 25 at the second mixing position BB, and the flow rate of hydrogen peroxide supplied from the branch pipe 26a to the first supply pipe 25 at the first mixing position AA. In other words, the flow rate of hydrogen peroxide supplied to the ejection nozzle 21b is the largest at the fourth mixing position DD where the flow path length from the ejection port OH is the shortest.

[0076] The flow control unit 505 controls the main regulating valve NV, the first regulating valve NVa, the second regulating valve NVb, the third regulating valve NVc, and the fourth regulating valve NVd based on the flow rates acquired by the flow acquisition unit 504. Specifically, the flow control unit 505 controls the main regulating valve NV so that the flow rate of sulfuric acid supplied to the first supply pipe 25 becomes the same as the flow rate (main flow rate) acquired by the flow acquisition unit 504 for the first supply pipe 25. The flow control unit 505 controls the first regulating valve NVa so that the flow rate of hydrogen peroxide supplied to the first supply pipe 25 at the first mixing position AA becomes the same as the flow rate (first flow rate) acquired by the flow acquisition unit 504 for the first mixing position AA. The flow control unit 505 controls the second regulating valve NVb so that the flow rate of hydrogen peroxide supplied to the first supply pipe 25 at the second mixing position BB becomes the same as the flow rate (second flow rate) acquired by the flow acquisition unit 504 for the second mixing position BB. The flow control unit 505 controls the third regulating valve NVc so that the flow rate of the hydrogen peroxide solution supplied to the first supply pipe 25 at the third mixing position CC becomes the same as the flow rate (third flow rate) acquired by the flow acquisition unit 504 for the third mixing position CC. The flow control unit 505 controls the fourth regulating valve NVd so that the flow rate of the hydrogen peroxide solution supplied to the ejection nozzle 21b at the fourth mixing position DD becomes the same as the flow rate (fourth flow rate) acquired by the flow acquisition unit 504 for the fourth mixing position DD.

[0077] In addition, for example, a flow sensor for detecting the flow rate of the liquid flowing in the first supply pipe 25 may be provided on the downstream side of the main control valve NV of the first supply pipe 25. In this case, after the flow control unit 505 switches the main opening and closing valve V to the open state, it performs feedback control on the main control valve NV based on the flow rate detected by the flow sensor. The same is true for the first control valve NVa, the second control valve NVb, the third control valve NVc, and the fourth control valve NVd.

[0078] Figure 8 : is a flowchart for explaining an example of the process of substrate processing. Substrate processing is a process performed by CPU511 of control unit 50 by executing a substrate processing program stored in RAM512. Here, substrate processing for a substrate W is described. The substrate processing here is a process of spraying SPM liquid toward the substrate while the substrate W held by the spin chuck 10 on the spin base 11 is rotating at a predetermined rotation speed. The time required for substrate processing for a substrate W is called processing time. The processing time is a predetermined time. The processing time is stored in Figure 6The storage device 514 is provided. When the substrate processing starts, the main opening and closing valve V, the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc and the fourth opening and closing valve Vd are set to be closed. In addition, before the substrate processing starts, the ejection arm 21a having the ejection nozzle 21b is arranged at a standby position on the outer periphery of the protection plate 40.

[0079] Reference Figure 8 , the CPU 511 of the control unit 50 determines whether the processing of the substrate has started (step S1). The time point when the substrate W rotated by the spin chuck 10 reaches a predetermined rotation speed is detected as the start time point of the substrate processing. The CPU 511 moves the ejection nozzle 21b from the standby position to the substrate. The CPU 511 waits until the start of the substrate processing is detected, and when the start of the substrate processing is detected, the processing enters step S2.

[0080] In step S2, the CPU 511 obtains the main flow rate, the first flow rate, the second flow rate, the third flow rate, and the fourth flow rate, and the process 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 an electrical signal indicating the main flow rate obtained in step S2 to the main regulating valve NV, and the process proceeds to step S4. As a result, the main regulating valve NV is adjusted to an opening degree at which the flow rate of sulfuric acid flowing from the first supply pipe 25 toward the discharge port OH becomes the main flow rate.

[0081] In step S4, the CPU 511 provides an electrical signal indicating the first flow rate acquired in step S2 to the first regulating valve NVa, and the process proceeds to step S5. Thus, the first regulating valve NVa is adjusted to an opening degree at which the flow rate of hydrogen peroxide flowing from the branch pipe 26a toward the first mixing position AA becomes the first flow rate.

[0082] In step S5, the CPU 511 supplies an electrical signal indicating the second flow rate obtained in step S2 to the second regulating valve NVb, and the process proceeds to step S6. As a result, the second regulating valve NVb is adjusted to an opening degree at which the flow rate of hydrogen peroxide flowing from the branch pipe 26b toward the second mixing position BB becomes the second flow rate. In step S6, the CPU 511 supplies an electrical signal indicating the third flow rate obtained in step S2 to the third regulating valve NVc, and the process proceeds to step S7. As a result, the third regulating valve NVc is adjusted to an opening degree at which the flow rate of hydrogen peroxide flowing from the branch pipe 26b toward the third mixing position CC becomes the third flow rate. In step S7, the CPU 511 supplies an electrical signal indicating the fourth flow rate obtained in step S2 to the fourth regulating valve NVd, and the process proceeds to step S8. As a result, the fourth regulating valve NVd is adjusted to an opening degree at which the flow rate of hydrogen peroxide flowing from the branch pipe 26d toward the fourth mixing position DD becomes the fourth flow rate.

[0083] In step S8, CPU511 sets the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc and the fourth opening and closing valve Vd to the open state at the same time. In this case, hydrogen peroxide is supplied to the first mixing position AA to the fourth mixing position DD of the first supply pipe 25 at a determined flow rate (first flow rate to fourth flow rate). In step S9, CPU511 sets the main opening and closing valve V to the open state. Sulfuric acid is supplied to the first supply pipe 25 to which hydrogen peroxide is supplied in advance at a determined flow rate (main flow rate). In this case, sulfuric acid is mixed with hydrogen peroxide in sequence from the first mixing position AA farthest from the nozzle OH to the fourth mixing position DD closest to the nozzle OH. In addition, as for setting the main opening and closing valve V to the open state, it can be any time as long as it is after the second processing liquid in each branch pipe is supplied to each mixing position of the first supply pipe 25. In step S10, CPU511 starts the scanning action of the ejection nozzle 21b. As a result, the SPM liquid is ejected from the ejection port OH of the ejection nozzle 21 b , and the ejection port OH of the ejection nozzle 21 b moves above the substrate W on the movement line YL.

[0084] In step S11, the CPU 511 determines whether a predetermined processing time has passed since the start of the substrate processing. Before the processing time has passed, it is in a standby state, and when the processing time has passed, the processing enters step S12. During the period until the processing time has passed, the SPM liquid is ejected from the ejection port OH of the ejection nozzle 21b, and the ejection port OH of the ejection nozzle 21b moves in parallel in the horizontal direction above the substrate W. In step S12, the CPU 511 ends the substrate processing. Specifically, the CPU 511 stops the scanning action of the ejection nozzle 21b, and sets the main opening and closing valve V, the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc, and the fourth opening and closing valve Vd to a closed state at the same time.

[0085] Here, the state of the liquid in the first supply pipe 25 during the substrate processing is described. The sulfuric acid flowing from the first supply part 23a toward the discharge port OH in the first supply pipe 25 is mixed with the hydrogen peroxide supplied from the branch pipe 26a at the first mixing position AA. Then, between the first mixing position AA and the second mixing position BB 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), thereby generating peroxymonosulfuric acid.

[0086] The stirring section 27 is arranged between the first mixing position AA and the second mixing position BB of the first supply pipe 25. At the inlet of the stirring section 27, the temperature of sulfuric acid is 170°C and the temperature of hydrogen peroxide is room temperature. Therefore, the state of sulfuric acid and the state of hydrogen peroxide are liquid. Therefore, the stirring section 27 efficiently stirs sulfuric acid and hydrogen peroxide.

[0087] In addition, between the first mixing position AA and the second mixing position BB of the first supply pipe 25, as the first chemical reaction shown in the above formula (1) proceeds, the second chemical reaction shown in the above formula (2) proceeds simultaneously. Therefore, 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 higher than the boiling point of water, the water contained in the liquid vaporizes. Therefore, between the first mixing position AA and the second mixing position BB, the liquid and the gas exist in a mixed state.

[0088] The sulfuric acid and permonosulfuric acid that have not undergone the first chemical reaction with the hydrogen peroxide solution flow toward the second mixing position BB between the first mixing position AA and the second mixing position BB of the first supply pipe 25. The hydrogen peroxide solution supplied from the branch pipe 26b merges with the sulfuric acid and permonosulfuric acid that have not undergone the first chemical reaction at the second mixing position BB of the first supply pipe 25. In this case, between the second mixing position BB and the third mixing position CC of the first supply pipe 25, a part of the sulfuric acid and the hydrogen peroxide solution undergo the first chemical reaction shown in the above formula (1), thereby generating permonosulfuric acid.

[0089] Next, the sulfuric acid and permonosulfuric acid that have not undergone the first chemical reaction with the hydrogen peroxide solution flow toward the third mixing position CC between the second mixing position BB and the third mixing position CC of the first supply pipe 25. At the third mixing position CC of the first supply pipe 25, the hydrogen peroxide solution supplied from the branch pipe 26c merges with the sulfuric acid and permonosulfuric acid that have not undergone 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 undergoes the first chemical reaction represented by the above formula (1) with the hydrogen peroxide solution to generate permonosulfuric acid.

[0090] Furthermore, between the third mixing position CC and the fourth mixing position DD of the first supply pipe 25, sulfuric acid and permonosulfuric acid that have not undergone the first chemical reaction with hydrogen peroxide flow toward the fourth mixing position DD. At the fourth mixing position DD of the ejection nozzle 21b, the hydrogen peroxide supplied from the branch pipe 26d merges with the sulfuric acid and permonosulfuric acid that have not undergone the first chemical reaction. In this case, sulfuric acid and hydrogen peroxide are mixed in the mixing space MSP between the fourth mixing position DD of the ejection nozzle 21b and the ejection port OH. As a result, sulfuric acid and hydrogen peroxide undergo the first chemical reaction shown in the above formula (1) to generate permonosulfuric acid. Finally, the SPM liquid containing permonosulfuric acid is supplied from the ejection port OH to the upper surface of the substrate W.

[0091] (4) Effects of Implementation

[0092] The flow path lengths from the first mixing position AA to the fourth mixing position DD of the first supply pipe 25 to the ejection port OH are different from each other. Since hydrogen peroxide is supplied to the first mixing position AA to the fourth mixing position DD of the first supply pipe 25, it is possible to mix hydrogen peroxide at different times at each mixing position with respect to sulfuric acid flowing in the first supply pipe 25. In addition, the amount of hydrogen peroxide present in the first mixing position AA to the fourth mixing position DD can be made to be greater than a predetermined ratio relative to the amount of sulfuric acid, and the first chemical reaction can be performed at different times. Therefore, the first chemical reaction can be performed efficiently while reducing the amount of hydrogen peroxide used. As a result, it is possible to provide a substrate processing device that can reduce the consumption of the used chemical solution.

[0093] Furthermore, hydrogen peroxide is supplied at the maximum flow rate to the first supply pipe 25 at the fourth mixing position DD which is closest to the discharge port OH. Thus, hydrogen peroxide is mixed at the maximum flow rate with sulfuric acid at the highest temperature, so that peroxymonosulfuric acid can be efficiently produced.

[0094] The contact area between sulfuric acid and hydrogen peroxide can be increased by stirring the sulfuric acid and hydrogen peroxide in the first supply pipe 25 by the stirring unit 27. This can promote the first chemical reaction between sulfuric acid and hydrogen peroxide at the first mixing position AA.

[0095] (5) Examples and Comparative Examples

[0096] Two experiments were conducted to compare the stripping performance of the resist film on the substrate W by the substrate processing apparatus 100 according to the present embodiment. Here, the first experiment is described. Figure 3 The substrate processing apparatus 100 includes a nozzle arm 21 . Fig. 9 It is a schematic diagram for explaining the nozzle arm 21Z of the substrate processing apparatus 100 used in the first comparative example. Figure 3 The nozzle arm 21 and Fig. 9 The nozzle arm 21Z of the first comparative example is different in the following aspects. The second supply pipe 26 of the nozzle arm 21Z is not branched, but is connected to the first supply pipe 25 at the fourth mixing position DD. The second supply pipe 26 includes an auxiliary opening and closing valve V1 and an auxiliary regulating valve NV1. The functions of the auxiliary opening and closing valve V1 and the auxiliary regulating valve NV1 are the same as those of the main opening and closing valve V and the main regulating valve NV. In the nozzle arm 21Z of the first comparative example, the hydrogen peroxide solution is mixed with the sulfuric acid flowing in the first supply pipe 25 at one place.

[0097] In the first experiment, the stripping performance of the resist film of the embodiment and the first comparative example was 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 the sulfuric acid flowing in the first supply pipe 25 and the hydrogen peroxide flowing in the second supply pipe 26 of the nozzle arm 21 of the embodiment and the nozzle arm 21Z of the first comparative example was adjusted to 10:1. In addition, the rotation speed of the substrate W held on the spin chuck 10 was set to 200 rpm.

[0098] Fig.10 is the first figure showing the results of the first experiment, Fig.11 FIG2 is a second diagram showing the results of the second experiment. Fig.10 , images of the surface of substrate W after substrate processing in the embodiment and the first comparative example are shown. Here, an example of supplying SPM liquid to the surface of substrate W for 60 seconds, an example of supplying SPM liquid to the surface of substrate W for 120 seconds, and an example of supplying SPM liquid to the surface of substrate W for 180 seconds are shown. In the image of each substrate, the stripping condition of the resist film on substrate W is shown in shades. Specifically, the portion where the stripping of the resist film on substrate W has been completed is shown in black, and the portion where the stripping of the resist film on substrate W is in progress is shown in a light color with a lower concentration than black. The higher the degree of stripping, the higher the concentration of the portion. The numbers shown under the multiple images show the stripping rate. The stripping rate is the ratio of the total area of ​​the region where the stripping of the resist film has been completed to the area of ​​the upper surface of substrate W. Fig.11 Yes means Fig.10 A graph showing the peeling rate of each of the embodiments and the first comparative example. Fig.11 The vertical axis of the graph shows the peeling rate (%) of the resist film, and the horizontal axis shows the processing time.

[0099] When the SPM liquid was supplied to the surface of the substrate W for 60 seconds, the peeling rate of the resist film in the embodiment was 2%, while the peeling rate of the resist film in the first comparative example was 1%. When the SPM liquid was supplied to the surface of the substrate W for 120 seconds, the peeling rate of the resist film in the embodiment was 27%, while the peeling rate of the resist film in the first comparative example was 20%. When the SPM liquid was supplied to the surface of the substrate W for 180 seconds, the peeling rate of the resist film in the embodiment was 71%, while the peeling rate of the resist film in the first comparative example was 53%.

[0100] 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 is found that the stripping rate of the resist film of the nozzle arm 21 of the embodiment is improved by 18% compared with the nozzle arm 21Z of the first comparative example. As described above, from the fact that the stripping rate of the resist film of the nozzle arm 21 of the embodiment is improved compared with the nozzle arm 21Z of the first comparative example, the usefulness of making the hydrogen peroxide merge with the sulfuric acid flowing in the first supply pipe 25 in multiple stages as in the nozzle arm 21 is confirmed.

[0101] Next, the second experiment is described. Figure 3 The substrate processing apparatus 100 includes a nozzle arm 21 . Fig.12 It is a schematic diagram for explaining the nozzle arm 21Y of the substrate processing apparatus 100 used in the second comparative example. Figure 3 The nozzle arm 21 and Fig. 9 The nozzle arm 21Y is different from the nozzle arm 21Y in that the stirring portion 27 is not provided in the nozzle arm 21Y.

[0102] In the second experiment, the amount of resist film stripping of the embodiment and the second comparative example was compared. 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 in the first supply pipe 25 and the hydrogen peroxide flowing in the second supply pipe 26 of the nozzle arm 21 of the embodiment and the nozzle arm 21Y of the second comparative example was adjusted to 4:1. The substrate W used was a substrate W with a diameter of 300 mm. In addition, in the second experiment, the SPM liquid was ejected from the ejection nozzle 21b in a state where the ejection nozzle 21b was fixed above the center of the substrate W.

[0103] Fig.13 It is a figure which shows the result of the 2nd experiment. Fig.13 The vertical axis of the graph shows the amount of resist film peeling, and the horizontal axis shows the radial position in a cross section of the substrate W. 0 mm on the horizontal axis shows the center of the substrate, and -150 mm and 150 mm on the horizontal axis show the two ends of the substrate in a cross section. Fig.13 The graph of FIG. 1 shows the amount of resist film peeled off at multiple locations in the radial direction in each cross section of the substrate W subjected to substrate processing in the embodiment and the second comparative example. Since the nozzle arm 21 of the embodiment and the nozzle arm 21Y of the second comparative example respectively performed substrate processing in a state where the upper surface of the substrate W on the spin chuck 10 was stopped, the portion with the largest amount of peeling off is located near 0 mm on the horizontal axis. In the second experiment, as shown in FIG. Fig.13As shown, it can be seen that the peeling amount of the resist film of the example is larger than that of the comparative example 2. Thus, it was confirmed that the peeling amount of the resist film was improved when the stirring part 27 was provided in the first supply pipe 25 of the nozzle arm 21.

[0104] <First Modification>

[0105] In the above-mentioned embodiment, the main opening and closing valve V is set to the open state after the second processing 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 and closing valve V and the opening and closing valves arranged in each branch pipe can also be set to the open state at the same time. In this case, the length of the pipe from each opening and closing valve arranged in each branch pipe to each mixing position of the first supply pipe 25 is configured so that when the main opening and closing valve V and each opening and closing valve Va~Vd arranged in each branch pipe 26a~26d are opened at the same time, the second processing liquid is supplied from each branch pipe 26a~26d to each mixing position AA~DD of the first supply pipe 25 earlier than the first processing liquid is supplied to each mixing position. In this case, at the start of substrate processing, the second processing liquid is ejected before the SPM liquid is ejected from the ejection port OH.

[0106] In the above-mentioned embodiment, an example is shown in which the first processing liquid (sulfuric acid) is supplied to the second processing liquid (hydrogen peroxide) supplied to each mixing position in advance to 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 farthest from the nozzle OH to the fourth mixing position DD closest to the nozzle OH, but the present invention is not limited to this. It can also be configured so that the second processing liquid is sequentially supplied to the first processing liquid flowing in the first supply pipe 25 in a state where 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 first supplied to each mixing position, 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 substrate processing, the first processing liquid is ejected before the SPM liquid is ejected from the nozzle OH.

[0107] As a structure for adjusting the moment (timing) when the second processing liquid is supplied to each mixing position, the opening and closing moments of the first opening and closing valve Va to the fourth opening and closing valve Vd are made different. In the first variant, first, the CPU 511 sets the main opening and closing valve V to the open state, and supplies the first processing liquid to the first supply pipe 25. Then, the CPU 511 controls the first opening and closing valve Va to the fourth opening and closing valve Vd so that the second processing liquid is supplied to each mixing position in a state where the first processing liquid is supplied to each mixing position. In other words, from the first mixing position AA farthest from the ejection outlet OH to the fourth mixing position DD closest thereto, the corresponding first opening and closing valve Va to the fourth opening and closing valve Vd are set to the open state in sequence. According to this structure, the second processing liquid is mixed with the first processing liquid in sequence at each mixing position.

[0108] <Second Modification>

[0109] In addition, a second variation of another structure for adjusting the timing when the second processing liquid is supplied to each mixing position is constructed by making the distance from the on-off valve arranged in each branch pipe to each mixing position of the first supply pipe 25 different, and setting each on-off valve to an open state at the same time. Fig.14 1 is a first schematic diagram of a nozzle arm of a substrate processing unit for explaining the second variant. More specifically, the length of the pipe from each on-off valve arranged in each branch pipe to the mixing position is configured from short to long in the order of the length of the pipe from the nozzle OH to each mixing position, so that the second processing liquid is supplied to each mixing position while the first processing liquid flowing through the first supply pipe 25 is supplied to each mixing position. Fig.14 As shown, the flow path length from the first opening and closing valve Va of the branch pipe 26a to the first mixing position AA, the flow path length from the second opening and closing valve Vb of the branch pipe 26b to the second mixing position BB, the flow path length from the third opening and closing valve Vc of the branch pipe 26c to the third mixing position CC, and the flow path length from the fourth opening and closing valve Vd of the branch pipe 26d to the fourth mixing position DD are different from each other and increase in this order. According to this structure, when the CPU 511 is controlled in a manner that the main opening and closing valve V and the first opening and closing valve Va to the fourth opening and closing valve Vd are simultaneously set to the open state, the second processing liquid is supplied to each mixing position in the state where the first processing liquid flowing through the first supply pipe 25 is supplied to each mixing position. Therefore, the second processing liquid is sequentially mixed with the first processing liquid at each mixing position.

[0110] According to the above two modified examples, the hydrogen peroxide can be mixed with the sulfuric acid flowing in the first supply pipe 25 at different multiple times at each mixing position. In addition, the amount of hydrogen peroxide present in the first mixing position AA to the fourth mixing position DD can be set to be greater than a predetermined ratio relative to the amount of sulfuric acid, and the first chemical reaction can be performed at different multiple time points. Therefore, the first chemical reaction can be performed efficiently and the amount of hydrogen peroxide used can be reduced. As a result, a substrate processing device that can reduce the consumption of the used chemical solution can be provided.

[0111] <Third Modification>

[0112] Fig.15 2 is a second schematic diagram for explaining the nozzle arm of the substrate processing unit of the third modified example. Fig.15In the nozzle arm 21, 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 connecting path 26Aa. The connecting path 26Aa is provided between the second supply section 23b and each of the branch pipes 26a to 26d. A switching valve Vv is provided on the connecting path 26Aa. The switching valve Vv switches the supply and stop of the second processing liquid from the second supply section 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 second shortest, the flow path length from the switching valve Vv to the third mixing position CC is the third 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 the branch pipes 26a to 26d, respectively, the second processing liquid can reach 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 at which the second processing liquid reaches each mixing position can be made different.

[0113] <Fourth Modification>

[0114] In the first variant, an example is shown in which one of the first processing liquid and the second processing liquid reaches multiple mixing positions first when the substrate processing starts, but the first processing liquid and the second processing liquid may also reach multiple mixing positions at the same time. The adjustment of the time when the first processing liquid and the second processing liquid reach multiple mixing positions can be made to make the opening and closing time of the main opening and closing valve V, the first opening and closing valve Va to the fourth opening and closing valve Vd different as in the first variant, or the distance from the main opening and closing valve V, the first opening and closing valve Va to the fourth opening and closing valve Vd to each mixing position of the first supply pipe 25 different as in the second variant. In this case, at the start of the substrate processing, the SPM liquid can be ejected from the ejection port OH. 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.

[0115] <Fifth Modification>

[0116] In the above embodiment, an example is shown in which the first treatment liquid is set to sulfuric acid and the second treatment liquid is set to hydrogen peroxide, but the present invention is not limited to this. The first treatment liquid may also be set to hydrogen peroxide and the second treatment liquid may be set to sulfuric acid. In addition, the case where the combination of the first treatment liquid and the second treatment liquid is set to a combination of sulfuric acid and hydrogen peroxide is shown as an example, but the present invention is not limited to this. As long as the combination of the first treatment liquid and the second treatment liquid satisfies the conditions that the chemical reaction of at least one of the first treatment liquid and the second treatment liquid decomposes at a predetermined temperature or above and the chemical reaction performed by mixing the first treatment liquid and the second treatment liquid is an exothermic reaction, it will be fine.

[0117] <Second embodiment>

[0118] The substrate processing apparatus 100 in the second embodiment supplies hydrogen peroxide to the first supply pipe 25 from two or more selected branch pipes selected from the plurality of branch pipes 26a to 26d. In addition, the substrate processing apparatus 100 in the second embodiment does not supply hydrogen peroxide to the first supply pipe 25 from one or more unselected selected branch pipes from the plurality of branch pipes 26a to 26d. As described above, the distances between the branch pipes 26a to 26d and the nozzle OH are different. Therefore, if the two or more branch pipes selected from the branch pipes 26a to 26d are different, the concentration of permonosulfuric acid in the SPM liquid ejected from the nozzle OH is different. The substrate processing apparatus 100 in the second embodiment adjusts the concentration of permonosulfuric acid in the SPM liquid ejected from the nozzle OH.

[0119] The structure of the substrate processing apparatus 100 in the second embodiment is basically the same as that of the substrate processing apparatus 100 in the first embodiment. Hereinafter, the substrate processing apparatus 100 in the second embodiment will be mainly described with respect to the differences from the substrate processing apparatus 100 in the first embodiment.

[0120] Fig.16 2 is a block diagram showing an example of the functional configuration of the control unit in the second embodiment. Fig.16 ,and Figure 7 The functional differences of the control unit 50 shown in FIG. 5 are as follows: the switch control unit 503 is changed to the switch control unit 503A, and the processing condition acquisition unit 601 and the selection unit 603 are added. Figure 7 The functions shown are the same and therefore will not be repeated here.

[0121] The processing condition acquisition unit 601 receives the processing conditions of the substrate W. When processing the substrate W, the concentration of the permonosulfuric acid in the SPM liquid required may be different depending on the processing content. The processing condition acquisition unit 601 acquires the processing conditions of 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 performs a process of stripping the resist film. The processing conditions include information related to the resist film formed on the substrate W. The information related to the resist film includes, for example, the type and thickness of the resist film.

[0122] The selection unit 603 selects two or more selected branch pipes from the plurality of branch pipes 26a to 26d by referring to the allocation table stored in the storage device 514. The allocation table associates the processing conditions with the two or more selected branch pipes.

[0123] Fig.17This is a diagram showing an example of the format of the allocation table. Fig.17 , the allocation table stores one or more allocation records. The allocation record associates the used branch pipes among the branch pipes 26a to 26d with the processing conditions. The allocation record includes a field for the processing conditions and a field for selecting the branch pipe. The field for selecting the branch pipe includes four fields, namely, the 1st branch pipe to the 4th branch pipe. The field for the 1st branch pipe corresponds to the branch pipe 26a. The field for the 2nd branch pipe corresponds to the branch pipe 26b. The field for the 3rd branch pipe corresponds to the branch pipe 26c. The field for the 4th branch pipe corresponds to the branch pipe 26d.

[0124] The processing conditions are set in the field of the processing conditions of the allocation record. In the field of the selected branch pipe of the allocation record, a flag indicating which of the branch pipes 26a to 26d is used is set. Specifically, the flag indicating the use of branch pipe 26a is set in the field of the first branch pipe of the allocation record. The flag indicating the use of branch pipe 26b is set in the field of the second branch pipe of the allocation record. The flag indicating the use of branch pipe 26c is set in the field of the third branch pipe of the allocation record. The flag indicating the use of branch pipe 26d is set in the field of the fourth branch pipe of the allocation record.

[0125] In the second embodiment, a plurality of allocation records included in the allocation table each set a mark indicating the use of the branch pipe 26d in the field of the 4th branch pipe of the allocation record. In addition, a plurality of allocation records each set a mark indicating the use of the corresponding branch pipe in one or more fields of the fields of the 1st branch pipe to the 3rd branch pipe of the allocation record. Therefore, the plurality of allocation records each determine the use of two or more selected branch pipes.

[0126] return Fig.16 The selection unit 603 refers to the allocation table and selects a distribution record corresponding to the processing condition based on the input of the processing condition from the processing condition acquisition unit 601. The selection unit 603 determines the two or more selection branch pipes determined in the field of the selection branch pipe of the selected distribution record. The selection unit 603 outputs identification information for respectively identifying the two or more selected branch pipes determined to the opening and closing control unit 503A.

[0127] The selection unit 603 determines the branch pipe 26a as the selected branch pipe when a flag indicating the use of the branch pipe 26a is set in the field of the first branch pipe of the allocation record, and does not determine the branch pipe 26a as the selected branch pipe when the flag indicating the use of the branch pipe 26a is not set in the field of the first branch pipe. The selection unit 603 determines the branch pipe 26b as the selected branch pipe when a flag indicating the use of the branch pipe 26b is set in the field of the second branch pipe of the allocation record, and does not determine the branch pipe 26b as the selected branch pipe when the flag indicating the use of the branch pipe 26b is not set in the field of the second branch pipe of the allocation record. The selection unit 603 determines the branch pipe 26c as the selected branch pipe when a flag indicating the use of the branch pipe 26c is set in the field of the third branch pipe of the allocation record, and does not determine the branch pipe 26c as the selected branch pipe when the flag indicating the use of the branch pipe 26c is not set in the field of the third branch pipe of the allocation record. The selection unit 603 determines branch pipe 26d as the selected branch pipe when a mark indicating the use of branch pipe 26d is set in the field of the 4th branch pipe of the allocation record, and does not determine branch pipe 26d as the selected branch pipe when a mark indicating the use of branch pipe 26d is not set in the field of the 4th branch pipe of the allocation record.

[0128] The opening and closing control unit 503A controls the main opening and closing valve V, the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc, and the fourth opening and closing valve Vd. The opening and closing control unit 503A switches the main opening and closing valve V to one of an open state and a closed state. If it is switched from a closed state to an open state, sulfuric acid of a specified pressure is supplied to the first supply pipe 25. The opening and closing control unit 503A switches the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc, and the fourth opening and closing valve Vd to one of an open state and a closed state, respectively. If the first opening and closing valve Va is switched from a closed state to an open state, hydrogen peroxide is supplied to the first mixing position AA of the first supply pipe 25. If the second opening and closing valve Vb is switched 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 is switched from a closed state to an open state, hydrogen peroxide is supplied to the third mixing position CC of the first supply pipe 25. When the fourth on-off valve Vd is switched from a closed state to an open state, hydrogen peroxide is supplied to the fourth mixing position DD of the ejection nozzle 21b.

[0129] The opening and closing control unit 503A receives two or more identification information from the selection unit 603. The opening and closing control unit 503A determines the opening and closing valve provided corresponding to the selected branch pipe determined by the identification information. When the identification information identifies the branch pipe 26a, the first opening and closing valve Va provided in the branch pipe 26a is determined. When the identification information identifies the branch pipe 26b, the second opening and closing valve Vb provided in the branch pipe 26b is determined. When the identification information identifies the branch pipe 26c, the third opening and closing valve Vc provided in the branch pipe 26c is determined. When the identification information identifies the branch pipe 26d, the fourth opening and closing valve Vd provided in the branch pipe 26d is determined.

[0130] Hereinafter, the on-off valves provided corresponding to the selection branch pipes are referred to as selection valves. The on-off control unit 503A switches two or more selection valves determined from the first to fourth on-off valves Va to Vd to an open state, and switches the on-off valves other than the two or more selection valves to a closed state, based on two or more identification information input from the selection unit 603. When the on-off control unit 503A determines all the on-off valves of the first to fourth on-off valves Va to Vd, it switches all 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 positions of the first mixing position AA to the fourth mixing position DD.

[0131] Fig.18 2 is a flowchart for explaining an example of the flow of substrate processing in the second embodiment. Fig.18 , the CPU 511 of the control unit 50 determines whether the processing of the substrate has started (step S21). The time point when the substrate W rotated by the rotary chuck 10 reaches a predetermined rotation speed is detected as the start time point of the substrate processing. The CPU 511 moves the ejection nozzle 21b from the standby position to the substrate. The CPU 511 waits until the start of the substrate processing is detected, and when the start of the substrate processing is detected, the processing enters step S22.

[0132] In step S22, the processing conditions for the substrate W are obtained, and the process proceeds to step S23. The processing conditions input from the outside are obtained. In step S23, the selection branch pipe is determined from the allocation table, and the process proceeds to step S24. From the multiple allocation records included in the allocation table stored in the storage device 514, one allocation record corresponding to the processing conditions obtained in step S22 is selected. Then, two or more selection branch pipes determined to be used in the selected allocation record are determined.

[0133] In step S24, the flow rates corresponding to the first supply pipe 25 and the two or more selective 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 regulating valve NV. The main regulating valve NV is adjusted to an opening degree that the flow rate of sulfuric acid flowing from the first supply pipe 25 toward the discharge port OH becomes the main flow rate.

[0134] The first flow rate is the flow rate of hydrogen peroxide corresponding to the branch pipe 26a. The CPU 511 provides an electrical signal indicating the first flow rate to the first regulating valve NVa. The flow rate of hydrogen peroxide flowing from the branch pipe 26a toward the first mixing position AA is adjusted by the first regulating valve NVa to become the opening of the first flow rate. The second flow rate is the flow rate of hydrogen peroxide corresponding to the branch pipe 26b. The CPU 511 provides an electrical signal indicating the second flow rate to the second regulating valve NVb. The flow rate of hydrogen peroxide flowing from the branch pipe 26b toward the second mixing position BB is adjusted by the second regulating valve NVb to become the opening of the second flow rate.

[0135] The third flow rate is the flow rate of hydrogen peroxide corresponding to the branch pipe 26c. The CPU 511 supplies an electrical signal indicating the third flow rate to the third regulating valve NVc. The flow rate of hydrogen peroxide flowing from the branch pipe 26c toward the third mixing position CC is adjusted by the third regulating valve NVc to become the opening of the third flow rate. The fourth flow rate is the flow rate of hydrogen peroxide corresponding to the branch pipe 26d. The CPU 511 supplies an electrical signal indicating the fourth flow rate to the fourth regulating valve NVd. The flow rate of hydrogen peroxide flowing from the branch pipe 26d toward the fourth mixing position DD is adjusted by the fourth regulating valve NVd to become the opening of the fourth flow rate.

[0136] In step S25, the selector valves among the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc, and the fourth opening and closing valve Vd are simultaneously set to the open state. The selector valves correspond to the selected branch pipes determined in step S23. The first opening and closing valve Va corresponds to the branch pipe 26a, the second opening and closing valve Vb corresponds to the branch pipe 26b, the third opening and closing valve Vc corresponds to the branch pipe 26c, and the fourth opening and closing valve Vd corresponds to the branch pipe 26d.

[0137] For example, when the branch pipe 26a and the branch pipe 26d are determined as the selected branch pipes, the first opening and closing valve Va and the fourth opening and closing valve Vd are simultaneously opened. In this case, hydrogen peroxide is supplied from the first mixing position AA and the fourth mixing position DD of the first supply pipe 25, respectively. In addition, for example, when the branch pipes 26a, 26b, and 26d are determined as the selected branch pipes, the first opening and closing valve Va, the second opening and closing valve Vb, and the fourth opening and closing valve Vd are simultaneously opened. In this case, hydrogen peroxide 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. In addition, for example, when all the branch pipes 26a, 26b, 26c, and 26d are determined as the selected branch pipes, the first opening and closing valve Va, the second opening and closing valve Vb, the third opening and closing valve Vc, and the fourth opening and closing valve Vd are all simultaneously opened. In this case, the 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.

[0138] The processing of steps S26 to S29 is Figure 8 The processes of step S9 to step S12 are the same, and therefore, the description thereof will not be repeated here.

[0139] The substrate processing apparatus 100 in the second embodiment selects at least two of the four mixing positions AA, BB, CC, and DD, and at the at least two mixing positions, sulfuric acid and hydrogen peroxide are sequentially mixed from the mixing position farthest from the nozzle OH to the mixing position closest to the nozzle OH in the first supply pipe 25. Therefore, by making different combinations of the at least two mixing positions selected, the concentration of permonosulfuric acid in the SPM liquid can be changed.

[0140] In addition, at least two mixing positions are selected based on the processing conditions for processing the substrate W. Therefore, the concentration of the permonosulfuric acid in the SPM liquid can be adjusted according to the processing conditions.

[0141] <Third embodiment>

[0142] The substrate processing apparatus 100 in the third embodiment is similar to the substrate processing apparatus 100 in the second embodiment, and supplies hydrogen peroxide to the first supply pipe 25 from two or more selected branch pipes selected from the plurality of branch pipes 26a to 26d. The substrate processing apparatus 100 in the third embodiment changes the two or more selected branch pipes selected from the plurality of branch pipes 26a to 26d based on the processing result obtained by processing the substrate W. The structure of the substrate processing apparatus 100 in the third embodiment is basically the same as the structure of the substrate processing apparatus 100 in the second embodiment. Hereinafter, the differences between the substrate processing apparatus 100 in the third embodiment and the substrate processing apparatus 100 in the second embodiment will be mainly described.

[0143] Fig.19 1 is a block diagram showing an example of the functional configuration of the control unit in the third embodiment. Fig.19 ,and Fig.16 The functional differences of the control unit 50 shown in FIG. 5 are as follows: the processing condition acquisition unit 601 is deleted, the selection unit 603 is changed to the selection unit 603A, and the processing result acquisition unit 605, the history generation unit 607 and the change unit 609 are added. Fig.16 The functions shown are the same and therefore will not be repeated here.

[0144] When the substrate processing apparatus 100 is started, the selection unit 603 selects two or more selected branch pipes having the lowest concentration of permonosulfuric acid from the plurality of branch pipes 26a to 26d. The selection unit 603A outputs identification information for respectively identifying the two or more selected selected branch pipes to the opening and closing control unit 503A and the processing result acquisition unit 605. Here, the case where the branch pipe 26a and the branch pipe 26d are selected is used as an example for description. In this case, the identification information of each of the branch pipe 26a and the branch pipe 26d is output to the processing result acquisition unit 605.

[0145] 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 performs a process of stripping the resist film formed on the surface of the substrate W. The processing result is an index for evaluating the process. Here, the case where the stripping rate is used as an index is described as an example. The stripping rate is obtained by performing image processing on an image obtained by photographing the substrate W using a camera.

[0146] The history generating unit 607 generates history information including the processing result input from the processing result acquiring unit 605. The history information associates the selected branch pipe among the branch pipes 26a to 26d with the processing result. The history generating unit 607 outputs the history information to the changing unit 609.

[0147] Fig. 20 This is a diagram showing an example of the format of history information. Fig. 20 The history information includes four fields, namely, the first branch pipe to the fourth branch pipe and a field for the processing result. 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.

[0148] In the field of the processing result of the historical information, the peeling rate of the processing result input from the processing result acquisition unit 605 is set. In the four fields of the 1st branch pipe to the 4th branch pipe of the allocation record, a mark indicating that it is a selected branch pipe is set. Specifically, in a case where the identification information input from the processing result acquisition unit 605 identifies the branch pipe 26a, a mark indicating that the branch pipe 26a is the selected branch pipe is set. In a case where the identification information input from the processing result acquisition unit 605 identifies the branch pipe 26b, a mark indicating that the branch pipe 26b is the selected branch pipe is set. In a case where the identification information input from the processing result acquisition unit 605 identifies the branch pipe 26c, a mark indicating that the branch pipe 26c is the selected branch pipe is set. In a case where the identification information input from the processing result acquisition unit 605 identifies the branch pipe 26d, a mark indicating that the branch pipe 26d is the selected branch pipe is set.

[0149] return Fig.19 , the change unit 609 changes two or more selective branch pipes based on the historical information. When the difference between the processing result contained in the historical information and the target value exceeds the specified range, the change unit 609 changes the two or more selective branch pipes. The change unit 609 changes the group of the two or more selective branch pipes in such a way that the concentration of the permonosulfuric acid contained in the SPM liquid becomes larger. There is a tendency that the concentration of the permonosulfuric acid becomes higher as the position is closer to the nozzle OH among the 1st to 4th mixing positions AA, BB, CC, and DD. Therefore, the change unit 609 changes the selective branch pipe with the farthest distance from the nozzle OH in the current selective branch pipe to a branch pipe with a shorter distance from the nozzle OH. The change unit 609 outputs two or more identification information for respectively identifying the two or more selective branch pipes after the change to the selection unit 603A.

[0150] The selection unit 603A selects two or more selected branch pipes respectively identified by the two or more identification information from the plurality of branch pipes 26a to 26d, based on the input of two or more identification information from the change unit 609. The selection unit 603A outputs the identification information for respectively identifying the selected two or more selected branch pipes to the opening and closing control unit 503A and the processing result acquisition unit 605.

[0151] Fig.21 1 is a flowchart for explaining an example of the process of substrate processing in the third embodiment. Fig.21 ,and Fig.18 The substrate processing in the second embodiment shown is different in that step S22 is deleted, step S23 is changed to step S23A, and steps S30 to S32 are added. Fig.18 The processing shown is the same, so it will not be repeated here.

[0152] If it is determined in step S21 that the substrate processing 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 predetermined. Here, branch pipe 26a and branch pipe 26d are selected, where the concentration of permonosulfuric acid is the lowest.

[0153] In step S29, if the scanning operation and the ejection of the SPM liquid are stopped, the process proceeds to step S30. In step S30, the process result is acquired, and the process proceeds to step S31. The process result is an index that can evaluate the process of the substrate processing apparatus 100 to peel off the resist film formed on the surface of the substrate W. Here, the peeling rate is used as an index.

[0154] In step S31, it is determined whether there is a substrate to be processed next. If there is a substrate to be processed, the process proceeds to step S32, and if 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 two or more new selection branch pipes are changed in a manner that the permonosulfuric acid concentration becomes higher than that of the current two or more selection branch pipes. Therefore, during the execution of the next steps S24 to S30, hydrogen peroxide is supplied from the two or more new selection branch pipes.

[0155] The substrate processing apparatus 100 in the third embodiment selects at least two of the four mixing positions AA, BB, CC, and DD, obtains the processing results of processing the substrate W using the selected at least two mixing positions, and based on the processing results, changes the group of at least two mixing positions selected for the next processed substrate W. Therefore, the processing results of processing the substrate W are fed back to the processing of the substrate W to be processed next, so that the group of at least two mixing positions can be appropriately determined while a plurality of substrates W are processed in sequence.

[0156] <Fourth embodiment>

[0157] The substrate processing apparatus 100 in the fourth embodiment generates a distribution table used by the substrate processing apparatus 100 in the second embodiment based on the history information. The structure of the substrate processing apparatus 100 in the fourth embodiment is basically the same as that of the substrate processing apparatus 100 in the second embodiment. Hereinafter, the differences between the substrate processing apparatus 100 in the fourth embodiment and the substrate processing apparatus 100 in the second embodiment will be mainly described.

[0158] Fig. 22 1 is a block diagram showing an example of the functional configuration of the control unit in the fourth embodiment. Fig. 22 ,and Fig.16 The difference in the function of the control unit 50 shown is that a processing result acquisition unit 605, a history generation unit 607A, and an update unit 611 are added. Fig.16 The functions shown are the same and therefore will not be repeated here.

[0159] In the fourth embodiment, four branch pipes 26a to 26d are used. Two or more selective branch pipes include branch pipe 26d and include one or more of the other three branch pipes 26b to 26d. Therefore, the combination of two or more selective branch pipes is three groups of two selective branch pipes, three groups of three selective branch pipes, and one group of four selective branch pipes, totaling seven groups.

[0160] 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 performs a process of stripping the resist film formed on the surface of the substrate W. The processing result is an index for evaluating the process. Here, the case where the stripping rate is used as an index is described as an example. The stripping rate is obtained by performing image processing on an image obtained by photographing the substrate W using a camera.

[0161] The history generating unit 607A generates history information including the processing result input from the processing result acquiring unit 605. The history information associates the processing condition, the selected branch pipe among the branch pipes 26a to 26d, and the processing result. The history generating unit 607A stores the history information in the storage device 514.

[0162] Fig.23 FIG. 4 is a diagram showing an example of the format of history information in the fourth embodiment. Fig.23 ,exist Fig. 20 A processing condition field is added to the history information shown. The processing condition is set in the processing condition field of the history information.

[0163] return Fig. 22 After the history generating unit 607A generates history information for each of the seven groups of combinations of two or more selective branch pipes, the updating unit 611 updates the allocation table. For example, the updating unit 611 reads a plurality of history information stored in the storage device 514 by the history generating unit 607A, performs statistical processing on the plurality of history information, and thereby determines the optimal values ​​of the two or more selective branch pipes. Specifically, the updating unit 611 determines the group of two or more selective branch pipes for which the value obtained by statistical processing of the processing results for the same processing condition is the best as the optimal value.

[0164] Fig.24 1 is a flowchart showing an example of the flow of the allocation table generation process. Fig.24 The CPU 511 included in the control unit 50 obtains the processing result (step S41) and causes the processing to proceed to step S42.

[0165] In step S42, historical information is generated based on the processing result, and the process proceeds to step S43. Fig.23 The history information is stored in the storage device 514. The history information includes processing conditions, whether the first to fourth branch pipes 26a to 26d can be used, and processing results.

[0166] In step S43, the historical information is classified into processing condition groups, and the process proceeds to step S44. The processing condition group contains historical information with the same processing conditions. Therefore, the processing condition groups are the same number as the number of processing conditions. The historical information is classified into processing condition groups with the same processing conditions as the processing conditions included in the historical information. In step S44, the historical information is classified into branch pipe groups, and the process proceeds to step S45. The branch pipe group contains historical information that is the same as the branch pipes (selective branch pipes) used. Therefore, the branch pipe group has the same number as the number of groups of more than two selective branch pipes (seven in this example). The historical information is classified into a branch pipe group of a group of two or more selective branch pipes that is the same as the group of two or more selective branch pipes determined by the fields of the first to fourth branch pipes included in the historical information, among the multiple branch pipe groups included in the processing condition group.

[0167] In step S45, the average value of the branch pipe group is calculated, and the process proceeds to step S46. The plurality of history information included in the branch pipe group into which the history information is classified is taken as an object, and the average value of the processing results is calculated.

[0168] In step S46, the allocation table is updated and the processing ends. From the plurality of branch pipe groups included in the same processing conditions as the processing conditions included in the history information, the branch pipe group with the largest average value is selected. Then, from the plurality of allocation records included in the allocation table, an allocation record including the same processing conditions as the processing conditions included in the history information is determined. Furthermore, the field of the selected branch pipe of the determined allocation record is updated with a value indicating that two or more selected branch pipes corresponding to the branch pipe group with the largest average value are used.

[0169] The substrate processing apparatus 100 in the fourth embodiment obtains the processing result of processing the substrate W, generates history information that associates at least two mixing positions with the processing result, and determines the optimal value of the group of at least two mixing positions for the processing conditions based on the history information. Therefore, the group of at least two mixing positions for the processing conditions can be determined without measuring the concentration of permonosulfuric acid in the SPM liquid. In addition, since the allocation table is generated by processing the substrate W, the allocation table suitable for the substrate processing apparatus 100 can be generated.

[0170] <Correspondence between each component of the claims and each part of the embodiments>

[0171] The ejection port OH is an example of an ejection port, 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 a plurality of second supply paths, the first supply section 23a is an example of a first supply section, the second supply section 23b is an example of a second supply section, and permonosulfuric acid, water, sulfuric acid, and hydrogen peroxide are examples of liquids. In addition, the control section 50 is an example of a control section, the first to fourth on-off valves Va to Vd are examples of a plurality of first switching sections, the connection path 26Aa is an example of a connection path, the switching valve Vv is an example of a second switching section, and the stirring section 27 is an example of a stirring section. 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.

[0172] <Summary of implementation methods>

[0173] (Item 1) A substrate processing apparatus according to one embodiment 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 comprising:

[0174] Spout;

[0175] a first supply path connected to the discharge port;

[0176] a plurality of second supply paths connected to the first supply path at a plurality of mixing positions having different flow path lengths to the ejection port position;

[0177] a first supply unit that supplies the first processing liquid to the first supply path; and

[0178] a second supply unit that supplies the second processing liquid to the first supply path via the plurality of second supply paths,

[0179] 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 in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0180] In the substrate processing device described in the first item, the first processing liquid and the second processing liquid are mixed at each of the multiple mixing positions. The third processing liquid is generated by the first chemical reaction between the first processing liquid and the second processing liquid. There is a case where the first chemical reaction is an exothermic reaction, and the progress of the first chemical reaction is promoted at a temperature above a specified temperature, and the second chemical reaction in which the second processing liquid is decomposed into two or more substances at a temperature above a temperature lower than the specified temperature occurs. In this case, for each mixing of the first processing liquid and the second processing liquid, the first chemical reaction and the second chemical reaction occur simultaneously. Therefore, above the specified temperature, the first chemical reaction occurs, and at the same time, the second chemical reaction occurs. The second processing liquid is reduced by the progress of the second chemical reaction, so the first chemical reaction is hindered. 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 nozzle to the mixing position closest to the nozzle. Thus, the amount of the second processing liquid present in the first supply path can be set to a predetermined ratio or more relative to the amount of the first processing liquid at each of the plurality of mixing positions, and the first chemical reaction can be continuously performed. Therefore, the first chemical reaction can be efficiently performed and the amount of the second processing liquid used can be reduced. As a result, a substrate processing apparatus capable of reducing the consumption of the used chemical liquid can be provided.

[0181] (Item 2) The substrate processing device provided in Item 1 may also be,

[0182] further comprising a control unit that controls the first supply unit and the second supply unit,

[0183] The control unit controls the second supply unit to supply the second processing liquid to the plurality of 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.

[0184] According to the substrate processing apparatus described in item 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 produced by simply controlling the first supply unit and the second supply unit.

[0185] (Item 3) The substrate processing apparatus described in Item 1 may also be,

[0186] further comprising a control unit that controls the first supply unit and the second supply unit,

[0187] The control unit controls 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.

[0188] According to the substrate processing apparatus described in item 3, in the first supply path, the second processing liquid is supplied at each of the plurality of mixing positions while the first processing liquid is supplied. Therefore, the second processing liquid is sequentially mixed with the liquid in the first supply path. Therefore, the first chemical reaction can be efficiently performed and the usage amount of the second processing liquid can be reduced.

[0189] (Item 4) The substrate processing apparatus described in Item 1 may also be,

[0190] and further comprising a plurality of first switching parts, which are respectively arranged at the plurality of second supply paths and switch supply and stop of the second processing liquid from the second supply path to the first supply path.

[0191] The longer the flow path length between the mixing position where the second supply path is connected to the first supply path and the discharge port is, the shorter the flow path length from the first switching portion to the mixing position in each of the plurality of second supply paths is.

[0192] According to the substrate processing device described in the fourth item, when the moments when the plurality of first switching parts are switched from the stop state to the state of supplying the second processing liquid are at the same time, the second processing liquid is supplied in the order from the mixing position with the long flow path length between the nozzle and the nozzle to the mixing position with the short flow path length between the nozzle and the nozzle. Therefore, the time until the second processing liquid reaches each mixing position can be different. If the moment of switching the state of the first switching part is determined according to the moment of supplying the first processing liquid, the second processing liquid can arrive at each position of the plurality of mixing positions at the time when the first processing liquid arrives. 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.

[0193] (Item 5) The substrate processing apparatus described in Item 1 may further include:

[0194] a single connection path provided between the second supply portion and the plurality of second supply paths; and

[0195] a second switching unit provided in the connection path and switching supply and stop of the second processing liquid from the second supply unit to the plurality of second supply paths;

[0196] The longer the flow path length between the mixing position and the ejection port is, the shorter the flow path length between the mixing position and the second switching portion is in each of the plurality of mixing positions.

[0197] According to the substrate processing device described in the fifth item, the second processing liquid is supplied in the order from the mixing position with a long flow path length to the mixing position with a short flow path length to the ejection port. Therefore, the time until the second processing liquid reaches each mixing position can be different. If the time to switch the state of the switching part is determined according to the time when the first processing liquid is supplied, the second processing liquid can arrive at each position of the plurality of mixing positions at the time when the first processing liquid arrives. As a result, the consumption of the first processing liquid and the second processing liquid can be suppressed.

[0198] (Item 6) In the substrate processing apparatus described in any one of Items 1 to 5, it may be that:

[0199] The second supply section makes the flow rate of the second processing liquid flowing to the final supply path among the multiple second supply paths greater than the flow rate of the second processing liquid flowing to one or more other second supply paths, wherein the final supply path is connected to the first supply path at the mixing position where the flow path length from the ejection port is the smallest.

[0200] According to the substrate processing apparatus described in item 6, the second processing liquid is supplied to the first supply path at a position closest to the ejection outlet at a large flow rate. Thus, the amount of the second processing liquid mixed with the first processing liquid becomes the largest at the stage where the temperature of the first processing liquid is the highest, so that the third processing liquid can be efficiently generated.

[0201] (Item 7) In the substrate processing apparatus described in any one of Items 1 to 6, it may be that:

[0202] The device further includes a stirring portion provided in the first supply path and configured to stir the liquid flowing in the first supply path.

[0203] In the substrate processing apparatus described in item 7, the first processing liquid and the second processing liquid mixed in the first supply path are stirred by the stirring unit. Thus, since the mixing of the first processing liquid and the second processing liquid is promoted, the amount of the first processing liquid that becomes the object of the first chemical reaction can be increased.

[0204] (Item 8) In the substrate processing apparatus described in Item 7, it may be that:

[0205] The stirring section is provided at a position where a flow path length from a first mixing position having the largest flow path length from the ejection port among the plurality of mixing positions is less than a flow path length between the first mixing position and a second mixing position having the second longest flow path length from the ejection port.

[0206] In the substrate processing apparatus described in Item 8, the first processing liquid and the second processing liquid can be stirred before the gas is generated in the first supply path. This can promote the first chemical reaction.

[0207] (Item 9) In the substrate processing apparatus described in any one of Items 1 to 8, it may be that:

[0208] One of the first treatment liquid and the second treatment liquid is sulfuric acid, and the other is hydrogen peroxide solution.

[0209] According to the substrate processing apparatus described in Item 9, the first chemical reaction is a reaction of H2SO4+H2O2→H2SO5+H2O, and the second chemical reaction is a reaction of 2H2O2→2H2O+O2. Therefore, peroxymonosulfuric acid contained in the SPM liquid can be efficiently generated.

[0210] (Item 10) In the substrate processing apparatus described in Item 9, it may be that:

[0211] The first treatment liquid is sulfuric acid, and the second treatment liquid is hydrogen peroxide.

[0212] According to the substrate processing apparatus described in item 10, the first supply path can be supplied in multiple stages. The first chemical reaction is a reaction of H2SO4+H2O2→H2SO5+H2O, and the second chemical reaction is a reaction of 2H2O2→2H2O+O2. Therefore, peroxymonosulfuric acid contained in the SPM liquid can be efficiently generated, and the consumption of hydrogen peroxide can be reduced.

[0213] (Item 11) In the substrate processing apparatus described in any one of Items 1 to 10, it may be that:

[0214] A control unit is further provided, which controls the opening and closing of each of the plurality of second supply paths.

[0215] The plurality of mixing locations is at least three,

[0216] The control unit includes a selection unit that selects at least two of the at least three mixing positions.

[0217] The second supply unit is controlled so that, at the selected at least two mixing positions, 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.

[0218] According to the substrate processing device described in item 11, at least two of the at least three mixing positions are selected. Therefore, at the at least two mixing positions, the liquid in the first supply path and the second processing liquid are mixed in order from the mixing position farthest from the ejection port to the mixing position closest to the ejection port. Therefore, by making the combination of the at least two selected mixing positions different, the concentration of the third processing liquid can be changed.

[0219] (Item 12) In the substrate processing apparatus described in Item 11, it may be that:

[0220] The control unit further includes a processing condition acquisition unit that acquires processing conditions for processing the substrate.

[0221] The selection section selects at least two of the mixing positions based on the processing conditions.

[0222] According to the substrate processing apparatus described in Item 12, at least two mixing positions are selected based on the processing conditions for processing the substrate. Therefore, the concentration of the third processing liquid can be adjusted according to the processing conditions.

[0223] (Item 13) In the substrate processing apparatus described in Item 12, it may be that:

[0224] The control unit includes:

[0225] a processing result acquiring unit, which acquires a processing result of processing the substrate;

[0226] a history generating unit configured to generate history information in which at least two of the mixed positions selected by the selecting unit are associated with the processing result; and

[0227] A determination unit determines an optimal value for a set of at least two of the mixing positions of the processing conditions based on the generated history information.

[0228] According to the substrate processing apparatus described in Item 13, a processing result of processing the substrate is obtained, historical information is generated in which at least two mixing positions are associated with the processing result, and an optimal value of the group of at least two mixing positions for the processing conditions is determined based on the historical information. Since the group of at least two mixing positions for the processing conditions is determined based on the processing result, the group of at least two mixing positions for the processing conditions can be determined without measuring the concentration of the third processing liquid.

[0229] (Item 14) In the substrate processing apparatus described in any one of Items 1 to 10, it may be that:

[0230] A control unit is further provided, which controls the opening and closing of each of the plurality of second supply paths.

[0231] The plurality of mixing locations is at least three,

[0232] The control unit includes:

[0233] a selection section that selects at least two from the at least three mixing positions;

[0234] a processing result acquisition unit that acquires a processing result of processing the substrate using at least two of the mixing positions selected by the selection unit; and

[0235] A changing unit changes the set of at least two mixing positions selected by the selecting unit based on the processing result.

[0236] According to this aspect, the processing result of processing the substrate using at least two mixing positions selected from at least three mixing positions is obtained, and the group of at least two mixing positions is changed based on the processing result. Since the processing result is fed back, the group of at least two mixing positions can be appropriately determined.

[0237] (Item 15) Another embodiment of a substrate processing method is a substrate processing method performed by a substrate processing apparatus, wherein the substrate processing apparatus generates a third processing liquid from a first processing liquid and a second processing liquid, and processes a substrate using the third processing liquid,

[0238] The substrate processing device comprises:

[0239] Spout;

[0240] a first supply path connected to the discharge port; and

[0241] a plurality of second supply paths connected to the first supply path at a plurality of mixing positions having different flow path lengths to the ejection port, respectively;

[0242] The substrate processing method comprises:

[0243] a step of supplying the first processing liquid to the first supply path; and

[0244] a step of supplying the second processing liquid to the first supply path via the plurality of second supply paths,

[0245] 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 in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0246] According to the substrate processing method described in Item 15, at the plurality of mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are sequentially mixed from the mixing position farthest from the ejection port to the mixing position closest to the ejection port, so that the amount of the second processing liquid present in the first supply path can be made to be greater than a predetermined ratio relative to the amount of the first processing liquid at each of the plurality of mixing positions, and the first chemical reaction can be continuously performed. Therefore, the first chemical reaction can be efficiently performed and the usage of the second processing liquid can be reduced. As a result, a substrate processing device capable of reducing the consumption of the used chemical liquid can be provided.

[0247] (Item 16) A substrate processing program according to another embodiment is a substrate processing program executed by a computer controlling a substrate processing device, wherein the substrate processing device generates a third processing liquid from a first processing liquid and a second processing liquid, and processes a substrate using the third processing liquid,

[0248] The substrate processing device comprises:

[0249] a spray port for spraying the third treatment liquid;

[0250] a first supply path connected to the discharge port; and

[0251] a plurality of second supply paths connected to the first supply path at a plurality of mixing positions having different flow path lengths to the ejection port, respectively;

[0252] The substrate processing program causes the computer to perform the following steps:

[0253] a step of supplying the first processing liquid to the first supply path; and

[0254] a step of supplying the second processing liquid to the first supply path via the plurality of second supply paths,

[0255] 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 in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

[0256] According to the substrate processing program described in item 16, at the plurality of mixing positions of the first supply path, the liquid in the first supply path and the second processing liquid are sequentially mixed from the mixing position farthest from the ejection port to the mixing position closest to the ejection port, so that the amount of the second processing liquid present in the first supply path can be made to be greater than a predetermined ratio relative to the amount of the first processing liquid at each of the plurality of mixing positions, and the first chemical reaction can be continuously performed. Therefore, the first chemical reaction can be efficiently performed and the usage of the second processing liquid can be reduced. As a result, a substrate processing device capable of reducing the consumption of the used chemical liquid can be provided.

Claims

1. A substrate processing device, which generates a third processing liquid from a first processing liquid and a second processing liquid, and uses the third processing liquid to process a substrate, characterized in that: have: Spout; 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 having different flow path lengths to the ejection port; 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, 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 in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

2. The substrate processing device according to claim 1, characterized in that: further comprising a control unit that controls the first supply unit and the second supply unit, The control unit controls the second supply unit to supply the second processing liquid to the plurality of 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. The substrate processing device according to claim 1, characterized in that: further comprising a control unit that controls the first supply unit and the second supply unit, The control unit controls 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.

4. The substrate processing apparatus according to any one of claims 1 to 3, characterized in that: and further comprising a plurality of first switching parts, which are respectively arranged at the plurality of second supply paths and switch supply and stop of the second processing liquid from the second supply path to the first supply path. The longer the flow path length between the mixing position where the second supply path is connected to the first supply path and the discharge port is, the shorter the flow path length from the first switching portion to the mixing position in each of the plurality of second supply paths is.

5. The substrate processing apparatus according to any one of claims 1 to 3, characterized in that: Also available: a single connection path provided between the second supply portion and the plurality of second supply paths; and a second switching unit provided in the connection path and switching supply and stop of the second processing liquid from the second supply unit to the plurality of second supply paths; The longer the flow path length between the mixing position and the ejection port is, the shorter the flow path length between the mixing position and the second switching portion is in each of the plurality of mixing positions.

6. The substrate processing apparatus according to any one of claims 1 to 5, characterized in that: The second supply section makes the flow rate of the second processing liquid flowing to the final supply path among the multiple second supply paths greater than the flow rate of the second processing liquid flowing to one or more other second supply paths, wherein the final supply path is connected to the first supply path at the mixing position where the flow path length from the nozzle is the smallest.

7. The substrate processing apparatus according to any one of claims 1 to 6, characterized in that: The device further includes a stirring portion provided in the first supply path and configured to stir the liquid flowing in the first supply path.

8. The substrate processing device according to claim 7, characterized in that: The stirring section is provided at a position where a flow path length from a first mixing position having the largest flow path length from the ejection port among the plurality of mixing positions becomes less than a flow path length between the first mixing position and a second mixing position having the second largest flow path length from the ejection port.

9. The substrate processing apparatus according to any one of claims 1 to 8, characterized in that: One of the first treatment liquid and the second treatment liquid is sulfuric acid, and the other is hydrogen peroxide solution.

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

11. The substrate processing apparatus according to any one of claims 1 to 10, characterized in that: A control unit is further provided, which controls the opening and closing of each of the plurality of second supply paths. The plurality of mixing locations is at least three, The control unit includes a selection unit that selects at least two mixing positions from the at least three mixing positions. The second supply unit is controlled so that, at the selected at least two mixing positions, 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.

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

13. The substrate processing apparatus according to claim 12, wherein: The control unit includes: a processing result acquiring unit, which acquires a processing result of processing the substrate; a history generating unit configured to generate history information in which at least two of the mixed positions selected by the selecting unit are associated with the processing result; and A determination unit determines an optimal value for a set of at least two of the mixing positions of the processing conditions based on the generated history information.

14. The substrate processing apparatus according to any one of claims 1 to 10, characterized in that: A control unit is further provided, which controls the opening and closing of each of the plurality of second supply paths. The plurality of mixing locations is at least three, The control unit includes: a selection unit, which selects at least two mixing positions from the at least three mixing positions; a processing result acquisition unit that acquires a processing result of processing the substrate using the at least two mixing positions selected by the selection unit; and A changing unit changes the set of at least two mixing positions selected by the selecting unit based on the processing result.

15. A substrate processing method, which is performed by a substrate processing device, wherein the substrate processing device generates a third processing liquid from a first processing liquid and a second processing liquid, and uses the third processing liquid to process a substrate, wherein the substrate processing method is characterized in that: The substrate processing device comprises: Spout; a first supply path connected to the discharge port; and a plurality of second supply paths connected to the first supply path at a plurality of mixing positions having different flow path lengths to the ejection port, respectively; The substrate processing method comprises: a step 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, 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 in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

16. A substrate processing program executed by a computer controlling a substrate processing device, wherein the substrate processing device generates a third processing liquid from a first processing liquid and a second processing liquid, and uses the third processing liquid to process a substrate, wherein the substrate processing program is characterized in that: The substrate processing device comprises: a spray port for spraying the third treatment liquid; a first supply path connected to the discharge port; and a plurality of second supply paths connected to the first supply path at a plurality of mixing positions having different flow path lengths to the ejection port, respectively; The substrate processing program causes the computer to perform the following steps: a step 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, 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 in order from the mixing position farthest from the discharge port to the mixing position closest to the discharge port.

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